September 1992 · NREL/CP-412-5007

Current Status, Research Needs,

and Opportunities in Applications
of Surface Processing to
Transportation and Utilities
Technologies
Proceedings of a December 1991
Workshop
A.W. Czanderna and A.R. Landgrebe,
Editors
• Executive Summary
• Assessment of the Current Status in Surface
Characterization
• Assessment of the Current Status in Surface
Modification
• Discussion of Research Needs and Opportunities
for Advancing Transportation and Utilities
Technologies Through Applied Surface Science
and Surface Processing

National Renewable Energy Laboratory

1617 Cole Boulevard
Golden, Colorado 80401-3393
A national laboratory of the U.S. Department of Energy
Managed by Midwest Research Institute
for the U.S. Department of Energy
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Prepared under task number DO140101
September 1992
 NOTICE

This report was prepared as an account of work sponsored by an agency of the United States
government. Neither the United States government nor any agency thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy,
completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents
that its use would not infringe privately owned rights. Reference herein to any specific commercial
product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily
constitute or imply its endorsement, recommendation, or favoring by the United States government or any
agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect
those of the United States government or any agency thereof.

Printed on paper containing at least 50% wastepaper, including 10% postconsumer waste
 SUMMARY

Surface Processing is a subset of applied surface science for (1) preparing tailor-made surfaces for specific
end-use applications, (2) characterizing the surfaces, and (3) developing a theoretical framework. These _
proceedings document the principal discussions and conclusions reached at a workshop held on
December 10-12, 1991, and cosponsored by the U.S. Department of Energy (DOE), Office of
Transportation Technologies and Office of Utility Technologies; and the National Renewable Energy
Laboratory (NREL) under contract to DOE. The proceedings document eight chapters about the current
status of surface characterization with a principal focus on the composition, structure, bonding, and atomic-
scale topography of surfaces. The proceedings also document eleven chapters about the current status of
surface modification and include a summary of techniques-electrochemical, plasma-aided, reactive and
nonreactive physical ' vapor deposition, sol-gel coatings, high-energy ion implantation, ion-assisted
deposition, organized molecular assemblies, and solar energy. Three brief chapters in the Appendices
document basic research in surface science by the National Science Foundation, the Air Force Office of
Scientific Research, and the Division of Materials Sciences, Office of Energy Research, DOE that
underpins surface processing.

The purposes of the workshop were to bring together scientists and engineers from academia, indUStry,
and federally funded laboratories to form working groups with a mixture of expertise in surface
characterization and surface modification, and to identify and prioritize the research needs and
opportunities ofeach of 10 different topical areas of applied surface science as they relate to applications
in the transportation and utilities technologies. Each participant was invited to serve on one of 10 working
groups concerned with a topic in applied surface science. The topics were corrosion protection, solid
batteries and fuels cells, lubricating and wear surfaces, polymer/metal (oxide) interfaces, thin-film
multilayer solar collectors, accelerated life testing of devices with solid/solid and solidlliquid interfaces,
interfacial microchemical characterization, conducting polymers, photoelectrochemical systems, and
modification with organized molecular assemblies. The participants identified generic and specific
problems at materials interfaces in the 10 topical areas and conceived stimulating ideas on research and
development that focus materials and systems with targeted end-use applications. With these proceedings,
researchers and technologists can be exposed to the topical areas and deliberations of the workshop.

NOTICE

This report was prepared as an account of work sponsored by an agency of the United states government Neither the United
States government nor any lIgency thereof. nor any of their employ~s. makes any wmanty. express or implied. or aSsumes any
legal liability or responsibility for the accuracy. completeness. or usefulness of any information. apparatus. product, or process
disclosed. or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial
product, process. or service by trade name. trademark. manufacturer. or otherwise does not necessarily constitute or imply its
endorsement. recommendation. or favoring by the United States government or any agency thereof. The views and opinions of
authors expressed herein do not necessarily $tate or reflect those of the United States government or any agency thereof.
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Workshop Organizers

A. W. Czanderna, Ph.D.
Measurements and Characterization Branch
National Renewable Energy Laboratory

A. R. Landgrebe, PltD .
. Office of Propulsion Systems
Office of Transportation Technologies
U.S. Department of Energy

T. Vojnovich, Ph.D.
Office of Transportation Materials
Office of Transportation Technologies
U.S. Department of Energy

Supporting Organizations

National Renewable Energy Laboratory, Director's Office

Office of Transportation Technologies, U.S. DOE
Office of Utilities Technologies, U.S. DOE
 Table of Contents

Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

Executive Summary . . . . . . . . . . . . . .. " ....... : . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ES-l

Part I. Current Status of Surface Characterization and Surface Modification

1. Compositional Analyses of Surfaces and Thin Films by Electron and Ion

Spectroscopies. C. 1. Powell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1

2. Characterization of Surfaces: Current Status of Surface Structure Determination

(January 1991). C. B. Duke .......................................... 2-1

3'. A Summary of Critical Issues for Application of IR Spectroscopy to Characterization

of Surface Processing. D. L. Allara . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 3-1 .,

4. Optical Second Harmonic Generation Studies of Adsorption, Orientation, and Order

at the Electrochemical Interface. R. M. Com .............................. 4-1

5. Analysis of Interfaces Using Second Harmonic Generation and Sum Frequency

Generation. R. J. Anderson. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 5-1

6. Scanning Probe Microscopy. D. A. Grigg and P. E. Russell. . . . . . . . . . . . . . . . . . .. 6-1

7. Local Order and Bonding Primarily USing ~S and SEXAFS. R. A. Mayanovic . .. 7-1

8. High Resolution Electron Energy Loss Spectroscopic Characterization of Insulators

for Si Technology. M. Liehr and P. A. Thiry .............................. 8-1

9. Surface Modification Techniques: A Summary Report. K. Mittal . . . . . . . . . . . . . . .. 9-1

10. Electrochemical Deposition Techniques. P. C. Searson 10-1

11. Plasma-Aided Manufacturing. J. L. Shohet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. I l.. 1

12. Atomistic Inorganic Film Formation by Reactive and Nonreactive PVD Techniques.
D. M. Mattox . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 12-1

13. Particle Bombardment Effects on Thin-Film Deposition: A Review. D. M. Mattox ... 13-1

14. Sol-Gel Coatings for Energy-Related Materials. A. 1. Hurd 14-1

15. High-Energy Ion Implantation of Materials. J. M. Williams 15-1

16. Surface Treatments with Ion Beam Assisted Depositions. G. K. Hubler. . . . . . . . . . .. 16-1

iii
 Table of Contents (Concluded)

17. A Summary of Critical Issues for Application of Organized Molecular

Assemblies at Surfaces. D. L. Allara . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 17-1

18. Status of Surface Modification for Minimizing Dirt Retention: Organized

Molecular Assemblies. L. M. Speaker ................................... 18-1

19.. Applications of Solar Energy to Surface Modification Processes. J. R. Pitts,

E. Tracy, and Y. Shinton . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . .. 19-1

Part II. Research Needs and Opportunities for Applications to Transportation and Utilities Technologies

20. Panel on Corrosion Protection ............................... . ......... 20-1

2t. Batteries and Fuel Cells .......................... . ........ . ......... 21-1

22. Lubricating and Wear Surfaces ........................................ 22-1

23. Polymer-Metal(Oxide) Interfaces .................... ,.................. 23-1

24. The Impact of Surface Processing on the Fabrication and Performance of

Thin-Film, Multilayer Solar Collectors ................................... 24-1

25. Accelerated Life Testing of Devices with SIS, SIL, and S/G Interfaces. . . . . . . . . . . .. 25-1

26. Interfacial Microchemical Characterization Needs in Surface Processing . . . . . . . . . . .. 26-1

27. Conducting Polymers in Energy and Transportation Technologies -. . . . . . . . . . . . . . .. 27-1

28. Photoelectrochemical Systems ......................................... 28-1

29. Organized Molecular Assemblies .......................... . . . . . . . . . . . .. 29-1

Part III. Appendices: Fundamental Support Underpinning Surface Processing

At. Office of Basic Energy Sciences (OBES). M. Kassner, LBL for BES ... . ......... Al-1

A2. National Science Foundation (NSF). P. M. A. Sherwood, Kansas State University,

for NSF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . .. A2-1

A3. The Air Force Office of Scientific Research. L. Burgraff, AFOSR ........... . ... A3-1

A4. Glossary of Acronyms and Abbreviations ................................. A4-1

AS. Participants at the Workshop on Surface Processing .......................... AS-I

I. Index I-I

iv
 PREFACE

These proceedings document the principal discussions and conclusions reached at a workshop held
December 10-12, 1991, and cosponsored by the U.S. Department of Energy (DOE), Office of
Transportation Technologies and Office of Utility Technologies; and the National Renewable Energy
Laboratory (NREL) under contract to DOE. The purposes of the workshop were to bring together
scientists and engineers from academia, industry, and federally-funded laboratories to form working groups
with a mixture of .expertise in surface characterization and surface modification, and to identify and
prioritize. the research needs and opportunities of each of 10 different topical areas of applied surface
science as they relate to applications in the transportation and utilities technologies.

Surface Processing is a subset of applied surface science for (1) preparing tailor-made surfaces
for specific end-use applications, (2) characterizing the surfaces, and (3) developing a theoretical
framework. Participants were sent current-status, "plenary" summaries of the state of the art in the
relevant methods for surface modification and surface characterization prior to the workshop. They were
also sent documents that indicate the crucial importanCe of surface properties for applications in
conservation and renewable energy technologies, energy distribution, energy generation by utilities, and
buildings, and by other industrial energy users. At the workshop, overview lectures on surface processing
in the transportation industry by Dr. D. Schuetzle of the Ford Motor Company and surface processing
opportunities in the utility industries by Dr. R. McConnell of NREL. The current status summary papers
are contained in Chapters 1 through 8 for surface characterization and Chapters 9 through 19 for surface
modification. .

Each participant was invited to serve on one of 10 working groups concerned with a topic in
applied surface science. The topics were corrosion protection, solid batteries and fuels cells, lubricating
and wear surfaces, polymer/metal(oxide) interfaces, thin-fIlm multilayer solar collectors, accelerated life
-testing of devices with solid/solid and solidlliquid interfaces, interfacial microchemical characterization,
conducting polymers, photoelectrochemical systems, and modification with organized molecular
assemblies.

The participants identified generic and specific problems at materials interfaces in the 10 topical
areas and conceived stimulating ideas on interfacial R&D that focus materials and systems with targeted
end-use applications. With these proceedings, researchers and technologists can be exposed to the topical
areas and deliberations of the workshop. The needs and opportunities for surface processing R&D are
identified and discussed in Chapters 20 through 29.

- Basic research in surface science is well funded by several federal agencies including the DOE
Office of Energy Research, the Division of Materials Sciences (OERlDMS), the National Science
Foundation (NSF), the Air Force Office of Scientific Research (AFOSR), the Office of Naval Research
(ONR), and to a lesser extent, the Army Research Office. All these agencies were invited to summarize
their activities for the participants. Relevant summaries of the activities of OERlDMS, NSF, and AFOSR
are contained in Appendices Al through A3, and representatives from OERlDMS and NSF participated
in the working groups.

Acronyms and abbreviations (AAA) used throughout this document are given in a Glossary on
pages A4-1 through A4-3. Acronyms and abbreviations are also defined in each chapter with their initial
use, -but tables of AAA were generally eliminated from each individual chapter. The participants'
addresses and phone numbers are given on pages AS-I through AS-6.

v
 The editors express their deep appreciation to all participants for their analytical, creative, and
incisive involvement. We especially thank the authors of Chapters 1 through 19 and the (co)chairmen of
the working groups corresponding to Chapters 20 through 29 for their cooperation and effortS in producing
and/or coordinating the preparation of the written copy. We also gratefully acknowledge NREL staff
members for their significant administrative, coordinating, editing, and word processing contribu-
tions-Julie Baxes and Dori Nielsen, Conferences Group; Janet Fried, Pat Haefele, and Fran VanDerPol,
Word Processing Group; Barbara Spitz, Corporate Communications Section; and Regina Witherspoon,
Measurements and Characterization Branch; for their help before, during, and after the workshop.

vi
EXECUTIVE SUMMARY

A.W. Czandema and A.R. Landgrebe

The goal of surface processing is to develop and use innovative methods of surface modification
and characterization that will provide optimum performance and environmental protection for cost-effective
operational lifetimes of systems, materials, and components used for specific applications in the
transportation and utilities technologies.

Chemical and/or physical effects at surfaces determine the performance and the lifetime of devices
in a variety of technologies. This fact has become apparent in the last two decades as new techniques
have allowed .us to characterize surfaces at the atomic/molecular level with a great degree of sensitivity.
The ability to control the modification of surfaces and tailor-make surfaces for specific applications has
also improved significantly in the same period. Major advances have also been made in the theoretical
understanding of surface phenomena and the ability to model surface processes. These advances led to
the possibility of developing model systems to predict surface properties. The study of these phenomena
has spawned a new field of research that is commonly referred to as surface science.

Basic surface science research is well funded by several federal agencies, including the National
Science Foundation, the Office of Naval Research, the Air Force Office of Scientific Research, and DOE's
Division of Basic Energy Sciences, especially by the Division of Materials Sciences. Several research
centers have been created. The Center for Advanced Materials at Lawrence Berkeley Laboratory and the
Center for Surface and Interface Research ' at .the University of Connecticut are typical examples.
Furthermore, the Division of Materials Sciences has a long history of generously funding surface science
research at Lawrence Berkeley Laboratory, Ames Laboratory, Argonne National Laboratory, Oak Ridge
NatiQnal Laboratory, and Brookhaven National Laboratories, but has provided minimal funding for
mission-oriented laboratories (e.g., Sandia National Laboratories, Los Alamos National Laboratory,
Lawrence Livermore Laboratory, and National Renewable Energy Laboratory). In addition, federal
research laboratories, such as the Naval Research Laboratory, and several universities have developed
strong capabilities in basic surface science research.

Surface processing is a subfield of applied surface science for preparing tailor-made surfaces for
specific end-use applications, characterizing the surfaces, and developing a theoretical framework. The
crucial importance of surface properties is well known for applications in conservation and renewable
energy technologies, energy distribution, energy generation by utilities, and buildings, and by other
industrial energy users [1]. The unique aspects of these applications areas provide surface scientists and
engineers with unusual opportunities to carry out focused research and development on materials/systems
with targeted end-use applications. In the transportation technologies, for example, the efficiencies.
performance. and lifetimes for electrochemical storage and distribution, and surfaces for lubricating and
wear depend very much on the surface properties of the active materials. The ability to tailor-make
surfaces for specific applications will have tremendous impacts on these technologies. Concurrently, being
able to monitor the changes on these surfaces and characterize the chemical and physical processes
occurring on them will allow us to understand the underlying phenomena in microscopic detail and to
develop improved materials and surfaces for these applications.

Applications of surface processing include a broad spectrum of energy technolOgies. All conserva-
tion and renewable energy technologies will benefit from surface processing research and development
The National Materials Advisory Boards panel on corrosion estimated a potential savings of several billion
dollars annually if surface processing technologies can reduce corrosion problems. Additional billions,can
be saved if interface reactions that degrade device and component performance can be slowed or

ES-1 '
essentially eliminated. The lifetime of our aging power generation facilities will also be extended as new
materials and surfaces are defined by responding to the opportunities for research and development
identified in this document

Information on the current status of surface characterization and surface modification is contained
in Chapters 1 through 8 and Chapters 9 through 19, respectively. Progress in surface characterization and
modification has been spectacular since the early 1970s. Needs and opportunities in 10 topical areas of
applied surface science are contained in Chapters 20 through 29. .

I. OVERVIEW OF SURFACE PROCESSING AND INTERFACIAL PHENOMENA WITH SPECIFIC

APPLICATIONS IN TIlE TRANSPORTATION AND UTILITIES TECHNOLOGIES

The essential technical knowledge underpinning the need for a surface processing research and
development is:

• Surface processing combines surface characterization and modification into an applied surface sciences
subset of surface science.

• Essential components and systems in the conservation and renewable energy technologies consist of
using surfaces or thin-film multilayers.

• Surfaces/interfaces are thermodynamically unstable and ultimately determine the lifetime of systems,
materials, and components in conservation and renewable energy technologies.

• The rate of reaction at unstable interfaces must be slowed to achieve the desired lifetime while
maintaining performance.

• Surface modification may be successful in slowing reaction rates.

• Surface characterization of compositional, bonding, structural, and topographical changes that often
precede degradation are essential for monitoring the reaction rate.

A. Surface Characterization

Recent developments have provided the means for surface characterization with unprecedented
resolution. The variety of techniques all provide some aspect of the information required, and usually a
combination of techniques is required to explore a particular surface process to obtain a thorough
understanding of the particular phenomenon. Some of these techniques are labeled ex situ. meaning that
the sample needs to be removed from its operating environment into a specialized high vacuum chamber
for analysis. In some applications, questions arise concerning the extent to which the surface is modified
as it is removed from the operating conditions, and careful control of the transfer process becomes
essential for proper interpretation of the data. Other techniques are labeled in situ, because the surfaces
can be characterized in their operating environments. Usually, both types of characterization techniques
are essential for a thorough understanding of a particular surface phenomenon. The promising surface
characterization techniques include microscopies for surface structure (high resolution electron microscopy,
analytical electron microscopy, transmission electron microscopy, scanning tunneling microscopy, atomic
force microscopy, low energy electron diffraction, and ion scattering spectroscopy), compositional surface
analysis using ion (secondary ion mass spectrometry, secondary neutral mass spectrometry, surface analysis
by laser ionization, ion scattering spectroscopy, Rutherford backscattering spectroscopy, and nuclear
reaction analysis) and electron (X-ray photoelectron spectroscopy, Auger electron spectroscopy, scanning

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Auger microscopy, ultraviolet photoelectron spectroscopy, and core-electron energy loss spectroscopy)
spectroscopies, vibrational spectroscopies for chemical bonding (Fourier transfonn infrared-reflection
absorption spectroscopy, Raman, high resolution electron energy loss spectroscopy, surface enhanced
Raman spectroscopy, inelastic electron tunneling spectroscopy, and optical spectroscopic ellipsometry) and
synchrotron radiation methods (extended X-ray fine structure spectroscopy, surface extended X-ray fine
structure, and X-ray absorption near edge structure) for local bonding and ordering. Summaries of the'
current status of the most important techniques above are contained in Chapters 1 through 8.

B. Surface Modification Techniques

The techniques commonly used to modify or protect a surface include coatings, physical treatment,
and chemical modification. A variety of techniques are used to accomplish the treatment process in each
of the three categories, as discussed below.

Coatings technologies can be subdivided into polymer coatings and metal and ceramic coatings.
A wide variety of organic polymeriC coatings can be applied to surfaces. The preparation of a surface
prior to the application of any coating is critical, especially with organic coatings. The techniques for
application include brushing and spraying, electrostatic spraying and electrochemical deposition, and
coating with organics that are then cured to produce the protective layer.

A wide variety of high- and room-temperature processes are used in the preparation of metallic
and ceramic (including glassy) types of coatings. The room-temperature coating processes include:

• Electrochemical and electroless deposition of metallic coatings; pulsed electrodeposition of metallic

glasses

• Ion plating, which involves the deposition of vapor-phase ions at electrically charged surfaces to
produce metallic and alloy coatings

• Chemical vapor deposition, which involves chemical reactions of vapor-phase species to produce
metals, alloys, and other chemical compounds, including ceramics

• Evaporation and sputtering, which involve the deposition of materials and the combination of materials
by physical vapor transport.

Chemical vapor deposition, evaporation, and sputtering can also be conducted at high temperatures.
In addition, techniques specifically conducted at elevated temperatures include solar furnace processing,
laser-assisted spraying and annealing, spray and detonation gun coating, and sol-gel coating.

Physical treatments modify the surfaces physically using mechanical techniques, which include
either shot peening or shock hardening. Photon (solar furnace or lasers) or electron beam processing
involves the rapid scanning of a surface with a high-power photon source or electron beam. In the latter
cases, a thin molten surface layer is produced and rapidly solidified by heat transfer, thus produCing
metastable surface alloys and glassy alloy surface layers.

Chemical surface modification is usually accomplished with one of three approaches. These
include:

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(1) Chemical reactions at the surface, in which the surface composition is changed by reaction with a
gaseous species, usually at an elevated temperature. Nitriding and carbiding are examples of such
treatments, in which a surface phase is produced whose thickness is determined by diffusion.

(2) Electrochemical surface modification, which involves an electrochemical reaction to produce a

modified surface. Typical examples include the electrochemical formation of polypyrrole films and
the attachment of Silane-type ligands.

(3) Ion implantation, which involves the implantation of high-energy ions into the near-surface region.
'This produces new metastable surface compositions, usually without causing dimensional changes.

In addition to the above well-known techniques, there are chemical approaches in which the
adsorption of organic species in organized molecular assemblies improves the corrosion resistance. How
these inhibitors actually work is not very clear, and the whole effort is more of an art than a science.
Understanding the attachment chemistry of organized molecular assemblies onto inorganic surfaces and
the state of organization of organized molecular assemblies could assist us in developing another powerful
technique to modify specific surface properties.

n. NEEDS AND OPPORniNITIES FOR USING SURFACE PROCESSING WITH SPECIFIC

APPLICATIONS TO TRANSPORTATION AND UTll.ITY 'tECHNOLOGIES

A. Scope

The scope of the research and development needs and opportunities in surface processing can be
grouped quite naturally into three areas:

• Surface Processing Applications for Transportation Technologies.

• Surface Processing Applications for Utility Technologies.

• Generic Applications of Surface Processing.

Research and development in these three areas do overlap, as evidenced by the 10 subjects
considered at the workshop. These subjects and the principal technology applications areas are: corrosion
protection, fuel cells and solid batteries, lubricating and wear surfaces, and photoelectrochemical systems
for surface proceSSing applications for transportation technologies; polymer/metal(oxide) interface needs
and thin-film, multilayer solar collectors for surface processing applications for utility technologies; and
accelerated life testing of systems, materials, and components with solid/solid, solidlliquid, and solid/gas
interfaces, interfacial microchemical characterization needs, conducting polymers in energy technologies,
and organized molecular assemblies for generic applications of surface processing.

Other study areas could have been included in which surface properties are important, e.g.,
catalysis, coatings, adhesives, glass technologies, and low-energy surfaces such as diamond-like or silicon
carbide films. Except for catalysis, these study areas are included as subsets of aspects of the 10 subjects
given previously.

ES4
B. SURFACE PROCESSING NEEDS AND OPPORTIJNITIES FOR SURFACE PROCESSING
APPLICATIONS FOR TRANSPORTATION TECHNOLOGIES, SURFACE PROCESSING
APPLICATIONS FOR UTILITY TECHNOLOGIES, AND GENERIC APPLICATIONS OF
SURFACE PROCESSING

The technical approach for using surface processing includes identifying the degradation
mechanisms in candidate system, material, and component configurations primarily from experimental
work that simulates conditions of use, and interpreting the data to deduce the mechanisms of degradation.
The Reliability Research Group at AT&T Bell Laboratories has successfully used this approach for more
than 15 yearS. As the degradation mechanisms are understood, the materials and/or use configurations will
be modified as needed, or new materials options will be sought and recommended. The work in any
applied science area must be weight:ec.t-toward finding the limiting factors for a cost-effective, service
lifetime, i.e., the fastest degradation processes will be studied first and most intensively, and when those
degradation problems have been corrected, research will be focused on the next limiting issue(s). The
correlation between accelerated aging and lifetime prediction must necessarily be accomplished with results
from the other study areas. In each of the 10 topical areas of applied surface science listed below, key
research issues are indicated.

1. Corrosion Protection

There are major application areas for corrosion protection in the transportation industries,
particularly the application of paint on metals and plastics (see also II. B. 4., below). Examples include
galvanized steel, external mirrors, headlamps, trim, hood and door hem flanges, tailgate assemblies, and
bumpers. Surface modifications may be achieved by using high-energy processes, zinc protective layers,
sol-gel fllms, or alodine conversion coatings.

Key research issues are to:

(1) Improve galvanizing alloys on steel.

(2) Improve adhesion of protective layers (e.g., paint).

(3) Improve the understanding of light metal alloy corrosion systems and reduce the corrosion rate of
the protected metal.

(4) Identify cleaning processes that precede surface modification in (e).

(5) Select surface modification methods for achieving (b) and (c) (e.g., anodic oxide films, phosphate
conversion coatings, electrodeposition, and sol-gel coatings).

(6) Use in situ microchemical characterization of buried interfaces in light-alloy systems, electrochromic
windows, and photovoltaic modules to establish chemistry, morphology, mechanical stress, and
mechanisms of degradation.

(7) Establish compatibility and retarded degradation after (5).

(8) Measure accurately the interfacial adhesion by a physical process.

(9) Assess the relative contribution of chemical versus physical bonding to surface adhesion.

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(10) Develop methods for homogeneous modification of irregular shapes.

(11) Perform research and development on those surface processing methods with potential for use on
a manufacturing scale with on-line process control.

Corrosion protection is also required in batteries and fuel cells, in mirrors for concentrating solar
radiation (e.g., the Aglpolymethylmethacrylate interface); in photovoltaic cells (e.g., metallization, busline,
and interconnects), and in electrochromic devices. The research needs are considered below in
Sections II. B. 2. and II. B.S., respectively. Other corrosion problems considered to be oflower priority
include the compatibility of working fluids in solar thermal systems, biofouling in ocean thermal systems,
corrosion of ceramics, glasses, and sensors, and corrosion in fuel systems.

2. Solid Batteries and Fuel Cells

The major application area for solid batteries and fuel cells is in the transportation industry for
the electric vehicle program. Overlapping exists with corrosion protection (e.g., carbon and graphite),
polymer/metal(oxide) interfaces (e;g., lithium batteries), conducting polymers (e.g~ , electronic and ionic),
microchemical characterization (surface composition and microstructure of pores), and catalysis.

Because no generic examples ·exist for all battery/fuel cell systems, model systems identified for
study include polymer electrolyte membrane fuel cells, direct methanol fuel cells, zinc/air batteries, and
lithium/polymer batteries. The key research issues, which are related to catalysis, corrosion,
electronic/ionic contact, and hydrophobic/hydrophilic behavior at thesolidlboundary interface, are to:

(1) Define or identify the interfacial function, desired properties, and specific problems.

(2) Identify the surface modification needed to solve the problem.

(3) Identify the in situ characterization needed to elucidate reaction mechanisms and degradation
mechanisms.

(4) Conduct durability testing on the modified fuel cellslbatteries.

3. Lubricating and Wear Surfaces

The major application areas for lubricating and wear surfaces are in the transportation (e.g.,
engines, fuel delivery systems, valve trains, and power transmissions), metal forming, and foundry
industries. The key research issues are to identify surface modifications (e.g., nitriding, ion implantation,
plasma processing, phosphating, and sol-gel coatings) to:

(1) Reduce wear in valve guides/stems and piston ringlliners systems.

(2) Reduce wear in power gearslbearings and clutch materials.

(3) Reduce wear on cam rollers and journal bearings.

(4) Reduce wear on injector plungers, spray holes, and plunger tips.

(5) Improve cylinder kits and fuel pumps for alternate fuels.

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(6) Reduce wear on lightweight materials.

(7) Improve the surface finish on composites.

(8) Reduce the wear.: on nonferrous forming tools, ferrous forming dies, and aluminum foundry patterns.

(9) Model wear and adhesion between moving parts.

4. PolymerlPolymer and PolymerlMetal(Oxide) Interfaces

The principal applications areas for polymer/polymer and polymer/metal(oxide) interfaces are in
the utilities technologies (e.g., photovoltaic, solar thermal, power transmission, windows, and wind
turbines), although significant applications exist in the transportation technologies. For practical purposes,
polymer/metal interfaces is a misnomer except for polymers on gold. Even the noble metals (e.g., silver,
platinum, and iridium) have a monolayer of oxidized surface in practical use, and this oxidized monolayer
or multilayers (e.g., aluminum, copper, and iron) will dictate the interface behavior. The interphase regime
is better nomenclature as it indicates the material in the region between two different solid phases.

The key research issues are related to painted metal or plastics; adhesively bonded components;
electronic devices including photovoltaic modules, sensors, and microelectronics; and metallized polymers
such as mirrors to reflect solar radiation. The issues are to:

(1) Select materials in the design stages for recyc1ability, compatibility, processibility, and performance.

(2) Select the optimal surface modifications (e.g., cleaning, vapor deposition, adhesion promoters,
plasma treatments, and ion implantation) for each specific materials system.

(3) Understand polymer coating formation methods.

(4) Elucidate interphase formation mechanisms.

(5) Elucidate interphase degradation mechanisms.

(6) Characterize surfaces and the interphase (morphology, composition, bonding, and structure).

(7) Develop in situ in-process monitors for large scale production.

(8) Develop nondestructive testing methods for assessing the adhesion strength.

(9) Perform accelerated aging as screening tests-and then to establish degradation mechanisms and make
lifetime predictions.

(10) Establish tolerance in processing treatments that will stiII yield.adequate quality of the interphase.

S. Thin-Film, Multilayer Solar Devices

The principal application areas for thin-film, multilayer solar devices are for the utilities
technologies from photovoltaic, solar thermal, and solar buildings (i.e., electrochromic windows). Surface
modification methods (e.g.; plasma deposition and rapid thennal annealing) are again component- _or
device-specific and must be chosen as part of the research program. Most of the key research issues have

ES-7
been delineated in DOEJNREL 5-year program plans or initiatives related to these technologies. These
issues are to:

(1) Identify interface degrad~on mechanisms that limit device lifetime or reduce the performance.

(2) Improve the durability of encapsulated photovoltaic devices by lowering the rate of degradative
interface reactions (e.g., metallization corrosion, surface-catalyzed pottant degradation,
environmentally tight edge seals).

(3) Improve the durability of silvered polymers by eliminating polymer/silver interface corrosion.

(4) Develop thin-film photovoltaic modules with improved junction properties to raise the voltage and
,fIll factors.

(5) Improve the durability of electrical contacts in general, and specifically for cadmium telluride thin-
film modules.

(6) Develop low-energy, antisoiling surfaces for mirrors, photovoltaic modules, and electrochromic
windows.

(7) Improve · photovoltaic and electrochromic window materials to minimize interface charge-carrier
trapping effects.

(8) Devise diffusion barriers to minimize problems resulting from interdiffusion at interfaces.

(9) Modify surfaces to enhance adhesion in multilayer stacks.

(10) Modify semiconductor/metallization interfaces to obtain long-term stability, high performance, and
corrosion resistance.

(11) Develop deposition processes that eliminate the need for extractive patterning processes.

(12) Identify surface processed interphases that eliminates mechanical stresses between thin film
multilayers.

(13) Conduct accelerated life testing, establish degradation mechanisms, and estimate service lifetimes
for photovoltaic, solar thermal, and electrochromic window devices.

(14) Improve glass surfaces with and without deposited thin films for stability.

(15) Reduce metallization patterning costs by using a solar furnace.

6. Accelerated Ufe Testing

The application areas for accelerated life testing certainly include all utilities and transportation
technologies, but the areas are as broad as industry itself. Surprisingly, the current status is almost
universally dependent on the single point method of:

ES-8
 t.(real time, outdoors) = kft (failure in accelerated test) (1)

where k is really thought to be a constant.

The key research issues are to:

(1) Identify critical accelerating stresses including the maximum allowable stress before a mechanism
change occurs and the range of the stress as it relates to reality.

(2) Expand the use of the Spearman rank correlation method.

(3) Identify new approaches to relating lifetime prediction from failure in accelerated test, including
defining what is a failure (e.g., percent of performance loss, change in appearance).

(4) Develop predictive models based on mathematical models, correlation methods, and data analysis,
and compare them with results from large quantities of samples stressed to failure.

(5) Understand degradation mechanisms that lead to failure, depending on the variable (time,
temperature, ultraviolet, relative humidity, water, etc.) and their synergism.

(6) Quantify real-time. stresses versus accelerated test stresses to establish the simplicity or complexity
of k in Equation 1.

(7) Educate perso~el and their managements on the limits of accelerated life testing.

(8) Define how stresses are characterized andlormeasured.

(9) Develop and consolidate data bases, especially for solar exposures in hostile terrestrial environments.

(10) Use extensive characterization of materialslinterfaces to explain degradation mechanisms.

7. Interfacial Microchemical Characterization Needs

As the surface characterization component of surface processing, the interfacial microchemical

characterization needs are applicable to all components of conservation and renewable energy technologies
wherever an interface is present. The limiting stability of any system or component is the
thermodynamically unstable interface. The current status of present methods has been summarized in
Chapters 1 through 8. The crucial key research issues are to:

(1) Improve chemical specificity to detecting bonding, organic materials, and hydrogen.

(2) Develop real time techniques for use in on-line dynamic processing steps.

(3) Improve/develop new techniques (e.g., atomic force microscopy/scanning tunneling microscopy, X-ray
optics, greater spatial resolution), especially for nondestructively studying real and buried interfaces,
impurities at solid/solid interfaces, surface contaminants, interdiffusion, and interface and thin-film
stability (degradation).

(4) Expand the availability of sophisticated measurements and analysis experts through collaboration,
sharing, and more efficient use among universities, industry, and national laboratories.

ES-9
(5) Improve detectability of defects, microtopography, and microphase formation.

(6) Extend more surface science techniques to characterizing the solidlliquid interface.

(7) Imp'rove the monolayer sensitivity of Fourier transform infrared-reflection absorption and optical
spectroscopic ellipsometry.

8. Conducting Polymers

The principal application areas for conducting polymers in the transportation technologies are in
fuel cells, solid batteries, sensors, variable transmission windows and reflectors, and fuel tank surfaces (to
prevent static charge buildup). In the utility technologies, applications/areas include supercapacitors,
electromechanical actuators, electromagnetic shielding, photon-based optoelectronic devices, sensors and
displays, and thin-film, high-temperature superconductor multilayer stacks. The key research issues are
to:

(1) Understand the role of the interface in both electronic and ionic conduction mechanisms.
(2) Improve achievable electrical conductivity without decreasing the ease of processability.

(3) Obtain improved environmental and thermal stability.

(4) Minimize interfacial resistance between polymer electrolyte fIlms and electrode materials.

(5) Develop processing procedures for application to various materials.

(6) Improve cycle life and cycle rate limitations at the polymer electrolyte/electrode interface.

(7) Optimize polymer synthesis on substrates and subsequent modification to obtain desired
performance.

(8) Develop optically transparent conducting polymers.

(9) Improve adhesion between conducting polymers and various substrates.

(10) Fabricate polymers with improved physical properties such as tensile strength and flexibility.

9. Photoelectrochemical Systems

The principal application areas for photoelectrochemical systems can be in the utility or
transportation technologies depending on the design of the particular photoelectrochemical system. The
photoelectrochemical system may be constructed to yield electricity or a fuel, or to charge a battery. The
key research issues are to:

(1) Obtain more fundamental understanding of the interface issues to facilitate identifying the optimal
surface modification methods.

(2) Optimize long...term stability and improved efficiency of the photoelectrochemical system by interface
manipulation.

ES-I0
(3) Identify improved characterization methods for interfaces arid bulk materials in photoelectrochemical
systems.

(4) Identify most cost-effective fabrication of photoelectrochemical system interfaces and structures (e.g.,
use interphase protective layers, buried junctions, catalytic interfaces, or nanostructures).

(5) Improve the synthesis, detoxification, and stability of materials used in the fabrication steps.

to. Organized Molecular Assemblies

The opportunities for technology applications of organized molecular assemblies are plentiful in
areas 1 through 6, and 9 above. The most important effort is to focus on using self-assembled monolayers
in applied research areas while continuing fundamental feasibility studies. In the applied research areas,
the key research issues are to:

(I) Develop thermally and oxidatively stable self-assembled monolayers from organic and inorganic
molecules.

(2) Direct applications to technological substrates (e.g., steels, aluminum, copper, ceramics, glass, and
photostable polymers).

(3) Control interfacial properties in fuel cells at the gaslliquidlcatalystlmembrane interface.

(4) Develop self-regenerating self-assembled monolayers for passivating corrodible surfaces.

(5) Identify ·(self-regenerating) self-assembled monolayers for friction control.

(6) Prepare low energy optical component surfaces (e.g., mirrors and photovoltaic modules) that are
resistant to soiling and biofouling, and are easily cleaned.

(7) Employ self-assembled monolayers as self-cleaning, self-passivating materials in industrial processing

steps.

In the areas of fundamental research, the key research issues are to:

• Develop methods for forming in-plane patterns and features in self-assembled monolayers.

• Use self-assembled monolayers with deposited overlayers as a model system to elucidate interactions .
between organic functional groups and inorganic species.

• Study self-assembled monolayers as model systems for complex phenomena, including but not limited
to wetting, adhesion, friction, wear, fouling, soiling, biofouling, corrosion, mass transfer, change
transfer, and electron transfer adhesion.

• Use self-assembled monolayers to understand ·phenomena in condensed-matter science, cooperative

behaviors, phase separations, and the influences of defect frequency and nature.

• Develop new types of self-assembled monolayers, focusing on enhanced stabilities and new types of
surface-monolayer chemistry.

ES-II
• Use self-assembled monolayers as nuclear ion centers for three-dimensional processes, e.g.,
condensation of water, growth of crystals, and attachment of polymers.

• Use self-assembled mono layers as model systems for two-dimensional organization of complex
molecules, in relation to molecular materials.

• Develop computational models for self-assembled monolayers and self-assembled monolayer-related

phenomena.

11. Other Areas of Impact

In addition to the examples mentioned above, a program in the surface proceSSing technologies
will greatly impact the microelectronic, semiconductor, corrosion protection, and caiaIyst industries.
Technologies dealing with ultrathin films, protective and decorative surface coatings, variable conducting
masks, and novel bimetallic alloy catalyst systems rely tremendously on the research progress on a surface
processing technology. A DOE-supported technology base program will assist U.S. industry substantially
in a wide variety of fields and will allow us to maintain and improve our competitive posture in the global"
marketplace.

Ill. EPILOGUE

In using surface processing, two potential major technical barriers need to be overcome. These
are:

• Securing stable materials that are compatible with each other, Le., long-term interface stability, without
compromising the performance of the systems, materials, and components for specific applications to
transportation and utility technologies.

• Developing combinations of materials that meet the criteria for performance, durability, economics,
and user acceptance.

A crucial need and timely opportunity exist to use and extend the scientific and engineering
knowledge base in surface processing and applied surface sciences to provide solutions to selected priority
problems in the transportation and utility technologies. Current components and systems represent
approaches taken in the 1980s that have been adequate for their purposes, but need to be enhanced for
future needs.

The emphasis of the surface processing research and development program needs to be on
formulating, preparing, characterizing, developing, testing and qualifying where applicable, modifying,
demonstrating, and understanding advanced systems, materials, and components for specific applications
to transportation and utility technologies that will meet lifetime, cost, and performance requirements for
the 1990s and beyond.

To ensure future success in the related transportation and utility technologies, surface processing
work needs to be initiated as soon as possible and aggressively pursued to reach the confidence level
needed for selecting, guaranteeing, and mass-producing future components/systems for long-term use. The
research and development need is cross-cutting or interdisciplinary in nature [2] and requires involvement
of industry, academia, and federally funded laboratories.

ES-12
 For DOE, a significant cross-cutting applied research program in surface processing technologies
will provide several benefits to all conservation and renewable energy technologies, Le., it will:

• Create a critical mass of researchers and equipment that each Program Office of conservation and
renewable energy technologies can draw upon to solve specific end-use problems.

• Provide a multidisciplinary approach, produce strong synergistic effects, and allow various avenues
to be explored to solve a specific problem.

• Make available to the emerging renewable energy technology industries in the United States well-
equipped facilities with talented experts to assist in solving specific problems and enhancing the
competitive position of U.S. industry in the global marketplace.

The need for a critical mass of researchers with multidisciplinary backgrounds, assisted by state-of-
the-art instrumentation, is essential to the success of surface processing research and development. Surface
characterization and modification technologies encompass techniques typically developed by physicists and
chemists; these techniques are being used and improv~ upon by physicists and chemists, as· well as by
materials scientists and electrical, chemical, and other engineers. The problems that need solving also
cover a wide spectrum of disciplines. The synergistic effect expected from a multidisciplinary approach
will make surface processing research and development unique and allow it to meet its goal of providing
~ genuine technology-based, cross-cutting, research support for all conservation and renewable energy
technologies. The ability of surface processing research and development to impact other major DOE
efforts makes it very attractive.

For U.S. industry, in general, a world-class leadership in surface processing is an equally strong
impetus for the planning of an research and development program. As indicated in the preceding sections,
a variety of technologies can benefit from this type of generic research, and advances in surface processing
will allow interested industrial concerns to be partners in this effort and to use the knowledge and the
equipment.

Although many different assessments will be made about this workshop, positive results can
already be stated. Another opportunity has been provided for increased communication among scientists
and engineers including those involved with basic and applied problems. Industrial, academic, and
federally funded members of the scientific and technological communities have been involved in the
planning and have been made aware of the difficulties in setting priorities, even in a focused subset of
surface science. Their dedicated effort in establishing the priorities and identifying the most relevant
research issues in surface processing for 10 typical areas of applied surface science has resulted in this
document The task now is for all of us to carry out the most important recommendations.

REFERENCES

1. A.W. Czandema and R. Gottschall, Eds., "Basic Research Needs and Opportunities on Interfaces in
Solar Energy Materials," Special Issue, Mat Sci. Eng., g 1-168 (1982).

2. A.W. Czandema, P. Call, and A. Zunger, Materials Sciences, in T.S. Jayadev and D. Roessner, Eds.,
"Basic Research Needs and Priorities in Solar Energy, Vol. n, Technology Crosscuts for DOE,"
SERI/fR-351-358, January 1980. (Available NREL, 1617 Cole Blvd., Golden, CO 80401.)

3. See listing of workshop and panel reports in Appendix AI.

ES-13
 1. COMPOSmONAL ANALYSES OF SURFACES AND 1HIN FILMS
BY ELECTRON AND ION SPECTROSCOPIES

C. 1. Powell
Surface and Microanalysis Science Division
National Institute of Standards and Technology
Gaithersburg, MD 20899

ABSTRACT

An overview is given of the current capabilities, advantages, and limitations of the six techniques
in common use for compositional analyses of surfaces and thin films: Auger electron spectroscopy (AES),
X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), sputtered-neutral mass
spectrometry (SNMS), ion-scattering spectroscopy (ISS), and Rutherford backscattering spectroscopy
(RBS). Information is also given on efforts to improve these techniques and on the potential of other
methods for determining surface compositions during processing.

I. INTRODUcnON

Surface and interface properties are crucial in many different energy and transportation~chniques,
as is clear from the present workshop. While particular properties such as corrosion- or wear-resistance,
reactivity, and electrical properties are needed for specific applications, these depend on the chemical
composition at the surfaces or interfaces of interest.

Six techniques are frequently used for determining the composition of the outermost several atomic
layers of a material: AES, XPS, SIMS, ISS, SNMS, and RBS. Measurements with the first four of these
techniques are generally made in an ultrahigh vacuum (UHV) environment; SNMS can be performed in
UHV depending on the method of ionization of the sputtered neutrals. Certain surface processing
operations (e.g., heating, film deposition, sputtering) can be carried out in UHV, but often the material
of interest has to be transferred to a separate chamber for other types of processing (e.g., interactions with
liquids or high-pressure gases). H surface layers of the specimen·material are removed by some method
(e.g., sputtering), the first five surface-analysis techniques listed above can be used to determine the
instantaneous surface composition as a function of time or of distance from the original surface. In this
way, the compositions of films with thicknesses up to about 1 J.IIIl can be determined together with the
local compositions in the vicinity of interfaces. The sixth technique. RBS, is an essentially nondestructive
method for measuring .near-surface and thin-film compositions in a non-UHV environment.

This report is in two parts. Fmt, the above six techniques are compared and contrasted, based
on their capabilities, advantages, and limitations-. This section of the report is drawn from a recent book
chapter [1]. Second, information is given on future prospects for technique improvements to make them
more useful for applications in surface processing. Mention is also made of other techniques that would
be useful for these applications.

ll. CURRENT STA11JS OF MAJOR 1ECHNIQUES FOR SURFACE ANALYSIS

Information on the major features of the six techniques is summarize9 in Tables 1-4. Tables 5-10
give information on the relative strengths and weaknesses of the techniques. These summaries are
intended only as a semiquantitative guide. The information pertains to commercially available surface
analysis systems, in their normal configurations, as opposed to custom-made instruments that optimize a

1-1
particular parameter. In many cases, trade-offs can and often must be made among the various parameters,
e.g., spatial resolution, accuracy and precision of analysis, sensitivity, sample damage, and cost.

A. Principal Features of Techniques

Table 1 gives an overview of the principal features of the techniques: One practical concern in
the application of these techniques is the potential for specimen damage by the incident beam. Such
damage can take the form of removal of specimen material (e.g., by sputtering or desorption), of changes
in specimen composition (e.g., decomposition or polymerization), or of atomic displacements. XPS and
RBS are relatively nondestructive, but some materials may be damaged during a prolonged surface
analysis. Decomposition is not common in XPS, but prolonged X-ray exposures may damage adsorbates,
organic compounds, and some ionic solids [2,3]. AES is essentially nondestructive for metals, alloys, and
many semiconductors, but electron beams will rapidly damage organic materials, adsorbates, glasses, and
some compounds [3,4]. Electron beam effects are generally proportional to the electron beam dose
(primary current density times bombardment time). An electron··beam-induced temperature increase is
most detrimental for thin films on substrates with low thermal conductivity. Electron-stimulated
desorption is often encountered in studies of ionic compounds. In extreme cases, e.g., for alkali halides,
the number of desorbed atoms or molecules per incident electron is greater than one [4]. Charging of
insulators is sometimes difficult to avoid and can even lead to induced electromigration. In general,
electron beam effects on fragile specimens can be minimized with a low primary electron beam current
density, short measuremept times, or scanning the incident beam to different regions of the surface.

SIMS, SNMS, and ISS are all intrinsically destructive (i.e., ion bombardment removes speCimen
material from the exposed surface, and it is not possible to remeasure the composition of a previously
sputtered surface). A trade-off must then be made between operating in the "static" mode for true surface
analysis and the data acquisition time. The "static" mode requires very low erosion rates [5] and thus low
current densities, which also may require optimization between the current density and detection limits
(i.e., signal-to-noise ratio). A low incident current density for AES, SIMS, SNMS, and ISS also means
that the lateral resolution will be degraded. Ion beams are also used for sputter depth profiling (SDP) to
obtain compositional information as a function of depth. Ion bombardment can damage specimens in
many ways including, for example, surface roughening, knock-on effects, atomic-scale cascade mixing,
preferential sputtering, amorphization and structural changes, decomposition, implantation, chemical state
changes, enhanced diffusion, enhanced adsorption, and redeposition [6].

The sampled depth (or information depth) for SIMS and SNMS is listed in Table 1 for the "static"
mode; in the dynamic mode (high erosion rates) [5], as often needed for thin-fum analysis, the sampled
depth may range from 1 to 5 nm or more, depending on the erosion rate, incident beam angle and beam
energy used In RBS, surface monolayers can be studied on single crystals using channeling techniques.
The sampled depth depends on the escape depth of the ejected electrons in XPS and AES, on
neutralization probabilities in ISS, and on erosion rates in SIMS and SMMS. The American Society for
Testing and Materials (AS1M) definition for information depth gives the depth from the exposed surface
from which a specified percentage of the detected signal originates. This depth should be distinguished
from two other terms, the detection limit (or detectability) and the sensitivity. The detection limit for a
particular technique is the minimum quantity of material that can be detected under specified operating
conditions and is often expressed as a fraction of an atomic layer; e.g., it is often assumed that the
detected material is present as an identifiable phase on a substrate of another material. The sensitivity is
the slope of a calibration curve in which the measured signal strength for a given element under specified
conditions is plotted versus elemental concentration.

1-2
 Table 1. Summary of Features of SIMS, SNMS, ISS, RBS, AES, and XPS,

Category SIMS SNMS ISS RBS AES XPS

Input "particle" 0.5-20 keV ions 0.5-20 keV ions 0.5-3.0 keV ions 0.5-3.0 MeV ions 2-20 keV Photons (X-rays)
electrons
Damage to Minimal to Minimal to Minimal for , Minimal 'except Minimal to Minimal
sample by input extensive extensive defocused beam for organics and extensive for (X-radiation)
particle depending on to moderate polymers focused e-beam
beam parameters
Output particles Secondary ions Secondary Input ion Input ions Electrons Electrons
neutrals
Measured Mass/charge of Mass/Charge of Energy of Energy of ion Energy of ejected Energy of ejected
quantity of sputtered surface postionized scattered ions backscattered Auger electrons core-level and
output particle ions surface species after binary from elastic Auger electrons
collisions collisions
Sampled depth 1-2 monolayers 1-2 monolayers Surface Many J.UIl into 2-20 monolayers 2-20 monolayers
("static") ("static") monolayer the solid
B. Data Collection

Table 2 summarizes factors important in data collection including vacuum re·quirements, data
acquisition rates, signal-to-noise (SIN) ratio, turnaround time, and depth profiling compatibility.
Measurements must be made with a pressure in the vacuum chamber of 10-4 Pa or better so that collisions
between electrons or ions and residual gas molecules are minimized. Residual gases may react with
specimens being analyzed, and pressures of 10-7 Pa or lower are generally required to minimize reactions.
Another factor is electron-stimulated adsorption, which can lead to oxidation or carburization [4] . Average
data acquisition times are given in Table 2, although the actual times may range from seconds to hours,
depending on the information desired. The SIN ratio governs the limit of detection; the ranges given
should be compared with the detection limits in Table 3.

For SDP, XPS is clearly inferior, because the ion beam etching and surface analysis must be done
alternately as a result of the relatively long data acquisition time and the relatively large X-ray beam size,
even for current "small-spot" XPS systems. Otherwise, a depth profIle is obtained with an inferior depth
resolution. However, XPS (as well as AES) can be used nondestructively to obtain depth profiles for
shallow depths ($ 50 A) by detection of ejected electrons at different takeoff angles. This technique
makes use of the variation of electron escape depth with takeoff angle; it is especially powerful when there
are electrons with widely different energies and thus escape depths for the same element. In custom-
designed RBS systems, near-surface nondestructive SDP may be obtained using channeling and grazing-
exit detector techniques. SIMS and AES combined with ion erosion are the two. most widely used SDP
techniques.

In recent years, the analog instrumentation for recording spectral intensities has been replaced by
digital data systems. These systems are extremely powerful for data acquisition and manipulation.

C. Features of the Analytical Methods

Important features of SIMS, SNMS, ISS, RBS, AES, and XPS are summarized in Table 3. Each
technique is able to directly identify elements with atomic numbers of 3 and higher. The elements H and
He can be detected by SIMS and SNMS, by forward scattering in ISS, or by nuclear reaction analysis
(NRA) with RBS equipment Hydrogen has been detected in some materials by AES and XPS from a
detailed analysis of the spectrallineshapes of other elements. The mass-sensitive techniques can detect
isotopes, but this capability is limited in ISS and RBS by poor peak resolution for mid- to high-Z
elements. SIMS and SNMS have the lowest detection limits, but SIMS suffers from wide sensitivity
variations with Z.

None of the ion spectroscopies provides the detailed chemical information obtained with the
electron spectroscopies, especially XPS. Small chemical shifts of elemental lines in XPS can be used to
identify different chemical states ·of an element; such identifications are extremely valuable (e.g., in
identifying surface reactions or processes) . . Auger lines also appear in XPS data and typically also show
chemical shifts. The difference in XPS and AES peak positions for an element, the so-called Auger
parameter, often has a chemical shift. Not only is the latter shift a useful diagnostic, but it may be the
easiest to measure reliably on nonconducting specimens. AES, as practiced with electron excitation, has
usually been done with analyzers of low energy resolution. Thus, the chemical information (shifts of
elemental lines and changes of peak shapes) obtained from the technique has been limited In some cases,
chemical species can be identified by AES data alone, but the supporting data are much less than for XPS.
Static SIMS is also very useful, although it can be difficult to extract this information due to the
complicating signals from sputtered cluster ions and molecular fragments. Recent experiments using SIMS
with high mass resolution have been particularly valuable in identifying organic materials on surfaces.

1-4
 Table 2. Factors Important for Data Collection in Surf~e Analysis by SIMS. SNMS. ISS. RBS. AES, and XPS

Factor SIMS SNMS ISS RBS AES XPS

Vacuum (Pa)· 10"' to 10-8 104 to 10-8 10"" to 10-8 < 104 I 0"" to 10-8 104 to 10-8
Acquisition time Seconds Seconds Minutes Minutes Seconds Minutes
Signal/noise ratio up to Hf 106 I~ to Ht 10 to I~ I~ to I~ 102 to I~
Turnaround time Fast+ Fast+ Fast+ Fast Fast+ Fast+
SOP·· Most natural for SIMSISNMS Easily done with Automatically Easily done with Laboriously done
because sample erosion is required bombarding done and non- an auxiliary ion with an auxiliary
beam destructi vel y gun ion gun
Other depth NA NA NA Yes" Yes" Yes"
profiling· methods

• Although data can be collected at pressures as high as 10-2 Pa, contamination of the specimen by the residual gases is a serious concern
depending on the reactivity of the surface. Note: I Pascal =7.5 x 10-3 Torr. .

+
Fast with instruments equipped with rapid-sample-introduction or load-lock facility. Turnaround is slow if samples are loaded onto a carousel
and a flange has to be reboIled to the vacuum system.

•• Does not include artifacts in the sample resulting from ion bombardment, which are the same for all analytical techniques except RBS .

.. Seetext.
 Table 3. Summary of Analytical Features of,SIMS, SNMS, ISS, RBS, AES, and XPS

Feature SIMS SNMS ISS RBS AES XPS

Elements not None None · H,He H,He H,He H, He
directly detected
Detection of H, Yes Yes 0< 190 (H)* With NRA Line shapes of other elements in a
He < 4r (D) compound
Isotopes Yes Yes LowZ ·LowZ No No
Detection limit 10-6 to 10-9 10-6 10-2 to 104 10-1 to 104 10-2 to 10-3 10-2 to 10-3
(at. fraction)
3
Variation of 10" to 10' 10 to 100 -1~ - 10 - 20 - 20
detection limit (Li to U) (Li to U)
withZ
Chemical Yes Yes Yes, but only for No Yes Yes
information and eight elements
value/usefulness Some Some NA Considerable Outstanding
Other information Polymers and organics, rnIZ to 10,000 Shadowing of Surfaces of Plasmon loss Chemical shifts,
and beyond for SIMS; spectra are adsorbate over- epitaxial films structure, oxidation states,
matrix-dependent, but much less so layers on single chemical shifts, valence band
for SNMS crystals, lineshape changes structure
Information on Yes Yes Rarely No Frequently Yes
compounds
Organic samples Yes Yes No No Damage likely Yes ,
Surface structure Some Some Adsorbates on Epitaxial films Adsorbates on single-crystal
single-crystal substrates, epitaxial films
substrates
Peak interference+ Rare Some None None+ Occasional Occasional
Elemental Excellent Very good Good-low Z; Good-low Z; Very good Very good
specificity ** Poor-high Z Poor-high Z
Lateral (x-y) 0.1 fJIIl 0.2-5 ~ 0.1 mm 1 mm 20-100 nm 20-100 ~
resolution
 Table 3. Summary of Analytical Features of SIMS, SNMS, ISS, RBS, AES, and XPS (Concluded)

Feature SIMS SNMS ISS RBS AES XPS

Lateral imaging Yes No Yes No Yes Yes
and value Very good NA Poor NA Outstanding Good
Charging Yes Yes Yes No Yes Yes
problems
Quantification Vary by up to 105 Yes for given Yes, but small Complete Yes Yes
sensitivity factors . in different instrument data base
matrices
Standard 5%-100% 5%-10% 5% 2% 1%-5% 1%
deviation (for
repeated
measurements)

• 9 is ion scattering angle.

I

+ Extent to which there may be accidental overlaps of spectral peaks due to tWo or more elements. For RBS, signals at energies corresponding
to certain elements can overlap signals due to other elements at different depths.

•• Extent to which two or more elements can be distinguished due to finite instrumental resolution.
It is possible now to·measure femtomoles of small organic molecules (molecular weight - 300) and to
obtain structural and molecular weight information for polymers. One can detect small molecules on
polymer surfaces or one polymer on another.

Each technique can provide different additional information about a specimen material. For example.
information about electronic structure can be obtained from XPS and AES. Structural information for
adsorbed molecules or thin epitaxial films can be obtained from the angular distributions of photoelectrons
or Auger electrons. The energy-loss structures in the vicinity of the elastic peak due to excitations of
valence and core electrons in electron-excited AES can be analyzed to give electronic and local structural
information.

Peak interferences can occur in AES and XPS but are usually only an annoyance (e.g., for compounds
with a large number of elements). An advantage of XPS is that accidental overlaps of photoelectron and
Auger peaks can be identified ·and overcome by changing the X-ray energy. High-resolution mass
spectrometers can separate peaks with nearly identical mass/charge ratios in SIMS, but the broader peaks
obtained with many SNMS instruments can lead to some ambiguity in peak identification for more
complex specimens. Both ISS and RBS are severely limited in elemental identification when analyzing
samples with several high-Z elements . .

The highest lateral resolution is attained at present wi~ AES. The indicated AES resolution in Table 3
is achieved, however, only with robust specimens that are not damaged by the high bombarding current
density. In addition, only major constituents of the surface region (with atomic concentrations - 10%)
can be detected with such lateral resolutions [5]. Very good lateral resolution, about 0.1 J.lIll, is achieved
in SIMS, although then with relatively high erosion rates of-the surface (Le., "dynamic" SIMS). TIme-of-
flight SIMS, however, enables greater efficiency in mass analysis compared to dispersive analyzers, and
correspondingly smaller erosion rates can be employed for a given lateral resolution. Considerable effort
has been made in recent years to improve the spatial resolution of XPS. Although'the lateral resolution
with XPS is now poorer than that in AES or SIMS, it should be remembered that X-ray excitation is
generally much less damaging to a surface than electron or ion bombardment and that the chemical state
information in- XPS can be very useful.

High spatial resolution is clearly important if the specimen is inhomogeneous. Practical materials can
have different types of inhomogeneities as well as finite roughness and perhaps complex morphologies.
High spatial resolution is then desirable for establishing the existence of multiple surface phases and, if
so, their spatial arrangement Even if a detailed compositional map of the surface is not needed, multiple
high-resolution analyses can be required at different surface regions to ensure that representative and
statistically adequate information is acquired [5].

Although most surface analyses performed are qualitative, there is increasing interest in quantitative
measurements, particularly with the availability of data systems for processing acquired spectra Physical
models have been developed for relating observed spectral intensities to elemental concentrations, but only
in the case of RBS is the model well established and the needed parameters readily available [5]. Most
quantitative analyses with AES and XPS are made with the use of elemental sensitivity factors, but matrix
effects, mainly the variation of attenuation lengths for Auger electrons or photoelectrons from a given
element from one matrix to another, can cause errors of about 20%-50% [7]. Matrix effects in SIMS can
be substantial (up to a factor of lOS), but useful quantitative analyses can be obtained with appropriate
standards [5,8]. Matrix effects in SNMS are much reduced compared to SIMS, but more studies are
needed of matrix effects on the energy and angular distributions of sputtered neutrals. In ISS, variations
of elemental signals in different matrices of up to an order of magnitude can occur; these variations are

1-8
due in large part to changing ion neutralization probabilities. Standard materials, with compositions
approximating those of the specimens to be analyzed, provide a relatively straightforward' means of
mininiizing matrix and instrumental uncertainties. It is not generally easy to prepare standards with similar
properties (distribution of surface phases, roughness, etc.) to the specimens, but ion implantation has been
shown to be a useful method for generating a reference signal in SIMS [8]. The high surface sensitivity
of ISS is such that care has to be exercised in avoiding surface impurities such as adsorbed gases.

D. Versatility, Ease of Use, and Supporting Data

Table 4 shows qualitative comparisons of selected feat.ures of the analytical techniques. The symbols
give a rough guide to the various features to supplement the information given in Tables 1-3.

Successful use of a particular technique depends on the availability of needed reference data Table 4
gives an indication of the extent to which needed data are available [8-11].

Information is also given in Table 4 on the relative use of the six techniques in recent years and the
effective takeoff year, that is, the year in which publications started to grow following the introduction
of commercial equipment [9].

E. Summary of Advantages and Limitations

Specific advantages and limitations of SIMS, SNMS, ISS, RBS, AES, and XPS are summarized in
Tables 5-10. These tables, together with the information in Tables 1-4, give an overview of these
techniques for surface analysis. More details concerning instrumental capabilities can be found in other
review articles [5,9,12-19]. Other reviews [20-22] give information on the applications of the surface
analysis techniques to many types of materials problems.

Table 4. Comparisons of Selected Features of SIMS, SNMS, ISS, RBS, AES, and XPS. The number of
plus symbols indicates a value from poor (+) to very good (I I I I I).

Feature SIMS SNMS ISS RBS AES XPS

Versatility ++++ +++ +++ +++ ++++ ++++
Ease of use +++ (dynamic) +++ ++++ ++++ ++++ I I I II
+ (static)
Thin-film SDP I I I I I IIIII +++ I III I I I I I I ++
Simplicity of data ++++ IIII I III II II I I I +++ ++++
interpretation
Accuracy of quantita- + ++++ ++ I I I I I ++++ ++++
tive analysis
Availability of ++++ (dynamic) + +++ +++ II III 11111
reference data + (static)
Approximate percentage 24 2 3 5 33 33
of use 1985-1990
Effective takeoff year 1973 1984 1974 1967 1969 1969

1-9
 Table 5. Major Advantages and Limitations of SIMS for
Surface Analysis and Sputter Depth Profiling (SDP)

. Advantages

• is sensitive to outermost 1-2 monolayers (static mode)

• can detect 10 ppm or less
• can acquire SDP data as surface is eroded during analysis
• can detect isotopes
• can detect H and D
• can acquire data rapidly
• has lateral imaging capability
Limitations

• requires destruction of sample for the analysis

• is quantitative with difficulty, at best
• has varying elemental sensitivity
• has complex spectra
• may cause chemical state changes from ion bombardment

Table 6. Major Advantages and Limitations of SNMS for

Surface Analysis and Sputter Depth Profiling

Advantages

• is sensitive to outermost 1-2 monolayers (static mode)

• can detect to ppm or less
• can acquire SDP data as surface is eroded during analysis
• can detect isotopes
• can detect H and D
• is quantitative with modest use of standards (a major
improvement over SIMS)
• can acquire data rapidly
Limitations

• requires sample destruction

• has poor lateral resolution
• may cause chemical state changes from ion bombardment

I-to
 Table 7. Major Advantages and Limitations of ISS for
Surface Analysis and Sputter Depth Profiling

Advantages

• is sensitive to first monolayer

• can detect 10-2 to 104 monolayer
• is good for SDP .
• is useful for studying ordered surfaces and adsorbates
• is excellent for segregation and/or altered layer studies
• can detect isotopes e~lSO, 14N",1~, 32S_34S)
• has simple spectra
• provides chemical information for a few surface compounds
• can be quantitative with standards
Limitations

• has poor lateral resolution

• has poor specificity for bigh-Z elements*
• is destructive although erosion rate can be less than a
monolayerlh
• requires better understan~ng of ion neutralization
• generally provides no chemical information

* For example, with incident 4He ions and a scattering angle of

138°, the following pairs of elements can be resolved: Na and
Mg, Fe and Cu, and Ba and Ta. Better resolution can be
obtained for bigh-Z elements with incident neon or argon ions.

1-11
 Table 8. Major Advantages and Limitations of RBS for
Surface Analysis and Sputter Depth Profiling

Advantages '

• is quantitative without standards

• can detect atomic fractions of 10-1 to 104 depending on Z
• directly measures depth distributions below the surface without
sample destruction
• has rapid data acquisition
• is especially sensitive to high-Z elements
• has modest vacuum requirements except for surface studies
• c~ be customized to study surface monolayers
• can resolve some low-Z isotopes
• can be combined with nuclear reaction an21ysis for detection of
H, He, and other low-Z elements
Limitations

• has poor lateral resolution

• provides no chemical information
• cannot resolve different elements of the same mass
• is limited for detecting low-Z elements
• requires lateral uniformity of sample
• is limited by overlapping signals due to mass and depth
• is limited to specimens with only a few elements

Table 9. Major Advantages and Limitations of AES for

Surface Analysis and Sputter Depth Profiling

Advantages

• is sensitive to 2-20 monolayers

• can detect ca. 10-3 atomic fraction
• is outstanding for SDP
• has a sensitivity range within a fact9r of 20
• has superb lateral resolution
• gives chemical information for some elements
• can acquire data rapidly
Limitations

• may alter surface composition

• may have severe charging problems for nonconducting
specimens
• is of limited value for organic materials
• has a slow rate of element mapping

1-12
 Table 10. Major Advantages and Limitations of XPS for
Surface Analysis and Sputter Depth Profiling

Advantages

• is sensitive to 2-20 monolayers

• can detect 10-3 atomic fraction
• is especially useful for chemical shifts from the same element
in different compounds
• is least destructive of all techniques
• has a sensitivity range within a factor of 20
• has minimal sample charging
Limitations

• has moderate lateral resolution

• is slower for SDP than other methods

m. FUTURE PROSPECTS

. While AES. xps. SIMS. SNMS. ISS. and RBS have proven to be very useful for solving a wi~e
range of materials and surface processing problems. they each have significant limitations. as summarized
in Tables 5-10. A brief summary will now be given of recent efforts to overcome or minimize some of
the major limitations of these techniques. Information will also be given on other techniques for surface
and thin-film analyses in surface processing applications.

A. Recent Improvements to Current Surface Analysis Techniques

1. Spatial Resolution

Strong efforts are being made to improve the lateral resolution of AES. XPS. and SIMS, in
particular. For AES. field-emission cathodes and parallel-detection schemes are being used to improve
lateral resolution without reducing data-acquisition times. Different types of X-ray focusing optics are
being developed to utilize the very intense photon beams at new synchrotron light sources for XPS with
lateral resolutions in the 0.1-1.0 J.Ull range. Liquid-metal ion sources and time-of-flight mass analyzers
have recently led to improved lateral resolution for SIMS. Depth resolution in sputter-depth profiling can
be optimized by careful attention to the factors that can degrade measured profiles [6]. Measurements of
Auger-electron or X-ray photoelectron intensities as a function of takeoff angle can be analyzed to give
depth profiles for shallow depths (up to about three times the relevant electron attenuation length)
nondestructively. although statistical fluctuations in the data can lead to nonunique solutions. and angular
anisotropies due to specimen crystallinity may cause additional complications [23].

2. Quantitative Analyses

Despite the conceptual simplicity of the surface analysis techniques, there are many sources of
systematic errors and artifacts [24]. Seah. however. has reported calibration schemes for the energy and '
intensity scales of AES and XPS instruments [25]. Improved techniques. based on a valid physical model
of electron transport, have been developed for background correction in xps. and these should also be
applicable to AES [26]. The same techniques have also been used to obtain depth distributions (again for

1-13
shallow depths) nondestructively [27]. A major problem in quantitative AES and XPS concerns the so-
called matrix correction for elemental sensitivity factors [7]; recent calculations of electron inelastic mean
free paths (lMFPs) have led to the development of a predictive IMFP formula for 50-2000 eV electrons
that can be applied to various materials [28]. Prutton and coworkers [29] have developed an advanced
scanning Auger microscope and improved algorithms for the correction of topography effects, beam-
current changes, and backscattering effects. Both resonant and nonresonant laser postionization schemes
are being developed for quantitative analyses by SNMS [30].

3. Reference Data

Efficient use of any characterization technique on a wide range of materials requires the
availability and accessibility of needed reference data. For AES, XPS, and SIMS, handbooks have been
published with spectral data needed for most solid elements and for a limited number of compounds.
NIST has recently announced the availability of an XPS data base containing over 13,000 entries for core-
electron binding energies, doublet splittings, and kinetic energies of X-ray-excited Auger electrons that
appear in typical XPS measurements (with AI. or Mg characteristic X-rays) [11]. The American Vacuum
Society is in the process of creating a data base of AES and XPS spectra that will be published in a new
journal, Surface Science Spectra, beginning in 1992. An evaluated set of ion sputtering yield data for
elemental solids bombarded by ions and with energies relevant for SDP and SIMS will be published soon
[31].

B. Other Techniques

One of the limitations of AES and, to a lesser extent, XPS is the limited amount of chemical
information they provide. Other techniques such as high-resolution electron energy-loss spectroscopy
(HREELS), infrared spectroscopy, or Raman spectroscopy, can give useful supplemental information,
particularly for molecules adsorbed on surfaces [32].

A major limitation of AES, XPS, SIMS, and ISS is that they are generally restricted to UHV
environments; in one method of SNMS, the specimen is exposed to an argon plasma. Some scientists,
nevertheless, have used efficient differential pumping arrangements to analyze solids or liquids with XPS
in local environments where the pressure was in the vicinity of 10-2 Pa.. It also might be possible to
perform XPS at higher gas pressures with synchrotron sources of X -rays and in places where the gas
atoms or molecules near the specimen act as a "converter" [33]. Total-reflection X-ray fluorescence offers
a more general means of analysis at atmospheric or higher pressures but not, however, with the surface
sensitivity of the techniques considered here.

Electron microscopy is a highly developed technique for materials characterization [34-37].

Modern Scanning transmission electron microscopes equipped with electron energy-loss spectrometers can
be used to probe chemical changes in the vicinity of solid-solid interfaces with a lateral resolution of about
0.4 nm. Atom-probe field ion microscopy can also be used to characterize solid-solid interfaces and the
composition of small grains with comparable spatial resolution [38]. For both forms of microscopy,
special specimen preparation techniques are needed.

High resolution scanning electron microscopes have been developed to study surfaces and thin-film
nucleation and growth phenomena in a UHV environment [39]. Elemental analysis with submonolayer
sensitivity has been attained by measuring characteristic X-ray emission at near-grazing takeoff angles
[40]. Recent efforts to improve the spatial resolution in electron microscopy and various forms of electron
spectroscopy have been summarized in the report of a recent workshop [41].

1-14
 Scanning tunneling microscopy and atomic force microscopy can be used to obtain topographic
information and other surface properties. These techniques cannot be used, in general, for compositional
analyses of "unknown" surfaces.

IV. SUMMARY

AES, XPS, SIMS, SNMS, ISS, and RBS are powerful techniques for the analysis of surfaces and
thin fllms. A careful selection of one or more techniques is needed to ensure that a problem can be
solved, given the capabilities and limitations of each method. Complementary techniques may often be
needed, however, to provide more specific chemical information, higher spatial resolution, or the ability
to monitor chemical changes at solid-fluid interfaces. The report of an earlier workshop analyzes different
approaches for characterizing the microstructure and microchemistry of interfaces [42].

ACKNOWLEDGMENTS

The author is greatly indebted to Drs. D. M. Hercules and A. W. Czanderna for their contributions
to the book chapter [1] on which this report is based.

REFERENCES

1. C. 1. Powell, D. M. Hercules, and A. W. Czanderna, in A. W. Czandema and D. M. Hercules, Eds.,

Ion Spectroscopies for Surface Analysis, Plenum Press, New York, NY, 1991, pp. 417-437.

2. R. G. Copperthwaite, Surf. Interface Anal., b 7 (1980).

3. 1. Cazaux, Appl. Surf. Science, ~ 457 (1985).

4. C. G. Pantano and T. E. Madey, Appl. Surf. Science,L 115 (1981); T. E. Madey, in D. C. Joy, Ed.,
Analytical Electron Microscopy-1987, San Francisco Press, San Francisco, CA, 1987.

5. H. W. Werner and R. P. H. Garten, Rep. Prog. Phys., £, 221 (1984).

. 6. S. Hofmann, in D. Briggs and M. M. Seah, Eds., Practical Surface Analysis, 2nd Edit, Vol. 1, Auger
and X-Ray Photoelectron Spectroscopy, Wiley, New York, NY, 1990, pp. 143-199.

7. A. I. Zagorenko and V. I. Zaporozchenko, Surf. Interface Anal., 1$ 438 (1989).

8. J. T. Grant, P. Williams, J. Fme, and C. J. Powell, Surf. Interface Anal., 1146 (1988).

9. S. Hofmann, Surf. Interface Anal., 2, 3 (1986).

10. M. P. Seah, Surf. Interface Anal., 2, 85 (1986).

11. C. 1. Powell, Surf. Interface Anal., 1L 308 (1991).

12. A. W. Czanderna, Solar Energy Materials, ~ 349 (1981).

13. C. J. Powell, in H. Windawi and F. Ho, Eds., Applied Electron Spectroscopy for Surface Analysis,
Wiley, New York, NY, 1982, pp. 19-36.

1-15
14. M. P. Seah and D. Briggs, in D. Briggs and M. P. Seah, Eds., Practical Surface Analysis, 2nd Edit,
Vol. I, Auger and X-Ray Photoelectron Spectroscopy, Wiley, New York, NY, 1990, pp. 1-18.

15. · H. W. Werner, in H. Oechsner, Ed., 1bin Film and Depth Profile Analysis, Springer Verlag, Berlin,
Germany, 1984, p. 5.

16. A. Benninghoven, F. G. Riidenauer, and H. W. Werner, Secondary Ion Mass Spectrometry, Wiley,
New York, NY, 1987, pp. 1022-1047.

17. J. R. Bird and J. S. Williams, in J. R. Bird and J. S. Williams, Eds., Ion Beams for Materials
Analysis, Academic Press, New York, NY, 1989, pp. 515-537.

18. I. V. Bletso, D. M. Hercules, D. van Leyen, and A. Benninghoven, Macromolecules, 1Q, 407 (1987).

19. H. Hantsche, Scanning, 11257 (1989).

20. C. J. Powell, Appl. Surf. Science, .1143 (1978).

21. C. J. Powell, Aust J. Phys., li. 769 (1982).

22. D. Briggs, Surf. Science, 189/190. 801 (1987).

23. H. E. Bishop, Surf. Interface Anal., .!L 197 (1991); W. H. Gries, Surf. Interface ·Anal., .!L 803
(1991).

24. C. J. Powell and M. P. Seah, J. Vac. Sci. Tech., A 8. 735 (1990).

25. M. P. Seah, J. Vac. Sci. Tech., A 9. 1227 (1991); M. P. Seah and G. C. Smith, Surf. Interface Anal.,
ll, 751 (1990).

26. S. Tougaard, Surf. Interface Anal., .11453 (1988); J. Electron Spectrosc., g 243 (1990); H. Bender,
Surf. Interface Anal., .!L 584 (1991).

27. S. Tougaard and H. S. Hansen, Surf. Interface Anal., H. 730 (1989).

28. S. Tanuma, C. J. Powell, and D. R. Penn, Surf. Interface Anal., .11 577 (1988); S. Tanuma,
C. J. Powell, and D. R. Penn, Surf. Interface Anal., .!L 911 (1991).

29. I. R. Barkshire, M. M. El Gomati, J. C. Greenwood, P. G. Kenny, M. Prutton, and R. H .. Roberts,

Surf. Interface Anal.,.!L 203 (1991); I. R. Barkshire, J. C. Greenwood, P. G. Kenny, M. Prutton,
R. H. Roberts, and M. M. El Gomati, Surf. Interface Anal., .!L 209 (1991); I. R. Barkshire,
M. Prutton, and D. K. Skinner, Surf. Interface Anal., .!L 213 (1991).

30. D. G. Welkie, S. Daiser, and C. H. Becker, Vacuum, £., 1665 (1990).

31. G. P. Chambers and J. Fine to be published.

32. J. T. Yates, Jr., and T. E. Madey, Eds., Vibrational Spectroscopy of Molecules on Surfaces, Plenum
Press, New York, NY, 1987.

1-16
33. C. 1. Powell, 1. Vac. Sci. Tech.,li. 549 (1978).

34. A. Howie and U. Valdre, Eds., Surface and Interface Characterization by Electron Optical Methods,
Plenum Press, New York, NY, 1988.

35. G. W. Lorimer, Ed., Analytical Electron Microscopy, The Institute of Metals, London, United
Kingdom, 1988.

36. D. C. Joy, A. D. Romig, and J. I. Goldstein, Principles of Analytical Electron Microscopy, Plenum
Press, New York, NY, 1986.

37. Proceedings of TIlird Conference on Frontiers of Electron Microscopy in Materials Science,

Ultramicroscopy, 37 (1-4), 1991.

38. T. T. Tsong, Atom-Probe Field Ion Microscopy: Field Ion Emission and Surfaces and Interfaces at
Atomic Resolution, Cambridge University Press, New York, NY, 1990.

39. T. Doust, F. L. Metcalfe, and J. A. Venables, Ultramicroscopy, 11 116 (1989).

40. H. Daimon, C. Chung, S. Ino, and Y. Watanabe, Surf. Science, 235. 142 (1990).

41. Proceedings of Workshop on Electron-Beam-Induced Spectroscopies with High Spatial Resolution,

Ultramicroscopy, 28(1-4), 1989.

42. J. Silcox, P. H. Holloway, K. R. Lawless, D. Lichtman, R. G. Meisenheimer, L. E. Murr, and

C. 1. Powell, Materials Sci. Eng.,a149 (1982).

1-17
 2. CHARACTERIZATION OF SURFACES: CURRENT STATUS
OF SURFACE STRUCTURE DETERMINATION
(January 1991)

C. B. Duke
Xerox Webster Research Center
800 Phillips Road, 0114-38D
Webster, New York 14580

I. INTRODUCTION

The first purpose of this paper is to provide a brief overview of the current status of the
determination of the atomic structure of solid surfaces. We organize this survey by classifying surfaces
by type (clean versus overlayer geometries; metallic, semiconducting, and insulating substrates) and
presenting an aggregate view of the results for each type. We further consider only surfaces whose atomic
geometry is known quantitatively. which usually restricts our attention to epitaxial overlayer structures.
Finally, we cite the review literature almost exclusively, using original sources primarily for illustrative
examples. Coverage is restricted to solid-gas (i.e., vacuum) surfaces. as opposed to solid-solid or solid
liquid interfaces.

The second purpose of this paper is to indicate some of the current key issues in surface structure.
prediction and measurement For example, it has been proposed that the cleavage surfaces of both
zincblende [1] and wurtzite [2] crystals exhibit essentially universal structures if all distances are measured
in units of the bulk lattice constant Moreover, these nearly universal relaxed surface structures revert to
their bulk form on the adsorption of Sb or Bi [3,4]. Indeed, the issue of adsorption-induced
reconstructions is a topic of great interest in studies of surface chemical reactions, including catalysis [5].
In the case of compound semiconductors, a good example is AI on GaAs(1lO), which forms epitaxial
AlAs "layer by layer" on annealing [3]. Important issues concerning these reactions involve their
spontaneity (as opposed to activation), their dependence on the initial surface structure, and the extent to
which they disrupt the initial surface structure.·

The paper is organized into two context-setting sections on theoretical concepts and experimental
methods in the prediction and measurement, respectively, of surface structures. These are followed by
synopses of available results on clean and adsorbate-covered surfaces. The references are designed to
afford an entre into the pertinent literature.

n. CONCEPTS IN TIlE TIlEORY OF SURFACE STRUC1URE

Metallic surface structures are determined primarily by the self-consistent electrostatic responSe
of surface ion cores to the metallic electrons spilling out into the vacuum. Recent reviews have been
given by Hamann [6] and Inglesfield [7,8]. For close-packed surfaces (e.g., fcc <111», these ion-core
relaxations are oscillatory but small. They can, however, become quite significant for more open surfaces
(e.g., fcc <210:». An important general concept is the recognition that the electron density deviates from
its bulk value only for a few angstroms into the bulk, so the ion-core relaxations are confined to this depth
(which can be as many as 10 or so atomic layers on the more open faces). Exemplary systems and
models are discussed by Chen et al. [9], by Sokolov et ale [10], and by Marcus and Jona [11].

For transition metals, additional phenomena may occur. For example, at low temperatures
(T < 220-250 K), the (100) surfaces of both Wand Mo reconstruct to form lower symmetry structures that

2-1
are one-dimensional chains of atoms on the bee (lOO) substrate [7]. 1his phenomenon has been attributed
to both collective effects (charge density wave formation) [12] and to the formation of d-electron chemical
bonds [7,13]. If the latter is the case, then these surfaces are examples of surface rehybridization: a
phenomenon that is ubiquitous in the relaxation and reconstruction of semiconductor surfaces. W(l00)
and Mo(lOO) also are among the first systems in which adsorbate-induced (in this case hydrogen)
reconstruction of a clean metal surface was observed [14], and they remain [15] a topic of current interest
for this reason. Fcc transition metal surfaces also exhibit reconstruction, i.e., a surface structure that
exhibits lower symmetry parallel to the surface than the bulk substrate. Well-known examples include
the (100) and (110) surfaces of Jr, Pt, and Au. At high temperatures, these surfaces may revert back to
(tx1) structures via phase transitions that are believed to be order-disorder transitions. A review of the
theory of reconstructions and relaxations at clean metal surfaces has been given by Inglesfield [7].

Semiconductor surface reconstructions and relaxations are most easily interpreted in terms of the
rehybridization of the valence electron charge of surface species to minimize the "dangling bond" charge
density. In the case of elemental semiconductors and the polar surfaces of compound semiconductors,
this rehybridization drives massive structural changes in which chains [e.g., Si(l11)-(2x1)], dimers
[e.g., Si(100)-(2x1)], trimers [e.g., GaAs(-1-1-1)-(2x2)] and other more complex surface species
[e.g., Si(111)-(7x7)] are formed. In the case of the nonpolar surfaces of tetrahedrally-coordinated
compound semiconductors, the rehybridization results in large atomic displacements that are enabled by
surface topologies that admit bond-Iength-conserving surface relaxations. Recent reviews of both
experimental structures and their theoretical interpretation have been given by Duke [3] and Schluter [16]
for compound and elemental semiconductors, respectively.

An important concept that has emerged from the study of the atomic geometries of the cleavage
faces of tetrahedrally-coordinated compound semiconductors is the notion of surface-structure universality
[1-3,17]. 1his notion consists of an observation and its interpretation. The observation is that when scaled
with the bulk lattice constant, the (110) surface structures of all zincblende structure m-v and II-VI
compound semiconductors are identical to within experimental error. The interpretation is that this result
is due to a universal mechanism of rehybridization associated with the lowering of an anion-derived
surface state from mid-gap to the top of the valence band by virtue of a nearly bond-Iength-conserving
=
rotation of the uppermost chain of surface atoms to a tilt angle of co 29°±3° to the unrelaxed surface.
1his rotation, and its accompanying small contractions in the back and surface bond lengths, leads to the
redistribution of the surface state charge from the "dangling bond" on the unrelaxed surface to the back
and surface bonds in the relaxed surface. A similar universality of the surface structures and relaxation
mechanisms was predicted for the (10-10) and (11-20) cleavage surfaces of wurtzite structure compound
semiconductors [2,17] which current experiments are validating [18]. A consequence of this concept is
that in analogy to bulk crystal structures [19], the equilibrium surface structures of semiconductors
exhibiting homologous types of bonding will all be identical to within scale factors depending only on the
bulk crystal lattice constants. Similar concepts should apply to metals but have not yet been formulated
for this class of surfaces. .

The transition from semiconductors characterized by predominately covalent bonding to insulators

characterized by predominately ionic bonding is often defined in terms of correlations of ionicity with bulk
crystal structure [19]. In this view, "covalent" bonding results in tetrahedrally-coordinated structures
(e.g., zincblende, wurtzite), whereas "ionic" bonding results in six-fold coordinated structures (e.g., rock
salt). From the perspective of surface structure, this is an important distinction because the topologies of
the nonplanar cleavage (or fracture) surfaces are quite different in the two types of structures. The
cleavage surfaces of tetrahedrally-coordinated compound semiconductors admit large bond-Iength-
conserving relaxations in which the cations' local coordination can change from tetrahedral (Sp3) to planar
(sp2). Moreover, these surfaces exhibit large relaxations to approximately planar cation coordination. In

2-2
contrast, nonpolar surfaces of cubic crystals, e.g., rock salt(I00), require large bond-length distortions to
alter significantly the surfac~-atom coordination. Although the surface rehybridization may stabilize a
relaxetl surface structUre, materials with these structures exhibit only small surface relaxations because the
energy required to distort the bonds produces a large kinetic barrier to reaching such a structure under
reasonable processing conditions. Reviews of these ideas have been given by Duke and LaFemina [20,21].

Some species, like Xenon, adsorb gently and reversibly on clean surfaces ("physical" adsorption)
and may even be used to decorate surfaces to determine their topography [22]. Most, however, form
bonds with one or more surface atoms ("chemisorption"), thereby inevitably disrupting the clean surface
to some extent In such cases, the surface structures that are formed are usually out of equilibrium
because of kinetic barriers to the. energetically favored chemical and structural transformations. Indeed,
the semiconductor electronics industry is based on the generation of such nonequilibrium structures by
cycles of chemical and thermal processing.· Therefore, the central concept in the surface structure of
overlayer systems is that "what you get depends upon how you got it," Le., the structure is determined by
the process history of the sample.

Within this context, systematic studies of surface reactions have led various authors to propose
taxonomies of adsorbate-substrate systems depending on the degree to which the adsorption event disrupts
the surface. Somorjai and Van Hove classify systems according to whether they exhibit adsorbate-induced
relaxation, reconstruction, or compound formation [5]. Duke distinguishes between reactive chemi-
sorption and epitaxially constrained adsorbate bonding [23]. Avouris and Lyo classify reactions on silicon
according to whether they are "site-selective" or "involve extensive atomic rearrangement" [24].
Braicovich, on the other hand, introduces a complex taxonomy of the entire deposition process to describe
the many possible outcomes of metal deposition on elemental semiconductors [25], whereas an entirely
different taxonomy is used to describe reactive etching processes [26]. Thus, even a cursory inspection
of the literature reveals that, in contrast to clean surfaces, the establishment of general relations between
surface structures and the characteristics of equilibrium chemical bonding is of limited use for overlayer
systems due to the intimate dependence of these structures on the process steps used to prepare them.

ill. METHODS OF QUANTITATIVE SURFACE S1RUCTURE DElERMINATION

Our purpose in this section is to provide a brief indication of how the surface structures discussed
in subsequent sections were determined. It is useful to distinguish between methods used on surfaces
exhibiting long-range two-dimensional periodic order parallel to the surface, those employed to obtain the
local configuration around a given atomic species, and those used to assess surface topography (Le., steps,
terraces, etc.). Surveys of the various techniques may be found in the literature [27] and are given
elsewhere in these proceedings. Compilations of surface structures have been published in which the
technique used to obQJin a given structure is included in its description [27,28]. Our discussion reflects .
their content and the development of new techniques within the past few years.

For surfaces exhibiting long-range periodic order, the quantitative surface structure determination
method of choice is overwhelmingly low energy electron diffraction (LEBD) intensity analysis [11,29-33].
In recent years, this method has led to the determination of multilayer metal surface relaxations [5,11,28]
and small [e.g., (lxl), (2xl), and (2x2)] semiconductor surface structures [3,16,20,32,33]. The method
also has been used to refine large structures, e.g., Si(111)-(7x7) [33]. Historically, the determination of
the Si(111)-(7x7) structure was enabled by ultrahigh vacuum high resolution transmission electron
diffraction (HRTEM) [34] and refined by LEED and glancing angle X-ray diffraction [35]. The latter·
recently has become much more common [35]. It is the technique of choice to examine displacements
parallel to the surface of large unit cell semiconductor structures [35] and has been applied successfully
in other cases as well, such as W(I00) [36]. Finally, during the past 2 years, low energy positron

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diffraction (LEPD) intensity analysis has been shown to be a competitor to LEED for the determination
of semiconductor surface structures [37].

Ion beam techniques also have found extensive use .in quantitative surface crystallography,
especially for small unit cell structures [38]. These techniques are sensitive to displacements parallel to.
the surface and hence afford an important complement to LEED or LEPD which, as usually practiced with
near notmal incidence particles, are sensitive predominately to displacements normal to the surface. Since
quantitative analysis of the ion-scattering data is done by Monte-Carlo simulation, the methodology is
useful predominately for the a priori determination of simple structures or for discriminating between
different models of complex structures. A related technique, shadow-cone-enhanced secondary ion mass
spectrometry, has been proposed recently but its application to GaAs(1lO) failed to recover the well-known
structure of this surface [39]. .

In addition to their use" for the determination of the atomic geometries of ordered regions of
surfaces, electron diffraction techniques can be used to examine the topography (i.e., the occurrence of
steps, islands, terraces, etc.) of imperfect surfaces. A direct way to do this is to refocus the diffracted
LEED beams (in practice, the specular beam) to obtain an image of the surface [40]. This technique,
called low energy electron microscopy (LEEM), has been used to study steps on Si surfaces and overlayer
islands on both Si and Mo [40]. Alternatively, the shape of the diffracted beams as a function of exit
angle in the neighborhood of the diffraction direction can be measured and analyzed to obtain similar
information. Pioneered by Henzler [41] and Lagally [42], this methodology has been reviewed recently
by WollschUiger et al. [43]. Individual atomic defects also can be imaged directly by field ion microscopy
for those materials that can be formed into sufficiently stable tips [44]. This technique is particularly
useful for studying adsorbate diffusion and interactions between adsorbates, especially on transition metals
[44].

It is not necessary for a surface to exhibit long-range periodic order to be able to determine
features of its atomic geometry, as already noted above for field-ion microscopy. Historically, the analysis
of fine structure in various core-level excitation and filling processes, called Surface Extended X-ray
Absorption Fine Structure (SEXAFS) in the case of the detection of Auger electrons associated with the
fIlling of an empty core state near"the surface, has been used to determine the local coordination of the
excited species [45-47]. Similar local diffraction phenomena occur in photoemission and in the Auger
process itself, leading to the development of X-ray photoelectron and Auger electron forward ~cattering
as techniques for assessing local surface structure and its application to metal and semiconductor alloy
systems [48]. As widespread working tools for local surface structure examination, these techniques have
been eclipsed, however, by the development of scanning tunneling microscopy (STM) and scanning
tunneling spectroscopy (STS) [24,49,50]. Although of limited use for the precision determination of
atomic structural parameters [50,51], the vivid images illustrating the nature of the local surface atomic
geometry coupled with the ability to determine the local surface electronic structure has rendered STM
the leading new tool for the assessment of the qualitative features of local surface structures" on conducting
substrates (i.e., metals and semiconductors). STM results have not yet penetrated the surface structure
tabulations [27,28], but they have exerted a major impact on the qualitative understanding of reconstructed
metal and semiconductor surfaces (e.g., Si(111)-(7x7) [16,49,50]) as well as a variety of adsorbate systems
[24,51].

IV. CLEAN SURFACES

This section is devoted to an overview of the current status of knowledge about the atomic
geometries of clean surfaces. These structures are dynamic, although this fact is not commonly
emphasized. Surface defects in the forms of terraces, steps, and kinks are constantly forming and

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 reforming, leading to surface roughening and even melting at temperatures approaching the bulk melting
temperature [52]. The topic of phase transitions at surfaces, Le., roughening, melting, and wetting, has
. enjoyed a resurgence in interest during recent years, as described, e.g., in a Comprehensive overview by
.Dash [53]. Such phenomena have been studied by He atom scattering [52], ion-beam scattering [38],
glancing-angle X-ray diffraction [35], and LEED angular profiles [43], especially for the high-index
("vicinal") surfaces of Ni and Cu [52], and for Pb(llO) surfaces [53]. In the case of reduced-symmetry
surface structures ("reconstruction"), order-disorder transitions may occur prior to melting [7,36]. Our
ensuing discussion is focused, however, on the low-temperature atomic geometries in the absence of
defects, Le., the surface analogs of the perfectly periodic crystal structures of bulk solids.

A. Metals

The atomic geometries of the surfaces of metals have been determined primarily by LEBO
[27,28,54] and ion scattering [38,55]. Tables comparing the results of the two methods (mostly for fcc
transition metals) have appeared in several reviews [38,55]. For the close-packed faces, Le., fcc(lll),
bcc(1lO), and hcp(OOOl), relaxations from the truncated bulk structure are small, typically less than 2%
[7]: a result that characterizes transition as well as s-p bonded metals. These relaxations increase as the
surfaCes become more open, driven by the response of the surface ion cores to the smoothed electron
density at the surface [7]. The relaxations are oscillatory in nature (contractions of the top layer spacing,
expansions of the second layer, etc.), becoming smaller, more or less exponentially, with increasing depth
into the crystal. Alloy geometries are more complicated, with puckering between the various components
of the alloy occurring in surface and near-surface layers containing multiple components of the alloy
[9,55]. Relaxations parallel as well as normal to the surface occur for the more open surfaces [11]. The
magnitude of· the relaxations decays to less than a percent within a few angstroms of the surface,
independent of the crystallographic orientation of the surface [11). Diagrams of most of these structures
may be found in MacLaren et ale [28]. An updated version of the structural tables in References 27 and
28 has been given very recently by Van Hove et ale [56].

Certain transition metal surfaces exhibit reconstruction as well as relaxation. Highly studied
systems include the (100) and (110) surfaces of fcc Jr, Pt, and Au [7,38], as well as the (100) surfaces of
bcc W and Mo [7,36]. The latter consist of zig-zag chains of W (or Mo) atoms bonded to a slightly
relaxed substrate. The top-layer chains are thought to be caused by d-electron bonding of the surface
species, associated with the splitting of a partially-filled band of surface states into a fully occupied
bonding and an empty antibonding band [7,13]. The nature of the phase transition to the (lxl) high-
temperature phase has been the subject of extensive investigation and debate [7]. Recent glancing-angle
X-ray studies favor an order-disorder (rather than displacive [7]) transition [36], whereas He atom
scattering measurements of the surface vibrational spectra favor a soft-phonon displacive mechanism [57].
The situation with the reconstructed fcc metals is even less settled. LEEO, ion-scattering, glancing-angle
X-ray diffraction, and STM have been applied to these surfaces, with results that are not always fully
consistent [38]. The consensus seems to be that variants of the missing row model describe the
fcc(110)-(2xl) reconstruction [7,38], whereas the fcc(loo) reconstructions are generated by hexagonal
close-packed top layers slightly distorted to achieve epitaxy on the (100) substrate [7]. The nature of the
issues that arise in the determination and interpretation of the fcc reconstructed geometries is well
illustrated by the account given by Van der Veen [38] of the analysis of the (2xl) structures of the (1lO)
surfaces of Au, Jr, and Pt.

B. Semiconductors

The determination of the atomic geometry of the Si(lll)-(7x7) has been the benchmark
semiconductor surface structure problem for three decades. Virtually every surface structure analytical

2-5
method, i.e., LEED [33], ion scattering [38], glancing-angle X-ray diffraction [35], STM [49,50], ultrahigh
vacuum (UHV) .HR1EM [34], as well as others have been applied to this problem as reviewed, e.g., by
Schluter [16]. The key breakthrough was an analysis ofHR1EM Patterson maps by Takayanagi et al. [58]
to propose a dimer-adatom-sta~king fault (DAS) model, a refinement of which is the currently "accepted"
structure [16, 35, 38]. This is a three-distorted-layer model on top of a bulk unit cell one half of which
is separated from the other half by a surface stacking fault. Useful schematic diagrams and STM images
may be found in the reviews by Schluter [16] and Golovchenko [49]. Using atom-resolved tunneling
spectroscopy (ARTS), the electronic structure associated with the various inequivalent surface sites has
been measured explicitly [24] .. There are 200 atoms per unit cell in the top three layers plus the first
faulted substrate layer. In the LEED analysis, C3V symmetry was assumed, leaving 49 independent atomic
positions to be deteqnined [33]. The fact that a consensus has been reached on at least the approximate
positions of these atoms [34] is a measure of the complexity of the surface structures that can be
determined with modem surface analysis techniques and enough dedicated effort.

Two other Si surface structures, the (l11)-(2x1) cleavage structure (the (7x7) structure is obtained
by high-temperature annealing) and the (l00)-(2x1) structure, have attracted considerable effort over the
years. Histories of the structure determinations of both structures have been given by Schluter [16], and
a synopsis of a more recent STM analysis of the Si(lU)-(2x1) structure is contained in a review by
Feenstra [59]. For Si(111)-(2x1), the consensus surface structure is two layers of "pi-bonded chains" on
a relaxed (l11) substrate as illustrated in Fig. S69 of MacLaren et al. [28]. For Si(100)-(2x1), it is
asymmetric (i.e., tilted) dimers as illustrated in Fig. S68 of MacLaren et al. [28]. STM images have led
to questions about the tilting of the Si(100)-(2x1) dimers, a revealing discussion of which may be found
in the comments following a paper by Demuth et al. [60] at the 1987 Solvay Conference.

Turning to compound semiconductors, the (110) cleavage surface structures have been determined
by LEED for all known zincblende structure IIT-V and IT-VI materials [3]. Moreover, the LEED results
have been verified repeatedly by other techniques, especially ion scattering [38]. GaAs(11O) was the first
semiconductor surface structure to be determined quantitatively [61] and remains the benchmark. A
history of its determination by essentially all of the various surface structure analysis techniques is given
by Duke [3]. The resulting structure, an approximately bond-Iength-conserving rotation of the top-layer
GaAs zig-zag chains, is shown in Fig. S61 of MacLaren et al. [28]. Tables of references may be found
in Van Hove et al. [56]. The importance of these structures resides in their universality for all ITI-V and
IT-VI materials. The top-layer chains are twisted by 29°±3° for all materials studied to date, and surface
bond lengths are approximately conserved, within experimental uncertainty, although some surface bond
compression is suggested [3]. This universality prompted a search for its cause: the lowering of the
anion-derived filled surface state band on rotation [2,3]. This lowering depends primarily on the topology
of the (110) surface, rather than on the detailed surface electronic structure, thereby establishing a link
between surface topology and the character of the surface relaxations.

The current frontiers in this area are analyses of structures for polar surfaces (e.g., those used in
molecular beam epitaxy) [3,35], for germanium surfaces [16,35], and for the cleavage surfaces ofwurtzite-
structure compound semiconductors [17,18]. Accounts and diagrams of most of the quantitative structure
analysis are given in the compilations cited previously [3,16,28].

C. Insulators

Relatively little work has been done recently on the surface structures of compound
semiconductors that are not tetrahedrally coordinated. Early work on cubic oxides and layered com-
pounds is reviewed by Kahn [32]. Surface structure predictions are being made for other classes of
semiconducting and insulating oxides (e.g., cubic, rutile, cristobalite, and tridymite cleavage faces [21]),

2-6
which reveal system dependencies of the low energy structures on surface topology. These predictions
and the concepts on which they are based remain to be tested. Surface phonon spectra [57] and LEPD
intensities [37] have been measured for the (100) faces of several alkali halides, but no quantitative
analysis of the atomic geometries have been given. LEPD intensities also have been reported for the
(111) surfaces of solid rare gases (Le., Ne, Kr, Ar, and Xe) [37], so quantitative surface structure analyses
of these insulators certainly are possible, although not yet attempted. Ordered epitaxial oxides have been
reported to be grown at Ni [38] and Si [62] interfaces, but they are not yet well characterized structurally.
The deposition of inorganic .fluorides on semiconductor substrates is currently a popular topic [66], but
no quantitative studies of the vacuum surfaces have been reported.

V. OVERLAYERS

As noted in the introductory sections, the literature on the surface structural chemistry of ordered
adsorbed overlayer systems is extensive, complex, and difficult to classify due to the process dependence
of the structures. Major reviews, in order of appearance, include those of Somorjai and Van Hove in 1979
[27], MacLaren et al. in 1987 [28], Somorjai and Van Hove in 1989 [5], and Van Hove et al. [56] in
1989. All four of these reviews emanate from the same group of authors and hence exhibit a considerable
degree of overlapping. These authors characterize the resulting structures by the extent of the impact of
the adsorption on the initial surface structure, with the resulting taxonomy of adsorption-induced
relaxation, reconstruction, and macroscopic reshaping [5]. The tabular material in these reviews is
extensi ve, encompassing several hundred surface structures.

Overlayer systems exhibit two major new features relative to clean surfaces that influence the
nature of the literature. FIrst and foremost, they are inherently nonequilibrium systems whose analysis
is an integral part of studies of commercially important processes in the chemical and electronic industries.
Thus, one finds a focus on systems of interest in catalysis [5,63], semiconductor · processing for
microelectronics [23-26], and molecular beam epitaxy [64-66]. Second, since the adsorbates differ
chemically from the substrate, a different set of ~ctural techniques playa major role. The workhorses
ofLEED [3,5,27,28,54,56], ion scattering [38], glancing-angle X-ray diffraction [35], and STM [24,50,51]
are supplemented with vibrational spectroscopy [6,67,68] (especially for adsorbed H [69]), core-level
structural spectroscopies [45-48], and structural analyses based on induced desorption phenomena
[44,63,70]. Therefore the literature contains both process-oriented reviews that deal with surface structure
as one small part [26,64-66] and technique-oriented articles dealing with adsorbate selective techniques
[22,24,44-48,63,67-70].

Given the scope of the subject matter and the availability of recent tabulations of structures, we
proceed by considering two illustrative examples pertinent to semiconductor processing. As an example
of adsorption passivating a surface, we consider a monolayer (ML) of Sb for the system
GaAs(llO)-P(lxl)-Sb(1 ML). This topic has been reviewed regularly [3,32] and is the subject of recent
updates [4,71,72]. As an example of reactive adsorption used in semiconductor processing, we consider
the formation of silicides on Si, also a topic of current reviews [25,38]. For a discussion of the (hundreds
of) other systems, the reader is referred to the surveys cited [3,5,20,27,28,38,46,48,56,68-71].

A. GaAs(llO)-P(lxl)-Sb(1 ML)

When GaAs is cleaved to form GaAs(11O), we envisage the formation of two "dangling bond"
surface states: one on the As and one on the Ga. Both occur in the gap, but since the Ga state lies higher
than the As state, the Ga "dangling bond" electron is transferred to the As, which subsequently relaxes
into a distorted p3 geometry simultaneously with the Ga relaxing to an approximately sIT geometry,
yielding the 29°±3° tilt of the top zig-zag chain of GaAs as described earlier (e.g., FIg. S61 in [28]). The

2-7
 presence of an Sb monolayer permits a chemically saturated surface, however, removing the driving force
for the relaxation. The Sb species occupy sites roughly where the last layer of GaAs would have been.
Figures may be found in References 3,4,5,28 (Fig. S65), and 32. Each Sb is three-fold coordinated (one
substrate and two neighboring surface species) so that its valence of five is saturated. The surface is
nearly unrelaxed, with small tilt angles of approximately 3° in the Sb overlayer and 4° in the top layer
of the substrate beneath, as would be expected from the saturated valence. The addition of further Sb
leads to the formation of weakly adsorbed islands on top of the saturated monolayer.

The importance of this structure and its Bi analogs [4] resides in its illustration of a new type of
surface chemical bond [73]. The Sb overlayer consists ofp2 bonded chains whose pi electrons form bonds
with the Sp3 orbitals of the substrate. Several other chemically plausible ~orms of bonding have been
proposed [3,32,72], but all have been shown to be incompatible with the LEED [4] and STM [51] data
Confirmation of the proposed binding mechanism comes from comparison of the calculated [72,73] surface
states with those measured by angular dependent photoemission [3,71,72]. Therefore the literature on the
GaAs(llO)-p(1xl)-Sb system illustrates well the intimate interaction between structural spectroscopy
(LEED and STM), electronic spectroscopy (STS, photoemission, and inverse photoemission), and
theoretical predictions of the geometrical and electronic structure of the surface, which are required to
establish with confidence the nature and consequences of a new adsorbate..induced surface structure.

B. Silicide Growth on Si(lll)

A class of systems of considerable commercial interest in which certain adsorbates (e.g., Ni, Pd)
disrupt the initial surface structure and form compounds (e.g., NiSi2, PdSi, P~Si, P~Si) is that of metals
deposited on Si(lll) [25]. These systems constitute the scientific foundation for the multilayer
metallization technologies used in making interconnects on Si microelectronic circuits. The central puzzle
is the identification of the mechanism for the formation of silicides at the Si(lll) surface at temperatures
below those required for the growth of bulk silicides. In addition, some of these systems, e.g.,
. Si(l11)-P~Si«()()()l) and Si(111)-NiS~(111) constitute good examples of the epitaxial growth of metals
(the silicides) on semiconductors (Si) of interest as model interfaces for the examination of the electrical
properties of metal-semiconductor contacts [25,38].

Structural studies of silicide formation on Si(lll) have been reviewed by Van der Veen [38]. The
basic idea underlying models of this process is that the formation of metal "clusters" is a crucial
intermediate step at room temperature. The energy released in the metal-metal bonding presumably assists
in overcoming the kinetic barriers to metal-silicon bond formation, thereby enabling silicide formation.
An analogous situation for compound semiconductors is the formation of AlAs surface layers via deposi-
tion of Al on GaAs(110): a system studied in great detail a few years earlier [3,23]. The major tool used
to elucidate the process steps is ion-solid scattering with transmission electron microscopy (lEM) and
glancing-angle X-ray scattering playing important roles in the determination of the interface geometries
for epitaxial silicides on Si(111) once they have been formed [38]. As usual, these determinations occur
by successive hypothesis followed by verification or rejection using multiple techniques. An exemplary
and extensively studied example is the growth of NiSi2 on Si(111); a good account of this story may be
found in Van der Veen's review [38].

VI. Synopsis

Given motivation and financing, surface geometries of rather complex individual structures can
be obtained with confidence. Si(111)-(7x7) is the benchmark example [16,33,33-35,38]. In addition,
studies of variations of the geometries of a given surface across homologous series of materials have
greatly expanded our knowledge of the surface structural chemistry of tetrahedrally-coordinated compound

2-8
 semiconductors [2,3,17,18,20]. Studies of metal surfaces have revealed the occurrence of multilayer
relaxations and reconstructions, although their detailed interpretation remains controversial [36,57,74,75].
- Adsorbed overlayer structures tend to be even more controversial because of their nonequilibrium
character; good examples are AI on GaAs(110) [3,23] and NiSi2 on Si(111) [38]. Moreover, despite
claims to the contrary, the roie of these , structures in complex semiconductor and catalytic processes
remains uncertain [25,76]. ruus, the quantitative determination of surfaces has been useful primarily as
a testing ground for theoretical models of surface structure and chemistry [3,6-9,12,13,16-21,52,53,56,72,
73]. These ideas can then be extended to technologically useful situations in which the pertinent structures
are not directly accessible, as discussed explicitly, e.g., by Ertl [76] for catalysis and by Duke [23,77] for
semiconductor processing. Stated alternatively, essentially any interesting inorganic surface structure can
definitely be determined, given current surface analysis technologies, for a price. Whether the structure
is worth knowing at this price depends almost entirely on the ingenuity and insight of the users of this
information for a given purpose: a concept that was articulated and documented nearly a decade ago [77]
but which remains as pertinent in 1991 as in 1981.

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2-11
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Molecules with Solid Surfaces, Plenum, New York, NY, 1990, pp.375-379.

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The Chemical Physics of Solid Surfaces and Heterogeneous Catalysis, ~ Elsevier, Amsterdam, The
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 3. A SUMMARY OF CRITICAL ISSUES FOR APPLICATION OF IR SPECTROSCOPY TO
CHARACTERIZATION OF SURFACE PROCESSING

David L. Allara
Department of Materials Science and Department of Chemistry
Pennsylvania State University
University Park, PA 16802

I. INTRODUCTION

Although more than several dozen specific techniques are used for the analysis of surfaces and
thin fIlms, there always seems to be a need for a new technique. lbis is becaUse one technique alone
rarely solves a given sample analysis problem but rather contributes only pieces of the puzzle.
Characterization issues for complex surface and thin-film structures are usually resolved only by the
application of combinations of techniques, with each one providing complementary information. By
.careful evaluation of the limits and errors· involved in the interpretation of each piece of data, one can
arrive at a self-consistent analysis of important features of the sample of interest. Obviously every
technique cannot be applied in every case but rather optimal strategies must be developed to maximize
the information for an acceptable level of cost and effort Neglecting the issue of cost, which is properly
dealt with as a local institutional issue, the major issues associated with a given technique become those
stemming from information content, interpretative complexity, experimental (instrument and operation)
complexity, and sample limitation. In this regard, the purpose of this review is to provide relevant
information about infrared spectroscopy (IRS) that will assist in developing characterization for surface
and thin film structures in which IRS could be a contributing technique, whether the dominant critical
technique or simply a minor confirming one. Because of the much wider applicability of the mid-infrared
(IR) wavelength region in chemical analysis, relative to far- and near-IR wavelengths, only mid-IRS will
be discussed In this article, it is assumed that the reader already understands the types of analysis
problems for which IRS might be useful and that the reader has a general understanding of a simple IR
experiment. In particular, this article is not intended to be a review. Several recent texts treating
vibrational assignments [1,2] and instrumentation [3-5] are available for information on this aspect. In
Section II, typical characterization goals of a surface! thin-film analysis are presented. In Section III, a
general introduction to IRS is presented. With this as a backdrop, Section IV describes the special case
of IRS at surfaces and interfaces with a focus on applications to surface/thin-fIlm analysis. Finally,
Section V provides a summary of optimum applications of IRS and directions for future developments of
the technique.

n. TYPICAL CHARACI'ERIZATION GOALS OF A SURFACElI'HIN-FD...M ANALYSIS

Coverage. thickness. and density are three closely related features necessary for a quantitative
assay of a thin fIlm. For film thicknesses of less than a "monolayer," the smallest thickness possible for
a uniform film without breaking up the fundamental chemical composition unit of a unit cell or molecule,
the amount of film is often given in terms of "coverage," either as the fraction of a monolayer or as a
surface density of chemical species per unit surface area. For films with greater than "monolayer"
coverages, the thickness is usually used to describe the amount. However, to correctly characterize the
amount of material from the thickness, the volume density of the film must be known. Coverage,
thickness, and density are all one parameter (average) quantities and can never accurately describe film
structure without additional knowledge of density distributions, including such features as roughness and
interior voids.

3-1
 For ftlms of more than one element, it is useful to know both the atomic (or elemental)
composition and the chemical compOsition. The latter includes an assay of the number and types of
chemical groups and valence or bonding states associated with the different constituent elements. In
addition, for molecular films, other subtleties in structure may be very important, such as conformational
sequences and hydrogen bonding interactions. With regard to such molecular fine structure features, and
all others as well, it is critical that the analysis be nondestructive.

In many cases, the film structure may exhibit some degree of ordering both with respect to
uniform orientations and uniform spacings of chemical bonds or groups. The film thus must be
characterized by orientational and translational ordering, which in turn are given properly in terms of the
dimensions and symmetry of the simplest structural unit and a correlation length for the persistence of this
structure.

The film/substrate interface is characterized both by the nature of the bonding (e.g., physisorption
or chemical bonding), the orientations of the bonds, and the relationship between the location of substrate
surface sites and film bonding sites (e.g., epitaxial, commensurate, etc.)

The presence of defects and impurities within the film usually presents a severe challenge in
quantitative analysis. Defects include voids and boundary regions between ordered domains, and such
defects mayor may not be correlated with substrate defects. A typical and significant impurity in many
organic films on oxide substrates is water bound in the interfacial region.

For films of thickness greater than several atoms or chemical groups, the distribution· of
characteristics as a function of distance from the surface can be of interest This type of characterization .
is usually called depth profiling. Monitoring ftlm characteristics as a function of lateral location on the
surface is referred to as imaging. An ultimate goal in surface analysis is to obtain three-dimensional
characterization, including both lateral and depth distribution of important features.

The most tractable analyses are those invoiving isolated samples and unlimited sampling time.
However, the most significant problems (real world) are usually those involving a sample surrounded by
an ambient fluid (gas or liquid) environment in which sample characteristics are highly time-dependent.
Challenging examples for characterization are lubricant ftlms on a metal sheet during a rolling operation
and a growing polymer film on an electrode during electropolymerization. In this respect, an ultimate goal
from surface/thin-film characterization is to develop real time measuring capabilities, that is techniques
for following time-dependent changes in a sample directly (in situ) in a processing or service environment.
An additional challenge for "on-line" production environments arises when the sample is continually
moving (e.g., a rolling.operation), and the alignment of the analytical probe must be dynamic.

All the above analysis goals are summarized in Table 1.

ill. REVIEW OF THE PRINCIPLES OF IRS

A. Theory of IRS

All energy spectroscopies (as opposed to mass spectroscopies, etc.) involve transitions between
energy levels of a given system with accompanying emission or absorption of a quantum of energy in
some form. Infrared spectroscopy typically refers to emission or absorption of infrared photons. Almost
always this process involves transitions between vibrational quantum states, so IRS is typically a
vibrational spectroscopy, although other processes such as electronic excitation of narrow bandgap
semiconductors can occur at infrared frequencies. Photon spectroscopies that probe these vibrational

3-2
 Table 1. Ultimate Goals for Characterization of Surfaceflhin-Film
Structures and Compatability with Infrared Spectroscopy Probes

Average Compatibility of IRS

with Characterization Goal
Characterization Goal Good Poor None
Coverage, film thickness, density X
Atomic composition X
Chemical composition
Chemical bonds or groups X
Valence states of metals X
Bond or group orientation X
Molecular fine structure X
(conformations, etc.)
Ordering X
Surface/film bonding X
Defects X
Impurities X
Depth profiling X
Imaging
S I-J.UIl scale X
~ 10-J.UIl scale X
Real-time analysis X

transitions by more complex mechanisms than simple absorption and emission include Raman scattering,
sum frequency generation, and various other nonlinear techniques such as Raman gain and coherent
anti-stokes Raman scattering (CARS). In addition, vibrational transitions can be probed using the kinetic
energy and momentum of particles other than photons; in particular, electrons, helium atoms, and neutrons
can be scattered from molecules and surfaces to obtain vibrational spectra. Thus, a number of ways exist
for obtaining vibrational spectra of surfaces and films; IRS is just one of the choices. However, IRS can
safely be said to be the most generally useful technique by far because of experimental and interpretive
simplicity. IRS should be viewed as the overwhelming choice for solving practical problems.

The physical mechanism of IRS is well understood for the elementary case of a photon-electron
dipole transition. To clarify the· later discussion of spectroscopy at interfaces, the simple mechanism for
an isolated molecule in free space is presented very briefly here. Either a passing photon (or, alternatively,
a propagating electromagnetic wave) of IR frequency is absorbed via excitation of a given vibrational level
. to one of higher energy (absorption), or a photon is emitted by conversion of an exited state to a lower
state. The simple description of the excitation mechanism for the photon-electric dipole transition is that
when the electric field of the light varies at a frequency that corresponds to an energy very close to that
of the energy level spacing, absorption of the photon becomes highly probable with the exact probability

3-3
depending on the change in electric dipole moment during the transition. Further, the transition probability
is directly proportional to the electric field intensity (the light intensity). -

Because the probability -of absorption increases directly with the intensity of the electric field of
the propagating electromagnetic wave, a very simple quantitative relationship exists between the source
intensity, the fraction of power absorbed by the sample, and the inherent transition probability or cross
section. For a low density of noninteracting molecules in the sample beam, this leads to an ideal Beer's
law type of relationship:

(1)

where I is the power transmitted with the molecules present. 10 is the power transmitted with the molecules
absent. e is the extinction coefficient (an absorption cross section), c is the volume concentration of the
molecules, and Q is the path length of the light beam that contains the molecules. The emission process
is correspondingly simple. A freely radiating oscillator (electric dipole) generates a given intensity of light
(in all directions) as a function of the equilibrium temperature of the molecule and of an inherent fixed
probability (cross section) of radiation.

B. The Infrared Spectroscopy Experiment

To carry out the simplest IRS experiment. one requires several key components. For an absorption
experiment. these include a source of IR radiation of variable frequencies, a radiation detector, and a
mechanism for separating the response of the sample for each frequency interval of light (monochromatic
response). To set up this simple experiment. there are a large number of options. The most useful ones,
with their advantages and disadvantages, are given in Table 2. By far, the most cost-effective combination
for the majority of surface/thin-film analyses that involve mid-IR frequencies is a blackbody-type source,
a Michelson interferometer, and a photon semiconductor detector. Usually the specific items are a ceramic
glo-bar (peaked at - 10-~ energy), one of several variations of interferometers and a HgCdTe, liquid
nitrogen cooled detector. This type of combination is available commercially from several sources (a
typical "Fourier transform" or Fourier transform infrared [FTIR] instrument). However, one should note
that other specific combinations of components in some limited number of cases may solve critical
analyses problems better than typical commercially available instruments.

IV. Infrared Spectroscopy at Surfaces and Interfaces

A. Theory

There are two major points to be made in this section. FIrSt, for solid, multiphase samples, such
as metal or nonmetal overlayer fIlm on a massive substrate, the spectra can be highly complex and very
difficult to use for quantitative analysis of structure and thickness. Second, for the particular case of a
planar, parallel layer sample, the spectra can be quantitatively understood in terms of layer thickness( es)
and orientational ordering (if present) provided that all the necessary optical properties of the constituent
layers are known.

In contrast to IRS of an isolated molecule, the experiment involving a solid material is

significantly more complex with regard to the shapes of spectral features and the quantitative relationships
between the number of oscillators (groups) present and the spectral intensities. There are two main
reasons. The first is that the distribution and structure of vibrational levels is quite complex because of
the interactions between the onstittient atoms and groups in the solid. This effect is specific to each type
of sample and is not of concern in this more general discussion. The second reason, and the one of

34
 Table 2. Summary of Major Selected Advantages and Disadvantages
of Instrumentation Components in an IRS Experiment

Advantages Disadvantages
IR Photon Sources
Hot surface Broad band; portable; inexpen- Unpolarized, isotropic radiation;
(blackbody) sive; stable blackbody-type distribution of
intensity with wavelength; con-
centrated in mid-IR
Laser Very high power; monochromatic; Moderately expensive; tunability
coherent; collimated beam; possi- often slow and/or inconvenient;
bility for short time pulses and operation very dependent on
nonlinear spectroscopies particular laser or laser combina-
tion
Synchrotron Very high flux with collimated Travel to facility required;
beam; broad band; uniform limited access
intensity at all wavelengths from
far-IR to near-IR
Vapor lamp Portable; inexpensive; covers far- Unpolarized, isotropic radiation,
(Hg, 12 , etc.) IR and near-IR much better than peaks in power occur at specific
blackbody sources wavelengths associated with
each source
Energy Resolution
Mechanism
Michelson interfer- Wavelength multiplexing; high IDtimate speed limited by
ometer plus Fourier throughput; up to - .1<f scans per mechanical scan rate, requires
transform sec at low resolutions; capable of FT computation
very high resolution; highly
accurate wavelength calibration
from laser fringe
Monochromator,· Can measure single wavelength Slow; high resolution difficult
scanning element data over extended period
of time
Monochromator plus an Capable of very fast measure- High resolution difficult; narrow
array detector ment-limited by detector speed; band capability only
no moving parts
Monochromator plus Fast; similar to an interferometer Requires mask sequencing and
Hadamard transform computation of data via
masks Hadamard transforms

3-5
 Table 2. Summary of Major Selected Advantages and Disadvantages
of Instrumentation Components in an IRS Experiment (Concluded)

Advantages DisadvaIltages
Detector Type
Semiconductor, photon Can be very fast (-ps, but J,IS-ms Moderate to narrow bandwidth;
activated (photoconduc- typical operation) depending on nonlinear response at high flux
tion or photovoltaic) specific material; extremely sensi-
tive; low noise
Bolometer (resistive) Broad bandwidth operation, good Slow « 1 kHz); lower sensi-
in far-IR tivity than photon detectors
Thermocouple (voltage) Broad band; highly linear over High sensitivity only by direct
wide flux range sample contact at low tempera-
tures
Pyroelectric (polariza- Broad band; highly linear; Slow (S 1 kHz); lower
tion) inexpensive sensitivity than photon detectors
Photo acoustic Sensitive; favorable dynamic Direct contact or extremely close
range (measures only absorbed proximity to sample needed;
radiation); no optical coupling to response can be frequency-
sample needed dependent for modulated signals
(FTIR, etc.)

interest here, is that the interaction of the electromagnetic wave with the sample gives rise to a transmitted
component, a reflected component, and a diffusely scattered component [6]. Most important, the character
and fractional contribution of each of these components is govemedby a nonuniform distribution of
electric (and magnetic) field strengths throughout the sample. This distribution is the result of standing
waves generated in the sample. A simple (and proper) analogy for this distribution is the constructive and
destructive interference that occurs when light is reflected between parallel positioned mirrors. The
spectral phenomena are dependent on the nature of the sample, including the geometry and material
composition, and on the measurement variables, including the wavelength and polarization of the light,
the angle of incidence on the surface for an absorption experiment, and the viewing angle and polarization
of the emitted light for an emission or scattering experiment. The common sample structure for which
precise quantitative description is easiest is a planar sample consisting of parallel layers, each of variable
thickness and uniform composition. For this structure, the exact distribution of electric field intensities
throughout the sample can be determined provided that each of the materials in each layer can be assigned
accurate values of frequency-dependent dielectric or optical functions. In the latter description, the
appropriate values are the refractive index and absorption coefficient, nand k, respectively. When k > 0,
infrared absorption (or emission), spectral features will arise. From the ratios of the intensity values of
the input electric field intensity of the light at the sample surface and the output fields at the front and
back surfaces of the sample, the reflectivity (R) and transmissivity (T) (for a transparent substrate material)
can be determined. The calculation of R and T over a range of wavelengths constitutes a spectral
simulation. When the simulation exactly matches an experimental spectrum, the congruence implies that
the sample structure is characterized quantitatively. The k values for a given vibrational transition contain
the physics of the photon-electric dipole interactions. With respect to formulating the latter, there are two
points to note. First, the distribution of electric fields within a given layer will vary depending on the

3-6
values of n and k and the thickness for all the other layers. Thus it is not always possible to obtain simple
relationships between spectral intensities and layer thickness for a given layer without understanding the
entire sample structure in detail. Second, k is directionally dependent. The photon-dipole transition
depends on an electric field with an associated direction (a vector) interacting with an oriented electric
dipole (a vector). The interaction is thus directionally dependent (a scalar product maximized when the
field and dipoles are parallel), and to correctly describe the absorption (or emission)lIproperties of the
material phase, the quantities nand k must have directional character. Mathematically, this is done by
describing these quantities in the form of a tensor. Thus for samples containing IR active layers, the layer
orientations are a variable affecting the nature of the spectra. For isotropic (nonoriented) layers, n and
k are simple scalars, but as the net degree of orientational ordering increases, n and k become more
tensor-like quantities with the full description reached at complete biaxial symmetry (a single-crystallayer
with different responses along orthogonal directions). The above principles are presented in detail in a
recent publication [7].

B. Experiment

There are a variety of experimental methods for which IR radiation can be directed to andlor away
from a sample to perform a spect:rpscopic measurement These methods can be classified into distinct
types or modes. Each of these modes can be used to characterize surfaces and thin fllms, and each dis-
plays strengths optimized for different types of sample structures. Table 3 gives a list of modes that have
been used over the years and important characteristics associated with their utility. For a given
combination of mode and sample configuration, the ability to quantitate structural features depends on the
ability to apply electromagnetic theory accurately as outlined in the above section. There are several
sample features for which analysis is only possible, because of theoretical or practical limitations, using
certain sample types and experimental modes. Five.important sample features are film thickness, molec-
ular orientation, lateral distribution of sample features, depth distribution of sample features, and substrate/
fllm binding. Table 4 combines the above information to provide a description of which types of IRS
experiments are useful for specific sample types and features. In the discussion below, each of the IR
experiments is considered in detail. A general point to be made with regard to instrumentation is that
typically good FTIR systems operating in the mid-IR range under medium resolution conditions can
provide ~ 0.1 % precision in intensity per scan. The signal-to-noise ratio can be increased by up to nearly
two orders of magnitude by signal averaging. This level is more than sufficient to detect monolayer
quantities of a film, even for nonoptical sampling conditions. Some recent examples of applications of
IRS to monolayers are available [8,9].

1. Transmission

The transmission experiment is by far the most well known of all modes. It has a long history of
application to the analysis of gases and liquids. Because detection depends on transmitted light, the
sample must be somewhat IR-transparent For solids, the sample typically consists of an absorbing
powder dispersed in a transparent matrix (e.g, a KBr pellet); a very thin, unsupported absorbing film (e.g.,
a 2-~ polymer film); or a very thin film supported on a transparent substrate (e.g., a monolayer on a Si
wafer). .Detection and quantitative analysis of moderately absorbing monolayers in the latter sample
configuration can be considered routine for good quality commercial instrumentation, for the case of very
smooth, planar substrates. Rough surfaces scatter light and reduce the Signal/noise as well as the
researchers' ability to perform quantitative analysis. Curved or nonplanar surfaces distort the beam and
also reduce quantitative capabilities. In all absorption spectroscopy experiments, the analyses critically
depend on reliable reference spectra, e.g., a "clean" silicon wafer as a reference for a monolayer covered
wafer. Differences in optical characteristics of a few parts in 10" or so between the sample and reference
substrates can provide damaging spectral artifacts so sample/reference strategies are extremely important

3-7
 Table 3. Modes of Obtaining IR Spectra for Surfaces and lbin Films

.!!uili! Special Speclrometer

for Appropriate Sample Configuration Monolayer Special
Mode Liquids Configuration Requirements Advantages Sensitive "Disadvantages
Transmission No 1. Film on transparent window None - Simple experiment Yes None
2. Dispersed powder in - Easily quantitated
transparent matrix
External reflection Yes Film on planar, reflective Variable angle optics - Moderately simple Yes Transparent substrates are
substrate, usually but not experiment difficult
necessarily a metal - Quantitated with computer
calculations using EM theory
Internal reflection Yes Film on transparent internal Variable angle optics Moderately simple Yes Narrow selection of available
reflection element experiment IRS elements-may not be the
(rhombohedral or cylindrical- - Quantitated with computer substrate of interest
conic) calculations using EM theory
Diffuse reflectance No Powder dispersed in Collection-refocusing - Moderately simple Yes Only powders are useful
transparent powder matrix optics experiment
Photoacouslic No Powder or film on substrate Acoustic' detector - Moderately simple Yes Highly specialized substrates
attached to or very experiment and detector configuration
near sample needed for monolayer sensi-
tivity on planar substrates
Surface electro- ? Film on planar, reflective, Variable angle optics Yes Very difficult experiment
magnetic waves highly conducting metal
substrate with prisms mounted
for surface wave guiding
Spectroscopic . Yes Same as external reflection Variable angle optics, Highly precise, quantitative for Yes Difficult experiment
ellipsometry polarizer elements planar film/substrate
placed in beam before samples~btain optical
and after sample properties of film and thickness
Emission No Any sample type Collection-refocusing Any shaped sample can be Yes, but only Cooled optics mode requires
optics; heated sample examined for optimum controlled environment;
or cooled optical path experimental substrate background radiation
components work best conditions can be a serious problem for
monolayer and thin [tIms
 Table 4. IR Mode Applicable to Specific Sample Types and for Characterizing Specific Features

Description of Film and Features of External Itlternal Diffuse Photo- Emission Spectroscopic
Interest for Analysis Transmission Reflection Reflection Reflectance acoustic Ellipsometry

Substrate
1. Geometry
Planar X X X X X X
Nonplanar X (OK for cylindrical (Yes for (Yes for X
elements) powders) powders)
2. Roughness
Rough X X X
Smooth X X X X X X X
3. Materials
Metal X X X X
IR-absorbing nonmetal X X X X X
IR transparent X X X X X X X
Film
1. Thickness
Monolayer X X X X X X
Multilayer X X X X X X X
R!!Iuired Information
1. Film thickness or coverage X X X X
2. Molecular or bond orientation X X X (Yes for X
planar
substrates)
3. Lateral image O!: 10-J.1ID resolution X X
4. Depth profile O!: O.S-J.1ID resolution X X X
S. Bonding to the substrate X X X X X X
in transmission analyses. The same can also be said, in general, for all absorption modes discussed below.
The removal of these artifacts is a pervasive issue, but corrective strategies are toQ case-specific to be
discussed in detail here. If good quality spectra are obtained, then quantitative analyses can be carried
out using either Beer's law expressions (Eq. 1) as approximations or classical electromagnetic theory for
more exactness. For low refractive index support materials (e.g., KBr or NaCI), Beer's law
approximations are quite accurate, whereas for high index materials such as Si, errors of> 30% can result
for the Beer's Law approach using peak intensity measurements: The use of integrated peak areas,
however, provides good quantitation. Significant changes in peak positions and line widths also occur as
a function of the support refractive index, and a classical electromagnetic theoretical approach is necessary
to treat these optical effects properly to distinguish them from chemical effects [7]. There are two final
points to emphasize about transmission experiments. FIrst, depth profiling is not possible, because any
sample appearing in the IR beam can absorb light, and thus there is no way to differentiate the depth
location of an absorbing group in the beam. Second, lateral imaging is possible. Quite high-quality IR
spectroscopic microscopes are commercially available and provide spatial resolution to near the diffraction
limit (2: 10 mm) [10].

2. External Reflection

The external reflection experiment is, from a practical point of view, much more common than
the transmission experiment, because most overlayer films of interest for surface analysis are supported
on absorbing substrates for which the transmission experiment is not possible. Most of the time, metallic
substrates are encountered, e.g., copper and ferrous metal corrosion films and thin polymer coatings on
metal stock for cans. For cases in which the metal substrate is planar and reflective, IR spectra can be
generated by reflection off of the sample surface. Application of classical electromagnetic theory reveals
that the experiments are optimally done at grazing angles of incidence (~ 10° off grazing) with p-polarized
light Under such conditions, sufficient signal/noise can be obtained to allow detection of submonolayer
quantities of material and, most importantly, the spectra can be quantitatively analyzed using straight-
forward theoretical techniques [7]. Less frequently encountered are cases in which films are supported
on IR-absorbing but nonmetallic or weakly metallic substrates such as silicate glasses and highly doped
Si semiconductor wafers. Quantitative, monolayer sensitivity analyses are also possible on these substrates
using reflection techniques together with commercial instrumentation and correct application of theory both
to optimize the experimental conditions and to interpret the data [7]. In general, the signal-to-noise ratio
(SIN) can be as much as an order of magnitude less than for spectra of equivalent fllms on· highly
reflective, highly metallic substrates, due to the intrinsic physics of the light/surface interaction which
dictate that the electromagnetic fields at the surface are less for nonmetals than for metals, given optimum
experimental conditions. Again, as for transmission, the planar character of the substrate allows
quantitation of molecular and bond orientation relative to the surface plane. These analyses are viable for
any external reflection experiment for which the optical properties of the sample are well defined. Lateral
imaging is also possible on these planar substrates using IR microscopy, but for the case of metallic
surfaces, the requirement of grazing angles of incidence precludes very high spatial resolution. For
nonmetallic or weakly metallic substrates, angles of incidence in the range of normal to - 60° are possible,
depending on polarization, and reasonably good resolution can be expected, again limited by diffracti~n
effects, as for the transmission experiment Commercial microscope instruments are available for such
measurements [10]. Finally, the external reflection technique does not allow depth profiling, because the
electromagnetic fields generated at the surface extend as far away from the surface as the width of the
incoming beam (usually several mm) and are too slowly varying as a function of distance to allow
interpretation of the spectra in terms of vertical mapping of signal contributions at any useful distance
resolution. Some recent examples of surface analyses by external reflection IR spectroscopy have been
reviewed elsewhere [11].

3-10
3. Internal Reflection

Internal reflection IRS is a very specialized reflection experiment [12] which is, in general,
considerably less useful than external reflection for analyzing surface processes. In the internal r~flection
experiment, an IR transparent material is cut into a slab (trapezoid or parallelogram) or cylindrical rod
with conical ends and polished to give very smooth surfaces. By taking advantage of the phenomenon
of total internal reflection [12], IR radiation is brought into one face of the element and guided through
the interior along the long axis via multiple reflections. The electromagnetic field extends across the
element surface into the surrounding medium and decays in intensity exponentially away from the surface
with a falloff of the order of the wavelength of the light If an IR absorbing film is. located on the element
surface, an absorption spectrum can be obtained for that portion of the film located within the above fall-
off distance. Typical materials appropriate for fabricating the optical elements are Si, Ge, ZnSe, and
various specialized commercial materials such as KRS5. Unfortunately, these materials are usually not
the materials of interest in a typical analysis problem. Also, even if a given substrate material of interest
is IR-transparent, it often cannot be easily fabricated into the required element Thus, except for cases in
which fllms of interest can be placed on a reusable, inert element, e.g., Si, internal reflection is not useful.
One particularly useful case is when a soft polymer film is pressed into maximum contact with a hard,
highly smooth element such as one made of Si. In this case, the surface region of the polymer can be
examined up to a depth of the order of the wavelength of the light with an excellent SIN. However, if
the contact of the film with the element surface is incomplete, errors in quantitative analyses will
accordingly be present The SIN for an internal reflection experiment with multiple reflections can be
quite high, allowing submonolayer detection. The analyses can be carried out quantitatively with
molecular and bond orientations determined relative to the element surface plane in favorable cases. From
the physical. nature of the optical path, it is obvious that lateral imaging is not possible, at least with
multiple reflections. However, depth profiling is possible by carefully using the functional form of the
decaying electric field in the film overlayer. The decay function can be varied by changing element
materials and angle of incidence [12], which allows generation of a set of independent probes of spectral
contributions of the film interior as a function of distance from the surface. Solution of the
electromagnetic equations allows, in good cases, depth resolutions of better than tens of nanometers. In
general, however, such applications are rarely feasible for practical problems. A major practical problem
would be depth profiling a polymer surface region. In this case, the lack of completely reproducible,
uniform element/polymer contact from element to element precludes such detailed quantitative profiling
analysis, although qualitative analyses should be successful.

4. Diffuse Reflectance and Photoacoustic Detection

In cases for which surface films are to be analyzed on powders or high surface area granular
materials, the techniques of diffuse reflectance and photoacoustic spectroscopy are quite applicable. Uttle
will be said about such analysis in this paper, because these techniques are wen documented for powders
[3-5,13,14], and because quantitation of surface coverage, derivation of detailed structure such as
molecular and bond orientation, and imaging are rendered extremely difficult because of the ill-defined
analytical nature of the light/surface geometry and the distribution of sample characteristics such as surface
morphology. However, two comments will be made. First, qualitative analyses of overlayer fllms, even
monolayers, are quite simple, can be extremely useful, and can be carried out with commercial
instrumentation. Second, whereas diffuse reflectance works only for diffusely scattering samples,
photoacoustic spectra can be obtained, even for monolayers on highly smooth, planar substrates by
attaching a piezoelectric element directly to the substrate in such a way as to very sensitively detect the .
acoustic pulses generated from absorption events in the monolayer during IR irradiation [15]. Such an
experiment, however, is sufficiently difficult such that it should be considered a research tool rarely
suitable for practical purposes.

3-11
5. Emission

Emission spectroscopy is a useful and underused mode of obtaining IR spectra [3,5,9,16]. All the
above modes have referred to experiments in which spectra were obtained by measuring the fraction of
light beam power absorbed by various IR active groups in the irradiated sample. However, every sample
always emits a very weak but continuous IR spectrum from the decay of thermally populated excited
vibrational quantum states, and this spectrum contains contributions from the same individual groups as
seen in absorption. Thus it is possible, in principle, to obtain a spectrum from a film-covered sample just
by admitting the radiation into an IR spectrometer. However, there are two reasons why this doesn't work
well. First, the radiation is very weak at room temperature and is emitted in all directions. Second, most
of the flux is useless background (blackbody-like) radiation from the substrate and the film as well with
only a small fractional contribution from the IR vibrations of interest Related to the latter point is the
fact that all the parts of the spectrometer itself (mirrors, apertures, etc.) emit interfering background
radiation. However, strategies have been developed to overcome these problems, primarily by using
samples at substantially higher temperatures than the spectrometer and making very accurate corrections
for sample background radiation by using film free reference samples. Commercial instrumentation is
available for these experiments for use with heated samples. Monolayer detection is not possible by such
strategies because of the large background corrections. However, it is pQssible through the use of
cryogenically cooled spectrometers to detect monolayers on room temperature samples [9,17], but such
instrumentation is not available commercially. For cases in which samples can be heated above room
temperature, a major advantage of emission spectroscopy compared to reflection is that the sample can
be of any geometrical shape and surface roughness. This makes the method extremely attractive for
certain applications such as examining surface films on odd-shaped machine parts which; in fact, may be
normally hot Of course, such sample characteristics do not allow quantitative analyses. In general,
without extreme effort, emission spectroscopy cannot be performed in a quantitative manner relative to
the cases of transmission and reflection.

6. Spectroscopic Ellipsometry

Spectroscopic ellipsometry (SE) is really a special case of the external reflection experiment [18]
in which changes in the polarization state of the IR beam are measured rather than the fraction of beam
power· reflected, the traditional reflectivity measurement The major advantage of the ellipsometry
measurement is that the polarization state change contains information about both the amplitude change
and the phase change of the light, whereas reflectivity measurements~contain only intensity information.
The appearance of the additional variable of the phase shift allows two unknowns of the sample to be
evaluated, e.g., sample film thickness and density, whereas reflectivity allows only one, e.g., just sample
film thickness with the density evaluated independently. The calculations for ellipsometry are based on
standard classical electromagnetic theory. Ellipsometric spectra have the added advantage that the large
amount of data accumulated from the total numbers of spectral points can be used to accurately determine
wavelength-independent sample characteristics such as thickness, density, surface and interfacial roughness,
voids, and even density gradients perpendicular to the surface plane (depth profiling). This information
is in addition to the normal spectral information involving chemical structure, bond orientation, and other
features that affect vibrational modes and the absorption cross sections. By using the depth profiling
capability, composition gradients could be measured, in principle. The best demonstrations of the power
of ellipsometry as an incisive analysis tool for thin-film structures have been made for spectra obtained
in the ultraviolet (UV) and visible regions [19]. Here, for example, thicknesses ideally can be measured
to within 0.1 Aor better. Recently, interest in extensions into the IR region has accelerated [20-22], and
commercial instrumentation is now available. However, although it is possible to obtain spectra of
monolayer quantity films, because of signal/noise restrictions, it is not yet clear whether these films can
be analyzed quantitatively with present ellipsometry instrumentation. For various reasons related to the

3-12
basic physics of the experiment, it would appear that SE is most ideal for thin films on nonmetallic or
weakly metallic substrates as opposed to highly conductive metals. In addition, because the quantitative
value of the experiment derives from extremely high precision measurements, only highly smooth, planar
surfaces lead to high precision, analyses. However, even for rough surfaces, ellipsometric measurements
are of more value than reflectivity measurements simply because of the extra information. Finally,
because of the longer wavelengtli of the light, the ability of SE to measure thicknesses and perform depth
profiling is significantly less than in the UV-vis regions, by at least an order of magnitude. In general,
considering all the above points, it is always an advantage to use ellipsometric . spectra rather than
reflectivity spectra if possible, regardless of sample roughness or substrate material type.

V. IRS ANALYSIS APPLICATIONS, STRAlEGIES, AND ISSUES

In this section, the use of IRS is mentioned for several types of applications including both the
simpler ones involving "passive" types of samples in an analysis laboratory environment and the more
complex, challenging ones involving "active" samples that are to be analyzed directly in a processing
environment In all cases, it will be assumed that analysis of monolayer quantities of surface films is of
interest Thicker films can be accommodated easily if monolayer quantities are possible.

A. The Laboratory Environment

This class of analysis covers samples that have been removed from the processing environment
and have no special time limits or environmental requirements associated with the analysis.

Powders can easily be analyzed by diffuse reflectance, transmission, or photoacoustic methods with
the particular method chosen depending on the exact nature of the material. Small objects can be analyzed
individually by IRS microscopy if the objects are larger than - 10 J..IUl in diameter. For powders and small
objects, quantitation of coverage and film structure is not to be expected.

Sheet materials can be analyzed by transmission for IR transparent materials apd by external
reflection for nontransparent ones. As the degree of surface roughness decreases and the degree of surface
planarity increases, the degree of quantitation of film coverage and structure increases. Reasonably good
quality results can be expected for shiny metal sheet such as aluminum and steel alloys. The presence
of occasional surface scratches that occupy less than several percent of the surface area will have little
effect on the analyses, including even spectroscopic ellipsometry. It is also possible to analyze surface
fllms on IR-absorbing sheet such as polymers, particularly if the spectral contrast or difference between
surface films and bulk is large. The application of external reflection, and particularly spectroscopic
ellipsometry, to high-quality polymer sheet surface analysis has been highly underutilized. However, it
must be pOinted out that rigorous application of interpretive theory to these analyses is necessary for
quantitation.

Fmally, the case of analysis of large irregular objects presents a challenge, because the above
methods are only marginally applicable at best The use of IRS microscopy in the reflection mode is one
possibility if the sample is sufficiently small to fit in the microscope. However, quantitation of the
spectra, while not impossible, is very difficult because of the complex optical conditions and irregular
surface shapes. All irregular objects are capable of analysis by emission spectroscopy. However, in order
to generate analyzable spectral features attributable to the overlayer fllm, the object must be heated, the
film must be substantially thicker than one monolayer, and the substrate must not emit strong interfering .
background spectral features. It appears that the emission technique is probably underutilized for surface
analysis.

3-13
B. The Processing Environment

Analysis in the processing environment brings up two additional requirements not associated with
laboratory analyses as described above. The first is the ability to analyze directly in the presence of a
liquid or gas medium surrounding the sample and the second is the ability to analyze in real time, a
particularly severe requirement if the analysis object is constantly moving on a process line. This entire
class of analyses represents the cutting edge in analysis development.

The major problem with IRS analysis in gas and liquid media is that most Of the common media
are highly absorbing of IR radiation and thus provide large, interfering background contributions to the
analysis spectra Examples are ~O vapor, ~O liquid, CO2 , and most organic solvents. When the
contributions are extremely large, such as for liquid water, strategies involving corrections for the
background don't work suffiCiently well, and strategies involving reduction of the amount of the
interfering medium generating the IRS signal are necessary. This can be done in two ways: (1) reduce
the extension of the electromagnetic field from the sample surface into the medium and (2) reduce the
thickness of the medium adjacent to the sample. The first can be accomplished using internal reflection
and, in fact, this is the basis for several commercial IRS probes for monitoring the progress of processes
in bulk liquid (or gas) reaction media [23]. However, from the point of view of monitoring real processes
at surfaces, internal reflection would only be applicable when the internal reflection element could be
placed within one mm or less from the sample surface, a region within the effective range of the
electromagnetic field. This essentially amounts to the second strategy above, because the amount of liquid
present is contained to a very small thin layer equivalent to a thin cell that could be used for external .
reflection or transmission. The problem with this strategy is that the internal reflection element or ·the
infrared cell windows must be completely inert to the processing environment to prevent interfering signals
arising from chemical or physical changes at these surfaces. One area in which these strategies can work
is in electrochemical processing for which the electrode surface spectra can be freed of solvent and
window contributions by using the unique dependence of the electrode process on the electrode potential
[24,25]. A second problem of analysis in liquid and gas media is the coupling of the light in and out of
the local pr~cess environment One convenient way to accomplish this is to use optical ·fibers. This
strategy can provide an enormous Simplification in the optical path alignment and works extremely
efficiently in many regions of the visible and near-IR spectrum because of the existence of high
throughput, fibers with good mechanical properties. However, in the mid-IR region there are serious
performance limitations with the fiber materials available [26-29] although applications have been reported
[30-32].

From the above discussion, one can conclude that although IRS offers the possibility of in situ
analysis of surface processes in the presence of gas and liquid media, only analysis in the presence of
gases offers very realistic possibilities. Analysis in the presence of liquid media remains a case by case
possibility as the feasibility depends specifically on the type of liquid and the type of surface processing.
Developments of new methods of IRS analysis in this area would be of immense value.

A second important aspect of IRS processing analysis is that of analysis time. The speed of
surface processing could vary in principle from microseconds to hours. Although long processing times
present no problems, short processing times do. Some ideas as to possible measurement times can be
obtained by inspecting Table 2, in which the time scales associated with the use of possible IRS
experimental components are given. Although it is possible to operate well below the microsecond time
scale by using fast laser-based systems, it is generally impossible to obtain full spectra on these time ·
scales, because wavelength tuning of the lasers is comparatively slow. Measurements can also be done
on the microsecond timescale using time-resolved FfIR, for example, through the use of step-scan
instrumentation [33] now commercially available. However, in order to use this mode of time resolution,

3-14
the experiment must be capable of being rerun repeatedly in exactly the same manner with the same
results. This is fine for repeated pulsed experiments in the laboratory but not for one-shot processing.
However, a very practical time scale of about one second is obtained by using fast, commercial Fourier
transform systems. Complete spectra can be obtained in - 10 ms with limited resolution (- 16 cm·i ) and
with SIN sufficient for very thick film detection (~ 20 nm). However, with slower scan speeds and
multiple signal averaging, good resolution spectra (- 2 cm-I ) of strongly absorbing inonolayers in
appropriate sample structures (e.g., a reflective, planar sheet metal) can be obtained on the minute time
scale. This time scale is quite reasonable for monitoring typical surface processes such as photocuring,
sputtering, and plasma deposition. There are ample opportunities for developments of IRS strategies and
techniques in this area. The development of fast Fourier transform emission spectroscopy for heated
samples would be of interest.

The final aspect of IRS analysis to be discussed is that of characterizing moving objects, a real
concern for continuous, on-line processing such as sheet metal fabrication and polymer film plasma
treatment The major problem associated with these analyses, in addition to those covered above, is that
of dynamic alignment of the fluctuating target area on the processing line with the positioning of the fixed,
separate analysis optical line. This problem runs the gamut from the nearly "intractable application of
on-line spectroscopic ellipsometry, with its rigid demands of ultraprecise control of angle of incidence and
beam alignment, to the very tractable application of IRS emission for which extensive movement of the
sample is possible because by using very wide angle collection optics, the data are reasonably insensitive
to shifts in the sample positioning. This problem is compounded by the need to match the analysis time
to that of the average residence time of the target area in the analysis location. In view of the above
discussion on measurement times, it appears that given very fast rolling operation speeds with possible
residence times of - milliseconds or less for a one-cm target spot size, obtaining complete, high-quality
monolayer spectra is not currently possible by a factor of ~ leY. However, reasonable possibilities now
exist for monitoring changes involving, for example, whether or not thick (~ 100-nm) ftlms are present
or absent in a fast-moving target spot and obtaining some qualitative information about the physical nature
or chemical composition. Development of on-line analyses is of extremely great importance, and many
opportunities exist

REFERENCES

1. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th ed., John
Wiley, New York, NY, 1986.

2. D. Lin-Vien, N. E. Colthup, W. G. Fateley, and J. G. Graselli, The Handbook of Infrared and Raman
Characteristic Frequencies of Organic Molecules, Ac3demic Press, New York, NY, 1992.

3. P. R. Griffiths and J. A. DeHaseth, Fourier Transform Infrared Spectroscopy, Chemical Analysis,

Vol. 83, John Wiley, New York, NY, 1986.

4. Recent Developments and Applications of Infrared Analytical · Instrumentation, Symposium

Proceedings, Proc. SPIE--Int. Soc. Opt. Eng., 917, (1988).

5. Advances in Applied Fourier Transform Infrared Spectroscopy, M. W. Mackenzie, ed., John Wiley,
New York, NY, 1988.

6. M. Born and E. Wolf, Principles of Optics, 5th ed., Pergamon Press, New York, NY, 1975.

7. A. N. Parikh and D. L. Allara, 1. Chern. Phys., ~ en7 (1992).

3-15
8. Vibrational Spectroscopy of Molecules on Surfaces-Methods of Surface Characterization, Vol. 1,
1. T. Yates and T. E. Madey, Eds., Plenum, New York, NY, 1987.

9. Y. Chabal, Surf. Sci. Rep., ~ 211 (1988).

10. Infrared Microscopy, Practical Spectroscopy Series, Vol. 6, R. G. Messerschmidt and

M. A. Harthcock, Eds., Marcel Dekker, New York, NY, 1988.

11. M. D. Porter, Anal. Chem., ~ 1143A (1988).

12. For example, see: N. J. Harrick, Internal Reflection Spectroscopy, John Wiley, New York, NY,
1967.

13. D. Leyden and R. Murthy, Trends. Anal. Chem., L 164 (1988).

14. P. Belton, A. Saffa, and R. Wilson, in C. Creaser and A. Davies, Eds., Anal. Appl. Spectrosc., Proc.
Int Conf., 1987, Royal Soc. Chem., London, United Kingdom, 1988,245.

15. L. Rothberg, G. S. Higashi, D. L. AHara, and S. Garoff, Chem. Phys. Lett., 133,67 (1987).

16. S. V. Compton, D. A. C. Compton, and R. G. Messerschmidt, Spectroscopy, 35, (1991).

17. D. L. AHara, D. Teicher, and J. F. Durana, Chem. Phys. Lett., M. 20 (1987); S. Chiang, R. G. Tobin,
P. L. Richards, and P. A. Thiel, Phys. Rev. Lett., g 648 (1984).

18. R. M. A. Azzam and N. M. Bashara, Ellipsometry and Polarized Light, North-Holland, New York,
NY,1977.

19. For example, see: R W. Collins and Y. T. Kim, Anal. Chem., g, 2274 (1990).

20. A. Roessler, Nauch. Appar., b 57 (1987); A. Roessler, Mikrochim Acta, b 79 (1987).

21. F. Ferrieu and D. Dutarte, 1. Appl. Phys., ~ 5810 (1990).

22. B. Drevillon, Thin Solid Films, 163, 157 (1988).

23. For example, see: P. A. Wilks, Spectroscopy,!. 43 (1986); P. A. Wilks, Anal. Instrum., ~ 129
(1986).

24. S. M. Stole, D. D. Popenoe, and M. D. Porter, Electrochemical Interfaces: Modem Techniques for
in situ Interface Characterization, 1991, 339-410.

25. C. Korzeniewski and S. Pons, Prog. Anal. Spectrosc.,1Q, 1 (1987).

26. D. Pruss, P. Dreyer, and E. Koch, Proc. SPIE-Int Soc. Opt. Eng., 799. 117 (1987).

27. M. G. Drexbage and C. T. Moynihan, Sci. Am., 259. 110 (1988).

28. P. W. France, S. F. Carter, M. W. Moore, J. R. Williams, and C. R. Day, IEEE Conf. Pub!., 292. 428
(1988).

3-16
29. 1. A. Savage, Proc. SPIE-Int Soc. Opt Eng., 915, 52 (1988).

30. M. Saito, M. Takizawa, K. Ikegawa, and H. Takami, J. Appl. Phys., .§, 269 (1988).

31. M. A. Druy, L. Elandjian, and W. A. Stevenson, froc. SPIE-Int. Soc. Opt. Eng., 986, 130 (1989).

32. P. R. Young, M. A. Druy, W. A. Stevenson, and D. A. Compton, SAMPE J., 12.. 11 (1989).

33. R. A. Palmer, C. J. Manning, J. A. Rzepiela, J. M. Widder, and J. L. Chao, Appl. Spectrosc., ~ 193
(1989).

3-17
 4. OPTICAL SECOND HARMONIC GENERATION STUDIES OF ADSORPTION,
ORIENTATION, AND ORDER AT THE ELECTROCHEMICAL INTERFACE

Robert M. Com
Department of Chemistry
University of Wisconsin-Madison
Madison, WI 53706

ABSTRACT

The chemistry of solid-liquid interfaces affects a wide variety of important scientific and
technological areas such as electro analytical chemistry, heterogeneous catalysis, solar energy conversion,
tribology, chemical sensors, and biological membranes. In each of these systems, a very small number
of molecules at the surface can often control the macroscopic properties and direct the overall reactivity
of the device or structure. For this reason, spectroscopists are interested in devising methods of
monitoring the chemical and physical structures of such interfaces. A challenging problem for studies at
condensed-phase interfaces is distinguiShing between solution and interfacial species; this problem is
particularly difficult for optical methods, given that the light employed in spectroscopic studies normally
possesses a wavelength hundreds or thousands of times greater than typical interfacial distances.

Optical second harmonic generation (SHG) is an inherently surface-sensitive technique for studying
the interface between two centrosymmetric media that overcomes this distance disparity. The remainder
of the paper gives further examples of where SHG can be applied. It summarizes work under the headings
"Resonant SHG Studies of Molecular Orientation, Nonresonant SHG Studies of Chemisorption, SHG
Studies of Ordered Adsorption at Single Crystal Surfaces, and Future Extensions."

The complete article is published in Anal. Chem., 63(5) (March 1, 1991) (25 references).

4-1
 5. ANALYSIS OF IN1ERFACES USING SECOND HARMONIC GENERATION
AND SUM FREQUENCY GENERATION

Richard 1. Anderson
Sandia National Laboratories
Division 8342, P.O. Box 969
Livermore, CA 94551-0969

I. INTRODUCTION

The intent of this paper is to familiarize the reader with the analysis of interfaces using the
generation of new frequency components (second "harmonic generation [SHG] and sum frequency
generation [SFG]) at that interface. There are numerous excellent reviews [1-5] that go into considerable
detail describing the theoretical basis for these phenomena and that also focus on the application to certain
classes of problems (such as the gas-solid interface, the electrolyte-electrode interface, insoluble
monolayers at the air-liquid interface, etc.). I will touch briefly on the theory behind the phenomena, if
only to provide a vocabulary, then give as many examples of applications as possible, in the hopes of
stimulating the reader to think in terms of expanding these to include new problems. This is not intended
to be an exhaustive list of such applications, but is rather a selection derived from the author's
idiosyncrasies, with the anticipation it will serve the need for these proceedings. If the reader finds these"
techniques interesting and potentially useful, he will be well served by r~ferring to the reviews cited above.

II. BACKGROUND

I am reluctant to describe this section as theoretical. However, my experience is that it is

beneficial to provide those who have not actually practiced nonlinear optics with a basis for discussion
of the measured quantities and their origin. I will use a minimum of equations, hoping rather to describe
phenomena in words to give the reader a feeling for the processes in question. A rigorous treatment of
nonlinear optics is given in Prof. Shen's book [6].

Light interacts with a medium via a polarization caused by the presence of the optical
electromagnetic fields. The amplitude and phase of this polarization is determined by the susceptibility,
a property of the material. At low intensity, the polarization is described by the linear susceptibility and
leads to the familiar dielectric constant. a complex quantity manifest as the refractive index and
absorptivity of the material. However, at higher intensity, the polarization can become nonlinear in the
incident fields and must be described by including the higher order material susceptibilities. Because the
nonlinear polarization results from products of the field compOnents, the net polarization will now contain
frequency terms at sums and differences of the frequencies of the incident fields. This gives rise to the
rich spectrum of phenomena described as nonlinear optics, which includes multiphoton absorption, self-
fOCussing, sum and difference frequency generation, hyper-Raman scattering, and many other effects.

The electromagnetic fields of the light are vector quantities, therefore the material susceptibilities
that couple them are tensors and must reflect the symmetry of the medium. The lowest order coupling,
of two optical fields, is mediated by th~ second order susceptibility, which is a third rank tensor, and
which must, as a result. be nonzero only where there is no center of symmetry. This explains, for
example, why crystals used for frequency doubling and for sum- and difference-frequency mixing are not
"centrosymmetric. It also demonstrates the basis for the utility of frequency mixing at surfaces: when two
centrosymmetric media are in contact. the second order susceptibility vanishes except at the interface.
Thus, the bilinear (two at a time) coupling of frequency components can be used as a probe of a material
quantity that endures only at the interface.

5-1
 The experiment to probe the pairwise coupling of incident frequency components at an interface
is conceptually quite simple. In the easiest case, a single high-intensity pulsed laser beam is focussed at
the inte'iface, at a power density low enough to prevent sample damage. The incident field has a well-
defined propagation direction, so when it couples with itself to form the second harmonic (twice the
frequency) via the second order susceptibility at the interface, the induced dipole will radiate only in one
direction due to momentum conservation. Thus a new beam is created at half the wavelength of the
incident light, whose intensity can be measured by chromatic separation and suitable detection. When two
different colors are used, four new frequency components are created, at the harmonics and the sum and
difference frequencies, but each is still a well-directed beam that can in principle be treated as above for
isolation and' detection. Because the interaction length for pairwise coupling is very small compared to
the wavelength of light, there are no problems due to phase shift between the fundamentals and the
generated frequencies, but for this same reason the efficiency of generation is very low, typically one
photon for every 1012 to 1016 incident Nonetheless, because of the chromatic and directional purity of
the generated beams, one nearly always has sufficient intensity to perform an experiment

The induced dipole, which is the source of the generated light, is the product of the incident field
amplitudes and the coupling susceptibility. The detected intensity is the square of this amplitude; therefore
it is proportional to the squared modules of the susceptibility. Any susceptibility is a complex material
property that manifests the energetics of that material in its wavelength dependence. Consider as an
example the linear susceptibility. An electric dipole allowed (one photon) transition will cause the
i~aginary part of the susceptibility (the absorptivity) to increase to a maximum, determined by the width
and oscillator strength of the transition, for a photon energy resonant with the transition energy. The real
part of the susceptibility (the enhancement of the refractive index above the vacuum) goes through a sign
change at this energy, from a positive contribution at lower energies to a negative contribution at higher
energies. An experiment that is sensitive to the squared modules of the susceptibility thus sees a smoothly
rising intensity as a function of photon energy from above and below, to a maximum at the resonant
energy of the transition. The second order susceptibility includes resonances with all the input and output
photon energies, which give structure to the spectrum of generated intensity versus fundamental or
generated wavelength.

It would be remiss of me to proceed without mentioning that the discussion above is a somewhat
idealized picture of the generation of new frequencies by nonlinear reflection from a surface. In particular,
some second harmonic (SH) intensity arises from the nonzero third order susceptibility of the bulk of the
materials forming the interface. In the point dipole picture (fields only interact at a point by their dipole
fields at that point), this contribution is zero, but if the field gradients are included (nonlocal interactions),
the third order susceptibility can couple two fields and a gradient to form a bilinear frequency sum. The
weakness of this interaction is mitigated by the fact that it is integrated over the penetration depth of the
optical fields into the medium, which can be hundreds of times greater than the interaction length of the
surface process. However, generally this forms a background that is not affected by surface modification
and does not interfere as a practical matter [7,8].

For surface nonlinear optical spectroscopies, the resonances described above are between material
states at the interface. That is, the intensity of the generated light is determined by the electronic and
vibrational properties of the species at the surface, and gains utility as a means of measuring these
properties and the changes they undergo due to surface modification. Usually, transitions between
electronic states are about 1 to a few electron volts (e V) and are probed by the photon energy of the
fundamental or the second harmonic in the SHG experiment Transitions between vibrational states range
from hundredths to tenths of an eV (tens to hundreds of milli-electron volts, meV), and are probed by an
infrared photon in the SFG experiment Examples of both of these experiments will be described below.

5-2
 Finally, I will conclude this section with a brief historical note. The nonlinear optical properties
of a surface were first considered in 1962 [9], shortly after the demonstration of the fust optical maser
(laser). In a few years, nearly every nonlinear optical phenomenon had been observed, and surface SHG
was not an exception [10]. Indeed, the sensitivity of SHG to submonolayer quantities of adsorbates was
demonstrated by 1969 [11], but this work went unnoticed. When SHG was used to probe the optical
properties of a silver electrode used for surface-enhanced Raman scattering [12], it was realized that the
technique was sensitive to small fractions of a molecular monolayer even without the enhancement of
surface roughening [13]. This has led to the development of SHG as a general surface probe.

I will summarize a few important facts for the reader to carry to the rest of this presentation. One
(or two) intense laser beam(s) incident on the interface between two media, each of which is (bulk)
centrosymmetric, results in the generation of new beams at the second harmonic and sum/difference
frequencies of the incident beams. The coupling of the frequencies is mediated by the second order
. susceptibility, a material property that vanishes by symmetry everywhere except at the interface. The
intensity of the generated beamsis proportional to the squared modules of the second order susceptibility,
which has maxima at photon energies of the incident and generated light that are resonant with electronic
and vibrational transition energies of the interface species. Furthermore, the susceptibility is a tensor
quantity that must transform as the point group of the interface, thus it is sensitive to any anisotropy or
orientational pattern in the plane of the surface.

Ill. APPLICATIONS OF SURFACE NONLINEAR OPTICAL SPECfROSCOPY

A. SHG

The last paragraph of the preceding section can be summarized as the following equation:

1(200) oc Ie (2m) . X . e(m) e(m)12 12(00), (1)

where I is the intensity, X is the susceptibility, e is a polarization vector, and 00 and 2m are the
fundamental and second harmonic frequencies, respectively. When the . surface of a substrate, s, is
modified by the addition of an adsorbate, a, the net susceptibility can be expressed as

(2)

where X1 represents the change in susceptibility caused by the substrate-adsorbate interaction. All
applications of SHGutilize the change in susceptibility caused by adsorption, either as the additional
susceptibility of the adsorbate itself or that due to the interaction with the substrate. Usually, the substrate
susceptibility for metals and semiconductors is much larger than that of the adsorbate, so the change in
SH intensity due to surface modifi~ation is that ascribed to the interaction of substrate and adsorbate. On
the other hand, the contributions of substrate and adsorbate are comparable for dielectrics, and the
interaction is negligible. I will describe a number of examples of each interaction, for cases of solid-gas,
solid-liquid, and gas-liquid interfaces involving metals, semiconductors, and dielectrics. .

Metal and semiconductor surfaces in ultrahigh vacuum (UHV) provide a prototypical system for
the use of SHG to probe a surface subjected to modification by adsorption [14,15]. The substrate can be
prepared as a well-ordered crystalline surface, and both it and the substrate-adsorbate system can be
analyzed using the full arsenal of UHV surface spectroscopies. Thus the SH intensity can be correlated
with changes in the structure and energetics determined by other means. Furthermore, the high reflectivity
of most metals leads to a large transverse optical field, the source of appreciable SH intensity. A clean,
well-ordered single crystalline metal surface is anisotropic in the plane of the surface due to the crystalline

5-3
ordering. When the plane is not centrosymmetric, this anisotropy is evident in the dependence of SH
intensity on the rotation angle of the input polarization, in normal incidence [16], or of the substrate about
its surface normal for p-polarized, off-normal incidence, as shown in Figure 1. In this case, because the
SH intensity includes contributions from both isotropic and anisotropic elements of the susceptibility
tensor, the C3v symmetry of the surface causes a three-foid symmetric rotational pattern of SH
intensity [15].

Many clean metal surfaces have unoccupied surface electronic states in the gap between the Fermi
energy and the vacuum level [17]. Resonances between the experimental photon energies and transitions
connecting occupied and unoccupied surface states lead to maxima in the susceptibility. These surface
states are quenched or shifted when adsorbates are chemisorbed to the surface, which causes a reduction
in SH intensity with coverage, as shown·in Fig. 1 for the adsorption of hydrogen onto the Ni(111) crystal
face. Indeed, it is possible to account quantitatively for the coverage dependence of the susceptibility, at
least phenomenologically. These data are typical of many in the literature. However, it is also possible
for the adsorbate to shift the electronic transition into resonance with the fundamental or second harmonic,
as is the case for hydrogen on platinum [18].

Studies of semiconductors in UHV are quite similar to those of metals. The common
technologically important semiconductors are silicon and germanium [18-25]. Both are centrosymmetric,
and both have been studied using SHO, with the bulk of the effort. by far, devoted to silicon. Single-
crystal surfaces of silicon have been used as substrates to .study.hydrogen adsorption [24], thin-film oxide
formation [19], and the utility of SHO as a monitor of surface cleaning [26]. Additionally, because of the
technological significance of metal-semiconductor contacts, metal overlayers on silicon have been probed
using SHO [21,22,27]. In the case of a nonreactive metal such as gold, the rotational pattern was seen
to change as a function of multilayer coverage and was ascribed to a change in the symmetry of the gold-
silicon interface viewed through the few-monolayer-thick metal overlayer [22]. Recent work on the
nickellsilicon system, which forms nickel disilicide, has shown that the SHO contribution from the
silicide/silicon interface can be distinguished [27]. Also, an electronic transition at the Si(111)1CaF2
interface has been found using SHO [28].

Fmally, SHO is being used to study the surface diffusion of adsorbates on both metals and
semiconductors. Carbon monoxide on both Ni(111) and Ni(1lO) has been reported [29], as has hydrogen
on Si(111) [23].

Considerable effort has gone into the use of SHO to probe the modification of metal surfaces by
electrochemical deposition. A real synergy exists between the diagnostic technique and the surface
modification technique. Traditional analytical techniques of surface science can't be applied in situ.
because they require UHV conditions, whereas the electrolyte is transparent to the fundamental and
harmonic beams. Also, electrochemical deposition is a technologically significant technique whereby a
metal surface can be modified controllably and reversibly, and the surface coverage can be measured
independently by the integrated charge passed by the cell.

The electrode in contact with an electrolyte was among the first systems to be studied using
SHO [10]. The change of SH intensity with bias voltage was interpreted as arising from a change in
surface charge at a featureless conducting sheet (the electrode) due to either deposition or capacitive
charging. Recently, however, recently extensive work comparing SH intensity from single-crystal
electrode surfaces with similar surfaces in UHV has shown the situation to be more complex [3,30-33].
The rotational anisotropy and wavelength dependence of SH intensity are similar to those seen in UHV,
and for those cases in which adsorbate formation can be affected both by electrochemical deposition and
by gas phase adsorption (for example, hydrogen on platinum) [18,34], the coverage dependence of SH

5-4
intensity is similar. This implies that the surface states of clean metals are not completely quenched at
a metal electrode, and overlayer formation by electrochemical deposition may cause SH intensity changes
via mechanisms similar to those in UHV. Certainly, the complexity of potential dependence of the SH
intensity from an electrode surface remains a rich source of current research.

Despite the uncertainties indicated above, SHG is a valuable technique for monitoring the surface
of an electrode in contact with an electrolyte. Formation of submonolayer quantities of metal o verI ayers
by underpotential deposition causes a considerable change in SH intensity [35], as does charging of the
surface with adsorbed hydrogen prior to the evolution of hydrogen gas [36]. Another important aspect
of electrochemical modification of surfaces is the adsorption of charged organic species from the
electrolyte. SHO can also be used for such systems, and because of the structure of the adsorbate, even
more information can be gleaned on the electrode-adsorbate system. The susceptibility contribution from
the adsorbate, x., for organic species can be appreciable. For the chromophobe methylene blue on
platinum, selection ofa probe wavelength resonant with a molecular electronic transition permitted the
determination of the orientation of the molecule versus coverage on the electrode surface [37].

The application of SHO to the analysis of dielectric surfaces is somewhat different from that of
metals and semiconductors. The only surface states of dielectrics are similar to those of molecules; that
is, they are spatially localized and characterized by rather narrow resonances. X. and Xa are comparable,
and usually the change in SH intensity due to surface modification by adsorption at a dielectric is caused
not by the interaction susceptibility, but r~er by that of the adsorbate. Most adsorbates studied have
been organic chromophores, which have a well-known, polarized optical transition that is resonant with
the photon energy of the fundamental or second harmonic. SHO is used to follow the adsorption process,
and the polarization dependence of the resonant SHG is used to determine the orientation of the transition
dipole of the chromophobe, and thus of the molecule on the dielectric surface.

At the solid-gas interface, most examples are of dye molecules externally coated onto a substrate
(e. g., by spin coating). At the solid-liquid interface, adsorbed chromophores have been used to measure
the kinetics and thermodynamics of adsorption from solution, and to determine the orientation of these
molecules at the interface [38]. At the liquid-gas interface, both soluble and insoluble species have been
probed. Molecules in solution that are at the liquid surface instead of in the bulk have been shown to
have preferred orientation and to undergo different reaction dynamics from those in the bulk, because of
the anisotropy of their surroundings [39]. Insoluble monolayers can be formed at the surface of water as
Langmuir-Blodgett (LB) films. SHG studies ofLB systems have demonstrated surface-pressure-dependent
orientation, two-dimensional thermodynamics, and surface phOtolysis [5].

B. SFO

There have been considerably fewer studies using SFG than SHG. To probe electronic properties
of the interface, SFO is useful to defIDe an intensity maximum as arising from a resonance with the
fundamental or the generated beam [28], but eliminating this ambiguity only infrequently justifies the
added, complexity. On the other hand, SFO is critical in probing the vibrational structure at an interface.
In principle, vibrational spectroscopy is possible in SHO using an infrared (IR) beam as the fundamental
probe, but the problem of detection is inseparable. The net conversion efficiency of a surface nonlinear
optical process requires that detection be effected with single-photon counting sensitivity. This is not
possible with present IR detection techniques, so the dependence of surface susceptibility on vibrational
degrees of freedom must be shifted into the energy regime accessible with photomultiplier tubes, which
requires summing the IR frequency with that of a visible laser.

5-5
 The application of SFG to the analysis of surface species has been limited mostly to LB films and
self-assembled monolayers at a metal surface. Studies of the former system demonstrated the ability to
distinguish between different vibrations involving C-H bonds, showing the capability for chemical
specificity and determination of chemical bond orientation at the interface [5]. SFG of molecules self-
assembled at a crystalline metal surface, using picosecond pulse-width lasers, was used to probe for the
fIrst time the dynamics of excited vibrational states of molecules adsorbed at a metal surface [40].

Let me summarize by drawing some general practical conclusions concerning surface SHG and
SFG. Both techniques utilize an agonizingly small efficiency of generating new frequency components
as essentially invisible beams that must be separated and detected, and whose intensity must be monitored
to determine the effects of surface modification. However, in most cases, light of the appropriate color
can be found to which the intervening medium between the interface and observer is transparent; this
generates enough light via a resonance with the susceptibility to be detectable, and provides valuable
information concerning the state of the interface during submonolayer surface modification. SHG
primarily provides information on the electronic degrees of freedom of the interface, while SFG, although
a more complex experiment, provides information on the vibrational structure, which is of a truly chemical
nature.

REFERENCES

1. T. F. Heinz and G. A. Reider, TRAC-Trends in Analytical Chemistry, ~ 235 (1989).

2. J:F. McGilp, J. Phys.-Cond. Mat, b 7985 (1990).

3. G. L. Richmond, J. M. Robinson, and V. L. Shannon, Prog. Surf. ScL, ~ 1 (1988).

4. Y. R. Shen, Annu. Rev. Phys. Chern., ~ 327 (1989}.

5. V. Vogel and Y. R. Shen, Annu. Rev. Mat sCi., 11 515 (1991).

6. Y. R. Shen, The Principles of Nonlinear Optics, Wiley, New York, NY, 1984.

7. P. Guyot-Sionnest, W. Chen, and Y. R. Shen, Phys. Rev. B, ~ 8254 (1986).

8. J. E. Sipe, D. J. Moss, and H. M. v. Oriel, Phys. Rev. B, ~ 1129 (1987).

9. N. Bloembergen and P. S. Pershan, Phys. Rev., 128.606 (1962).

to. N. Bloembergen, R. K. Chang, S. S. Jha, and C. H. Lee, Phys. Rev., 174. 813 (1968).

11. F. Brown and M. Matsuoka, Phys. Rev., 185.985 (1969).

12. C. K. Chen, A. R. B. de Castro, and Y. R. Shen, Phys. Rev. Lett, ~ 145 (1981).

13. T. F. Heinz, C. K. Chen, D. Ricard, and Y. R. Shen, Phys. Rev. Lett, ~ 478 (1982).

14. H. W. K. Tom, C. M. Mate, X. D. Zhu, J. E. Crowell, T. F. Heinz, G. A. Somorjai, and Y. R. Shen, .

Phys. Rev. Lett, g 348 (1984).

15. R. J. M. Anderson and J. C. Hamilton, Phys. Rev. B, ~ 8451 (1988).

5-6
16. H. W. ~ Tom and G. D. Aumiller, ~hys. Rev. B, ~ 8818 (1986).

17. F. Greuter, I. Strathy,-E. W. Plummer, and W. Eberhardt, Phys. Rev. B, J1 736 (1986).

18. S. J. Grubb, A. M. DeSantolo, and R. B. Hall, 1. Phys. Chern., ~ 1419 (1988).

19. T. F. Heinz, M. M. T. Loy, and W. A. Thompson, J. Vac. Technol. B, l. 1467 (1985).

20. R. W. J. Hollering, 1. Opt. Soc. Am. B, ~ 374 (1991).

21.. P. V. Kelly, Z. R. Tang, D. A. Woolf, R. H. Williams, and J. F. McGilp, Surf. Sci., 251, 87 (1991).

22. J. F. McGilp, J. Vac. Sci. Techno}', A 5. 1442 (1987).

23. G. A. Reider, U. Hofer, and T. F. Heinz, Phys. Rev. Lett., M. 1994 (1991).

24. G. A. Reider, U. Hofer, and T. F. Heinz, 1. Chem. Phys., ~ 4080 (1991).

25. M. A. Verheijen, C. W. Vanhasselt, and T. Rasing, Surf. Sci., 251, 467 (1991).

1.6. R. W. J. Hollering, D. Dijkkamp, H. W. L. Lindelauf, and P. A. M. Vanderheide, J. Vac. Sci.

Technol., B 9. 1967 (1991). .

27. 1. C. Hamilton and H. W. K. Tom, in preparation (1991).

28. T. F. Heinz, F. J. Himpsel, E. Palange, and E. Burstein, Phys. Rev. Lett., §, 644 (1989).

29. X. D. Zhu, W. Daum, X. D. Xiao, R. Chin, and Y. R. Shen, Phys. Rev. B, 11. 11571 (1991).

30. R. Georgiadis and G. L. Richmond, J. Phys. Chem., 22.. 2895 (1991).

31. R. Georgiadis, G. A. Neff, and G. L. Richmond, J. Chem. Phys., ~ 4623 (1990).

32. A. Friedrich, B. Pettinger, D. M. Kolb, G. Lupke, R. Steinhoff, and G. Marowsky, Chern. Phys. Lett.,
163. 123 (1989).

33. R. A. Bradley, S. Arekat, R. Georgiadis, J. M RobinsOn, S. D. Kevan, and G. L. Richmond, Chem.

Phys. Lett., 168. 468 (1990).

34. D. J. Campbell and R. M. Com, 1. Phys. Chem., 2£, 5796 (1988).

35. D. A. Koos, J. Electrochem. Soc., 136. Pe218 (1989).

36. T'- D. Hewitt and D. Roy, Chem Phys. Lett., 181, 407 (1991).

37. D. J. Campbell, D. A. Higgins, and R. M Com, 1. Phys. Chem., ~ 3681 (1990).

38. T. F. Heinz, H. W. K. Tom, and Y. R. Shen, Phys. Rev. A,l.t 1883 (1983).

5-7
39. A. Castro. K. Bhattacharya, and K. B. Eisenthal. 1. Chern. Phys.• 22.. 1310 (1991).

40. A. L. Harris. L. Rothberg. L. Dhar. N. 1. Levinos. and L. H. Dubois. 1. Chern. Phys .• 94. 2438
(1991).

90

180 -+-~-I6---f4....--~--fi~+- 0
!I 0=0.0
c 8=0.2
• 8=0.4
A 0=0.6

• 8=0.8
• 0=1.0
270

Figure 1. Continuous curves show the calculated square root of the SH intensity (proportional to xo.> as
a function of azimuthal angle. 'II. for hydrogen coverages. a =0.0.• 0.2, 0.4, 0.6, 0.8, and 1.0
on the Ni(111) surface. Discrete data points are shown for the clean surface (outer curve) and
at inferred coverages from the adsorption/desorption data Details are given in Ref. 15.

5-8
 6. SCANNING PROBE MICROSCOPY

David A. Grigg
Digital Instruments
6780 Cortona Drive
Santa Barbara, CA 93117

and

Phillip E. Russell
Department of Materials Science and Engineering
North Carolina State University
P.O. Box 7916
Raleigh, NC 27695-7916

ABSTRACT

Several techniques have been developed over the past decade using near-field effects to obtain
high resolution microscopic images and surface microanalysis. These techniques are referred to as
scanning probe microscopies (SPMs). In each of these microscopies, a sharpened probe is used tomeaswe
a specific interaction between the probe and the surface of interest This new and expanding "field of
microscopy resulted from the invention of the scanning tunneling microscope (STM) in 1981 by Binnig,
Rohrer, and coworkers. The S1M measures the electronic interaction between a conductive (or semi-
conductive) probe and the sample to obtain atomic resolution images of the electronic surface structure.

Since the invention of the S1M, other near-field interactions between a sharpened probe and
sample have been used to image a variety of materials with nanometer to subnanometer resolution. The
scanning force microscope (SFM) was developed immediately after the S1M and is considered the cousin
of the S1M. In the SFM, various forces such as van dec Waals, adhesive, frictional, and capillary forces
are measured between the probe and the sample. By scanning across a sample at a constant force
(- 10-9 N), the topography of both conductive and nonconductive samples can be measured.

In a chapter on SPMs [1], we describe the history behind the development of SPMs and the
physics and mechanics of their operation. Examples are given from the literature that mark various
developmental steps. Also, several other scanning probe microscopic techniques are reviewed.

REFERENCE

1. D.A. Grigg and P.E. Russell, in B. Yacobi, Ed., Microanalysis of Solids: Scanning Probe
Microscopy, Plenum Press, New York, NY, 1993, in press.

6-1
 7. LOCAL ORDER AND BONDING PRIM.ARn.Y USING EXAFS AND SEXAFS

R. A. Mayanovic
Department of Physics and Astronomy
Southwest Missouri State University
Springfield, MO 65804

I. INTRODUCTION

A primary goal in understanding surfaces is determining the strucrural arrangement of surface

atoms. Because many surface problems involve surface structures lacking long-range order, an appropriate
technique for this instance is one with sensitivity to the local arrangement of atoms. One of the most
widely used such techniques involves conducting surface extended X-ray absorption fine structure
(SEXAFS) studies. The growth of SEXAFS as an investigative tool has largely been due to two important
occurrences: the development of synchrotron radiation and the progress made in the understanding and
theory of extended X-ray absorption fine structure (EXAFS). SEXAFS extended X-ray absorption fine
structure is important, largely because it is a nondestructive probe and has surface sensitivity.

Because it is impossible to adequately discuss all aspects of SEXAFS in a short review like this,
much detail has ~een omitted in the hope that the references provided are sufficient to locate other sources
where that detail can be found.

II. FUNDAMENTALS OF SEXAFS

SEXAFS owes its origin to the development of the understanding and .theory of EXAFS.
Although first discovered more than 70 years ago [1,2], EXAFS went relatively unnoticed until Sayers
et al. [3] showed that Fourier transforming the isolated data in photoelectron wave vector space could yield
reliable strucruraI results. To understand the results and developments of SEXAFS, we must first discuss
the principles of EXAFS in an overly simplified manner. More detailed discussions of the physics and
theory ofEXAFS can be ,found in reviews by Stem [4] and Lee et al. [5].

EXAFS can only be detected for atoms in the condensed state. The physics behind this process
is as follows: on penetration into a volume of atoms in the condensed state, X-ray photons with energies
up to approximately 40 keY may undergo absorption, with the effect dominated by photoelectron
absorption. In this process, a photon, having energy equal to or greater than the binding energy of a core
electron, is annihilated, transferring all of its energy to the photoelectron. The photoelectron is ejected
from the photoexcited atom with kinetic energy equal to the net energy of the incoming X-ray photon less
the binding energy of the core state, leaving behind a core hole. For most systems, photoelectrons having
low kinetic energies, typically below 30-50 eV, interact strongly with the potential of the surrounding·
atoms: the interaction becomes progressively weaker as the energy increases. 1his naturally delineates
the X -ray absorption near edge structure (XANES) region near the edge from the EXAFS region above
the edge. The significance of the photoelectron interacting weakly with the neighboring atoms' potential
is that, theoretically, this interaction can be treated as a perturbation on the final state of the photoelectron,
the initial state remaining unaffected because it is a tightly bound core state. To understand how the fine
structure above the edge originates, we must imagine the photoelectron as a wave propagating outward,
away from the photoexcited atom. As shown in Fig. 1, the photoelectron wave is backscattered by the
surrounding atoms. The final state of the photoelectron is given by a superposition of the outgoing and
scattered waves. The absorption rate is calculated quantum mechanically by a matrix element between
the initial core state and the final state of the photoelectron. Because the initial core state is nonzero only

7-1
at the location of the central atom, it is sufficient to determine how the final photoelectron state is affected
by the surrounding atoms at the center of the absorbing atom. The fine structure above the absorption
edge results from the alternate constructive and destructive interference of the outgoing and scattered
portions of the photoelectron wave, thus modulating according to its fmal state at the location of the
central atom. As the energy of the photoelectrons increases, their wavelength decreases, coinciding at
certain values to integral measures of the distance to the near neighbors. Thus, in the single scattering
scheme, the outgoing and backscattered waves add constructively to give a relative maxima to the final
state at the location of the central atom. This implies that the probability for the absorption of an X-ray
photon has relative maxima values for these particular photoelectron wavelength values, or, conversely,
for X -ray energies coinciding with these values. Similarly, when the photoelectron wavelength is
approximately equal to half integral measures of certain near neighbor distances, the probability for the
absorption of an X-ray photon has a relative minimum. Therefore, the phase of the EXAFS oscillations
depends on the distance from the photoexcited atom to the surrounding atoms, while the amplitude
depends on the type and number of these atoms backscattering the photoelectrons. Assuming that single
scattering events are dominant, the expression for the EXAFS oscillations is given by

...2 8 "" If" (k,x)1

_1_2 co:s- .
SID [2kR " + cpi1 (k)] e -2(J~1r' e"
-2R.I).(Ir)

k~
IJ 1 1
(1)

for s state excitations (K- or Lcedges). The expressions for the EXAFS involving p state excitations
~-and ~-edge) are similar to Eq. I, but are slightly more complicated because"the final state has an
admixture of states having s and d symmetry. In Eq. I, ~ is the X-ray absorption coefficient, J.Io is the
absorption coefficient of an isolated atom, ~ (k,x) is the backscattering amplitude of the photoelectron
wave, and A is the photoelectron mean free path in the condensed matter. The index i refers to the ith
shell of atoms; all at the same distance ~ from the absorbing atom, while the index j refers to the
individual atoms within each shell. 8ij is the angle between the X-ray electric field vector E and the
position vector r ij from the absorbing atom to the jth atom in the ith shell. The effect of backscattering
of the photoelectron by different atomic species is described by

(2)

where k is the magnitude of the photoelectron wavevector and 1 denotes the ·dipole allowed angular
momentum quantum number of the final state (the fmal state has p-like symmetry for which 1 1 by the =
dipole selection rule). The oscillatory nature ofEXAFS is contained in the sine term, within which 2~
is the phase resulting from single scattering of the photoelectron from the ith shell atoms and CPl i is given .
by

cP~ (k) = «Pi (k) + 251 (k) (3)

where «Pi is the backscattering atom phase shift and 51 is the central atom phase shift experienced by the
=
1 1 photoelectron traveling through the atomic potential of the backscattering atom and of the
photoexcited atom, respectively. The EXAFS oscillations undergo damping as described by the two
exponential terms in Eq. 1. The first term takes into account, assuming a Gaussian distribution about the
average distance ~, the disorder due to thermal vibrations and structural imperfections of the surrounding
atoms. The assumption is that the disorder is small. The EXAFS Debye-Waller factor ci is similar to
its namesake in X -ray diffraction, but different in the respect that it measures the disorder of each atom
in the ith shell relative to the ~ntra1 atom position and not relative to the mean lattice position of each

7-2
atOm. The second exponential term. takes into account the lifetime of the excited photoelectron state to
which there are two contributions: the lifetime of the core hole (- lO-ls s for the K-shell of copper) and
incoherent scattering of the photoelectron by other electrons and atoms. It is this effect that is responsible
for the EXAFS signal reflecting the local structure of the sample. In deriving Eq. 1, some of the
assumptions made about the phot~xcitation process occurring in the condensed state are that the
photoelectron can be treated as a plane wave, single scattering contributions to EXAFS are strongly
dominant over multiple scattering ones, and many body effects can be neglected, Le., the photoelectron
is considered an independent particle relative to other electrons in its vicinity. Unfortunately, these
assumptions have, in general, proved to be insufficient for direct fitting of EXAFS spectra using Eq. 1.
New advances in the theory of EXAFS (and photoexcitation in solids), notably by Natoli [6] and Rehr [7],
attack this problem directly by using multiple scattering as well as single scattering formalisms, spherical
waves in place of plane waves, and taking into account many body effects.

The polarization-dependent aspect ofEXAFS is especially important for surface study applications.
Because of the cos2 Ojj dependence, the EXAFS signal decreases substantially as the angle between the
X-ray electric field vector E and the position vector rjj of the neighboring atom relative to the location of
the central atom increases. Thus, by carefully orienting the surface of the sample relative to the·
polarization of the incoming X-ray beam, one is able to determine the geometric arrangement and type
of near neighbors surrounding the central atom on the surface. The polarization dependence of
~- and L:J- edge EXAFS is weaker than for K- and Ll-edge EXAFS due to the nature of the final states
involved in the p state and s state excitations, respectively. In order to illustrate this effect, we turn our
attention to.the example of a chemisorbed atom configured in a threefold hollow site, as shown in Fig. 2,
and calculate the term .

Nj
(4)
E 2
cos Ow
j=l

in a similar fashion to Stohr [8]. In this case, i = 1 refers to the first shell atoms, and the summation is
up to 3, because that is the number of nearest neighbors. Evaluating Eq. 4 gives

3
E cos 2
Ojj =3 cos2 a. cos2 J3 + 1.5 sin2 a. sin2 J3 (5)
j=l

For structures having threefold symmetry or higher, there exists a so-called "magic angle" (a. or 8 =54.7°)
for which one can obtain a measure of the total coordination number for the atomic shell in question. In
this way, 8 can be obtained from an amplitude analysis of the first shell data either by using a ratio of the
experimental data to a standard or by fitting the EXAFS oscillations. Using Eq. 4, Stohr derives similar
expressions in his review [1] for several of the most common atomic structural units found on surfaces.

Ill. DATA COLLECTION

The most straightforward way to measure EXAFS is to perform a transmission experiment place
a photon detector directly in front and one behind the sample to allow for a direct determination of the
X-ray absorption coefficient J.l{E). However, because transmission requires using sufficiently thick samples
that preclude performing surface stUdies, SEXAFS studies are done using processes involving radiative
and nonradiative electronic transitions associated with the annihilation of the core hole created by the

7-3
photoionization process. In this section, we discuss detection techniques used in SEXAFS studies; the
most common are fluorescence yield, Auger electron yield, total electron yield, and ion yield.

A. Fluorescence and Auger Yield

As mentioned above, there are two fundamental processes, involving radiative and nonradiative
electronic transitions, responsible for the annihilation of the core hole created during the photoionization
of the absorbing atom. As illustrated in Fig. 3, a fluorescence photon is emitted from the absorbing atom
on the filling of the lower energy core hole state (1 s in this example) by an .electron from a higher energy
state (21)3,0. The Ka fluorescence process has the highest transition probability in the case of the K shell
excitation. The background signal consists of elastically scattered and Compton scattered X-ray photons
having energies higher than the Ka fluorescence photons. The Auger electron detection for SEXAFS
studies was first suggested by Lee [9] and by Landman and Adams [to]. Auger emission process results
when the excess energy from the higher level core electron (2I>3n), in making the transition to an empty
lower energy core state (Is), is given up to another core electron (2P3n ) in the same shell. The
background in Auger electron detection is usually due to inelastically scattered electrons. These are
competing processes in which the Auger yield is the strongest for low-Z atoms, while the fluorescence
yield increases at the expense of the Auger yield and becomes the strongest for high-Z atoms. Several
groups have reported the dependence of the fluorescence yield [11] and Auger yield [12] on atomic
number Z.

Because the probability of the creation of the core hole is equal to the absorption rate in the solid,
the transition rates involving the fluorescence and Auger electron emission processes are therefore
proportional to the absorption rate. The expression for the surface signal strength Is , for a thin adsorbate
layer (J.lsX « 1), is given by [13]
(6)

where t; is the detection efficiency for photons or electrons, 10 is the incident X-ray intensity, c.o. is the
fluorescence or Auger electron yield, n is the solid collection angle, J.Is is the X-ray absorption coefficient,
and x is the adsorbate layer thickness. Thus, to extract the SEXAFS from the spectra obtained by
detection of Is, we use the definition for X in Eq. 1 [14].

Because the penetration depth for X-rays is much larger than the surface layer thickness (one
absorption length is - 42 J..IIIl for AI at 1 keY), the background signal is, generally, almost entirely due ·
to the bulk. In many cases of interest, specifically when the signal-to-background ratio is very small, it
is necessary to use an energy-discriminating detector to enhance the signal statistics. Electron signal
detection is generally more preferred than fluorescence detection for SEXAFS for several reasons:
(1) Auger electron yield is greater than fluorescence yield for all atoms having Z < 30 for K-edges, and
for all atoms having Z < 90 for all three types of L-edges, (2) electrons can be focused to. increase the
their collection efficiency, and (3) electron detectors are more compatible with the UHV environment used
for surface studies than photon detectors. However, there are instances when one detection mode is
preferred over the others due to complications that arise in relation to the experimental configuration and
system studied. Some of these complications include so-called "Bragg" diffraction peaks and related
effects contaminating the spectra, photoemission peaks entering the detector energy selection window
while sweeping the incident X-ray energy, and step height (signal-to-background ratio) versus signal-to-
noise ratio considerations. We discuss these and other complications in greater detail below.

Bragg peaks occur when the incident X-ray wavelength and angle satisfy the Bragg diffra~on
condition for the substrate or adsorbate crystalline atomic planes. Additionally, interference between the

7-4
incident wave and standing wave fields, established in die sample as a result of the Bragg diffraction
condition, modulates the photoabsorptioil to produce "derivative"-like glitches in the spectra [15]. Due
to the nature of detection, fluorescence yield is much more sensitive to the Bragg peaks, while electron
yield techniques are more se~itive to the derivative-like glitches. These effects become less problematic
at soft X-ray energies for which the Bragg diffraction condition is not fulfilled for most substrates.

In order to understand the criteria by which a detection mode is chosen to optimize the signal, we
first have to discuss sampling depths for electron detection. The manner in which the electron mean free
path in solids depends on kinetic energy has been well characterized [16]. However, the sampling depth
in tJ:tis case is not simply defined by the consideration of the electron mean iree path due to single
scattering events. Inelastic scattering of high-energy primary photoelectrons and Auger electrons produces
a large number of low-energy secondary electrons through a cascading process; a sizable number of these
secondary electrons can escape into vacuum. This increases the sampling depth beyond the mean free path
value. Jones and Woodruff [17] have estimated, from total electron yield EXAFS measurements at the
AI K-edge (1562 eV), .the sampling depth in aluminum metal to be 65 A and in aluminum oxide to be
130 A, while Martens et al. [18] estimated the sampling depth for copper metal to be 500-2000 Aat the
Cu K-edge (8979 eV).

Signal optimization is carried out in terms of the signal-to-noise ratio SN = IsII, where I is the
normalized incident flux count rate and is equal to the sum of the signal plus background count rates,
provided that the noise is purely statistical in nature. However, there exists, in addition to statistical noise, -
an instrumental noise contribution characterized by glitches or structures in 10 that persist in the fine
structure due to insufficient normalization [1,19]. The instrumental -noise becomes especially bothersome
for low adsorbate coverages and for low Z atoms. In this case, the ·signal-to-noise criteria has to be
discarded in favor of signal-to-background This was demonstrated rather eloquently by Stohr et al. [20],
from a SEXAFS study of 0.08 monolayer coverage of S on Ni(I00), who showed that, while the Auger-
electron signal rate was higher, its signal-to-noise ratio is very comparable to that of the fluorescence
signal measured on the same system. However, the signal-to-background ratio for fluorescence is about
a factor of 10 higher than for the Auger-electron signal, clearly establiShing in this case the criteria for
merit As demonstrated in this work, the fluorescence background signal can be lower than the
background for electron detection even though the penetration depth for X-ray radiation is much greater
than the electronic escape depth in solids. Stohr and coworkers attribute this, in large part, to a strong
reduction of elastically scattered X-rays at lower photon energies.

Another concern is the surface sensitivity of a detection technique for the particular system being
studied. There is no difference in the level of surface sensitivity for fluorescence and electron detection,
with or without energy discrimination, for a system of a well-defined layer of adatoms on a surface.
However, in the case of alloying, surface absorbing atom diffusion into the bulk, or a clean surface, close
attention must be paid to the sampling depth for each detection technique in order to select the one
appropriate for the measurement desired. As was shown by Comin et al. [21] for Si amorphi sized by ion
bombardment, it is possible to perform depth profiling with energy-discriminating electron detection, thus
taking advantage of the dependence of the sampling depth on the energy of the primary Auger electrons.

In the remaining portion of this section, we discuss in greater detail the elastic Auger, partial
Auger, and total electron yield techniques used in SEXAFS studies. A short discussion on ion desorption
yield is also presented.

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B. Elastic Auger Yield

As mentioned above, energy discrimination is an effective and sometimes absolutely necessary

method of optimizing the signal and enhancing surface sensitivity. The principle behind the elastic Auger
yield technique is the u~ of characteristic Auger electrons that have only been elastically scattered en
route to escaping from the surface of the solid. ,In Fig. 4, shaded rectangles are used to show
schematically the energy windows for electron emission after photoexcitation. The elastic Auger yield
is collected using a fixed energy window centered on the Auger peak while the X-ray photon energy is
varied during the SEXAFS measurement [22]. The electrons are typitally collected using photoemission-
type energy analyzers. It is apparent from Fig. 4 that when the X-ray photon energy is increased, the
photoemission peaks will appear at higher energies in the spectrum, thus possibly interfering with the
Auger peak. Therefore, before performing the experiment the, core level binding energy and the
characteristic Auger energy values for the absorbing atom must be used to assure at least a 300-eV spread
at the absorption edge between the Auger peak chosen and the next photoemission peak on the lower
energy side. The elastic Auger yield generally exhibits the best signal-to-background ratio characteristics
and has the best surface sensitivity, because of limited sampling depth compared to radiative and
nonradiative detection techniques. It also has the best discrimination capabilities against Bragg diffraction
glitches because of the small acceptance angle of the detector, allowing it to be moved along the polar
angle, relative to the sample normal and away from the directed peaks.

C. Partial Auger Yield

Most of the Auger electrons that leave the surface have suffered energy loss "due to inelastic
scattering. Because the inelastic scattering process is independent of the X-ray photon energy, the
intensity of these electrons as a function of hv will also exhibit the EXAFS. The collection of inelastic
and elastic Auger electrons leads to a decreased signal-to-background ratio, because the inelastic Auger
electrons are spread over a wide energy range in which they constitute a smaller part of the total signal
than the elastic Auger electrons do throughout the Auger peak. However, this is compensated for by an
increased EXAFS signal and better ability to avoid interference with photoemission peaks. Obviously,
surface sensitivity decreases for partial Auger yield (PAY) because the sampling depth is larger for
inelastically scattered Auger electrons.

D. Total Electron Yield

As shown in Fig. 4, using total electron yield (lEY) implies collecting the high-energy primary
photoelectrons and elastic Auger electrons, inelastic photoemission and Auger electrons, and secondary
electrons. An inherent problem associated with this technique is that the photoelectron intensity is angular
and energy dependent at any point in space [23]. It was first pointed out by Lee [9] that to have a direct
relationship between the photoelectron intensity and the absorption coefficient, such as in Eq. 6, there has
to be complete angular averaging of the photoemission signal. Martens et al [18] also pointed out that
the signal-to-background ratio depends on the incident beam angle; the optimal setting is 10°.
Comparison of lEY and transmission EXAFS measurements has shown that although there is good
agreement between the phases, the amplitude for lEY is generally smaller than for transmission.
Comparison between lEY and elastic Auger yield(EAy) results shows similar effects: for example, Stohr
et al [22] report an amplitude for lEY reduced by 15% relative to EAY at approximately 250 eV above
the AI K-edge for aluminum metal. The situation is still unresolved as results vary for different groups:
Erbil et al. [24] obtained a 5%-10% amplitude reduction for lEY compared to transmission, for several
different systems, while a more recent study made on gold metal and GaAs powders by Kemner et al. [25]
revealed practically identical amplitudes for the two techniques. lEY is an especially easy technique to
use, because collection of the electrons caD. be accomplished, in many cases, by simply suspending a

7-6
biased metal plate over the grounded sample and measuring the drain current. 'lEY is an appropriate
choice when it becomes impossible to avoid interference with photoemission peaks in the detector energy
window. -lEY is the worst of the electron detection techniques for surface sensitivity, Bragg diffraction
glitches, and signal-to-background ratio. . -

E. Secondary Yield

Collection of secondary electrons involves using a narrow energy window very close to the
vacuum level energy, because the energy for secondary electrons is typically 3-5 eV [23]. lbis way, it
is possible to avoid the amplitude problems inherent in lEX, however, the signal for secondary yield is
reduced.

F. Ion Desorption Yield

Our current understanding of electron stimulated desorption (ESD) of surface ions is that at least
two mechanisms exist: in the Menzel-Gomer-Redhead (MGR) model [26], electronic scattering of valence
electrons causes their ionization, resulting in repulsive ionic final states, while in the Knotek and
Feibelman (KF) model [27], applied to strongly ionic systems, the ionization is due to core electron rather
than valence electron excitation. In the KF model, desorption can occur as a result of intratomic Auger
transitions for ionization of adatoms, or interatomic Auger transitions for ionization of substrate atoms.
The Auger transitions involve valence electrons, some of which may be in bonding states, leading to the
breaking of the adatom-substrate bonds. If the core electrons are photoionized, the intensity of the ions
desorbed as a result of the KF mechanism will exhibit fme structure in direct relation to the EXAFS seen
in the absorption coefficient Jaeger et al. [28] reported the first SEXAFS study using ion desorption
yield, in which 0+ ions were collected from a monolayer coverage of oxygen on Mo(100). Two
complications severely limit using the ion desorption yield technique for SEXAFS studies. For many
systems, particularly covalent ones, the MGR and possibly other mechanisms beside the KF process,
contribute to the ion desorption yield but not to the EXAFS signal. The other limitation is that the ion
yield SEXAFS signal is inherently weak.

IV. EXPERIMENTAL DETAILS

Our aim in this section is to provide a brief discussion of some of the more essential details of
the experimental setup and data analysis. More details can be found elsewhere [1].

A. Experimental Setup

The most important components of the experimental setup are: the synchrotron radiation source,
the monochromator, the incident be,am and signal detection assembly, and the ultrahigh vacuum (UHV)
sample chamber. Because the signal detected for SEXAFS is relatively weak, X-ray flux intensities of
the order of at least 1010 photons/s are required. As a consequence, synchrotron radiation has played and
continues to play an instrumental role in the development of the field. Because the acceptance angle of
most electron energy analyzers is small, the X-ray beam requires focusing to approximately 1 mm2 at the
location of the sample. The energy resolution required is < 5 eV; however, 1-2 eV are more desirable,
especially for details in the near edge region, and are often obtainable. Spectral purity of the X-ray beam
is very important for a successful experiment One source of particularly bothersome spectral impurity
is due to harmonics, which are higher order reflections (the principal energy being the first order
reflection) from the gratings or crystals in the monochromator. The three most effective ways to deal with
harmonics are: (1) detuning monochromator crystals, that is, misorienting one crystal very slightly relative
to the other [29], (2) using harmonic rejection mirrors, and (3) using filters.

7-7
 Characterization of the surface using complimentary techniques such as low-energy electron
diffraction (LEED), Auger "electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) , and
therm3.I desorption, ensures a more definitive study and, if performed prior to the SEXAFS study, may
help in the optimization of the experiment. For example, identification of unwanted impurities on the
surface and their removal may eliminate potential interference between spectra. due to their overlap in
energy or may enhance the sensitivity if the impurity atoms contribute significantly to the background.

The signal intensity is normalized by the incident beam intensity, which is typically monitored
using the total electron yield produced in a coated metal grid intercepting the incoming beam. There are
cases for which glitches due to Bragg peaks, harmonics, etc., are not removed by normalization
sufficiently, and these features therefore remain in the spectra. This occurs when the response of the
signal and reference monitors to the source of the glitches is not the same. Stohr et al. [30] suggested
alternatively using the signal measured from a clean substrate as a reference signal and demonstrated the
technique for 113 monolayer of oxygen on Ni(lOO).

B. Data Analysis

SExAFs data are preferably analyzed by using the ratio method, and if that is not possible, one
resorts to fitting the data in wavevector k space. The fine structure oscillations are isolated by first
subtracting the pre-edge background from the reference-signal-normalized data, followed by subtraction
of the atomic-like background above the edge and normalized with respect to the step height [14]. The
dependence of the SEXAFS signal is converted from energy to a wavevector in this process. The isolated
data are then Fourier transformed from k space to R space. The Fourier transform generally looks like
a multipeaked profIle, in which each resolved peak corresponds to shell distributions of neighboring atoms
surrounding the absorbing atom. If the individual peaks are well resolved with respect to one another,
then another Fourier transform is performed, back to k space, over the region isolating a particular peak.
Thus, fine structure oscillations due to a particular shell are isolated in this way. Performing a ratio
between the isolated-shell sample data and similarly obtained model compound data can provide relative
amplitude and phase results. Otherwise, if the peaks are not well resolved, one has to resort to a
multishell fitting of the data.

V. APPLICATIONS TO SURFACE PROBLEMS

A. Gas-Solid Reactions

Most of the gas-solid systems studied using SEXAFS involve molecules of gas that dissociate on
reaction with the surface and become chemisorbed, typically in ordered overlayer arrangements determined
by the symmetry of the surface. Compound formation at the surface is also possible, as for example,
oxide formation at metal and semiconductor surfaces. The presentation in this section is chronological,
by system studied, with greater emphasis placed on studies completed after the publication of reviews by
Stohr [1] and Citrin [2].

1. Gas-Metal Reactions

I1Ag(111). This is the very first system to be studied using SEXAFS, demonstrating the power of the
technique for surface structure determinations. The studies of the system with 113 monolayer (ML)
(.f3x.f3)R30° iodine on Ag(111) by Citrin et al. [31,32] basically verified the structure determination using ·
LEBO but with much more precision. The data were obtained at the I ~-edge, using the EAY technique.
The I-Ag bond length was determined to be 2.87±O.03 A (compared with 2.80±0.15 A for LEED
determined by Forstmann et al. [33]) using 'Y-Ag1 as a model compound. The effective coordination

7-8
number was deduced using Eq. 4 according to which the chemisorption site was determined to be in the
threefold hollow configuration.

I1Cu(100) and Cu(111). Citrin et al. [34] also investigated the local structure of iodine on Cu(100) and
Cu(lll) using 'lEY SEXAFS measured at the I L3-edge. The polarization dependence of the EXAFS
signal was fully exploited to make an unambiguous determination of the chemisorption site for both cases.
LEED spot patterns revealed 1/3 ML (.f3x.f3)R30° iodine on Cu(111) and 1/4 ML p(2x2) iodine on
Cu(100). Using the ratio method and 'Y-Cul as the standard, the iodine on Cu(111) was found to have a
bond distance of 2.66±O.02 A, and the iodine on Cu(100) had a bond distance of 2.69±O.02 A. The
smaller error bar for this study relative to the authors' I1Ag(l1l) study was attributed to improved data
quality using 'lEY rather than EAY. The authors showed in a convincing fashion, from analysis of the
polarization-dependent isolated EXAFS amplitudes, that chemisorbed iodine sets in a threefold hollow site
on the Cu(111) surface and in a fourfold hollow site on the Cu(100) surface. Additionally, they showed
that EXAFS amplitudes may be transferred between bulk and surface systems within at least 25%.

I/Ni(I00). The 'lEY SEXAFS study by Jones et al. [35] of the 1-2 ML surface iodide phase formed on
a Ni(100) surface is significant because they were the fIrst to apply the fitting approach to data analysis.
Using Ni~ for a standard, they used both the conventional method of isolating the fIrst shell contribution
to the signal and performing a ratio and a curve fitting method, for which the calculated phase shifts are
adjusted by first fitting Ni~ data. Jones et al. found excellent agreement for the results obtained using
the two methods. However, a more recent study by the same group [36] showed that, in fact, the first and
second shells in the Fourier transform are not separable, thus excluding the ratio method in this case as
viable. In this study, the authors were able to show, for the 1/2 ML c(2x2)I on Ni(I00) structure, that the
fitting method can be used successfully to determine the local structure. They found the I-Ni bond length
to be practically unchanged relative to the value for the bulk o(Ni~ (2.78±O.02 A), and the absorption
is at the fourfold hollow site.

O/Al(111). Both Johansson and Stohr [37] and Bachrach et al. [38] perfoIll).ed SEXAFS studies, using
'lEY and measured at the 0 K-edge, on the - 1 ML(1xl) 0 on AI(III) structure and obtained differing
results. The O-AI near neighbor distance quoted by Johansson and Stohr was 1.79±O.05 A while Bachrach
et al. obtained a value of 1.92±O.05 A. Although polarization-dependent SEXAFS data were obtained,
the threefold hollow chemisorption site could not be confirmed as deduced from previous LEED studies
[39]. A reexamination of previous LEED data was prompted because the atomic distances obtained using
SEXAFS varied significantly from those obtained from LEED. The large error bars can in part be
attributed to a significantly oxidized aluminum underlayer contributing to the signal.

OINi(100). SEXAFS studies by Stohr et al. [30] on this system helped contribute to understanding oxygen
chemisorption on nickel surfaces. The 0 K-edge was measured in the PAY mode, and the polarization
dependence of the signal was exploited by collecting data for 100 and 900 incidence angles. The study
was stimulated by predictions made from generalized valence bond electronic structure calculations [40]
claiming that the P(2x2) and c(2x2) structures with 0 in the fourfold hollow site should have considerably
different displacements when measured along the surface normal. Using NiO for the standard,
unambiguous evidence for the fourfold hollow site for 0 was given in the c(2x2) structure, with a bond
length equal to 1.96±O.03 A, and no evidence was seen from a theoretical model of different displacements
for the two structures mentioned above.

OINi(IIO). The SEXAFS study of this system by Baberschke et al. [41] was, in execution, very similar
to the study by Stohr et al. [30], but it yielded unprecedented preciSion in structure determination. The
long bridge site of the - 1/3 ML O(2xl) on Ni(1lO) structure was identified having the O-Ni near
neighbor distance of 1.85±O.02 A. Due to the preciSion, the oxygen-induced reconstruction of the Ni(100)

7-9
surface was determined to be of the "sawtooth" type. while eliminating the possibility for the buckled-
surface, based on the absence of the third shell peak in the Fourier transform of the EXAFS data The
"sawtooth" reconstructed surface was established based on the intensity of the fourth shell peak and the
polarization dependence of the data [42].

O/Cu(1lO). This system, studied by Dobler et aI. [43,44] is very similar to the OlNi(llO) system that was
studied later. The investigation was carried out in much the same way as for the OlNi(110) system
discussed above and had similar precision. The twofold bridge site of the - 112 ML O(2xl) on Cu(llO)
structure was identified, with an O-Cu bond length of 1.84±0.02 A, using the relative amplitudes of the
frrst and second neighbor shell data. This low-~ymmetry site had been a source of controversy, because
metals were usually found to have high symmetry sites. It was suggested by Dobler et aI., based on the
evidence of the absence of the third shell peak and presence of the fourth shell peak in the Fourier
transform, that the CU(1OO) exhibited O-induced "missing-row" reconstruction. Their later studies [41,42]
on OlNi(llO) confirmed this. However, a possible explanation for the different reconstruction for the two
systems may be due to stronger OlNi than O/Cu chemisorption [42].

O/Cu(lll). Polarization-dependent SEXAFS studies above the 0 K-edge were performed on this system
by Haase and Kuhr [45] using PAY. For - 112 ML 0 on Cu(ll1), they found evidence for a
reconstructed and oxidized surface; the reconstruction was evident in the increased Cu-Cu distance on the
surface compared to bulk. The system is known to exhibit a disordered surface. The relative amplitudes
at different incident angles are used to identify the threefold hollow site for 0 (Rl = 1.83±0.02 A) close
to the surface. The authors could not determine if the 0 was above or below the surface Cu atoms.

O/Ag(llO). This system was found to be very similar to the O/Cu(llO) system. Two sets of studies have
been performed on O/Ag(llO), both in a very similar fashion to the studies on O/Cu(1lO) and OlNi(llO)
discussed above. Puscbmann and Haase [46] identified the twofold bridge site of the O(2xl) on Ag(1lO)
structure but were unable to establish the type of reconstruction due to reduced data quality. Recently,
Becker et aI. [47] were able to identify the reconstruction as the "missing-row" type, as in O/Cu(1lO), and
to confirm the surface structure. The first neighbor distance of 0 is quoted as 2.04±O.03 A and the second
neighbor distance as 2.l9±O.03 A.

SlNi(1oo). The first study performed on this system was by Brennan et aI. [48]; this system was chosen
because it was one of the best known systems at the time. The measurements were made in the EAY
mode, at the S K-edge, for different angles of incidence. The high quality signal-to-noise ratio allowed,
for the first time, a determination of the fourfold hollow site of the - In ML c(2x2)S on Ni(1oo) structure
from the combination of the determined first and second neighbor distances without the relative amplitude
analysis. The S-Ni bond length was determined to be 2.23±O.02 A. Thiophene (C4H4S) chemisorption
on Ni(1oo) was later studied by Stohr et aI. [20], with varying S coverages, for which the molecule was
found to dissociate on a clean surface at temperatures as low as 100 K to the c(2x2)S on Ni(1oo) structure.
Thiophene was found intact for an experiment performed with an oxygen-predosed Ni(IOO) surface.

SlNi(111). The model proposed for the local structure of Son Ni(lll) by Kitajima et aI. [49] is presently
somewhat in question. Based on their relative amplitudes for the polarization-dependent first shell data,
Kitajima et aI. proposed that, for the (S/3x2)S on Ni(111), drastic surface reconstruction into a pseudo-
c(2x2)S on Ni(1oo) results from sulfur adsorbed on the pseudo-fourfold hollow site. Ohta [50] performed
X-ray standing wave experiments on the same system and determined that the results for the two
experiments cannot be reconciled if one assumes a standard type of site occupation for sulfur on Ni(111).
However, if one assumes a reconstructed surface as proposed by Kitajima et aI. and an outward expansion
of the surface by 0.15 A, then the results agree. '

7-10
S/Cu(lll), (100), and (110). Prince et al. [51] have performed a SEXAFS and X-ray standing wave study
of the S/Cu(lll) system. LEED patterns revealed a (.f7x.f7)R19° S on Cu(111) structure after exposure
of a clean Cu(111) surface to ~S in excess of 5 L. The SEXAFS data were collected for two angles of
=
incidence using the EAY technique. This study suffers from a lack of precision (Rl 2.30±0.1 A) due
to the high level of noise and because the fitting method was chosen for data analysis. Although the exact
structure of the surface was not determined, the authors were able to infer from their results that S lies
both below and above the Cu atoms. The S atoms below the Cu layer occupy sixfold hollow sites, while
the Cu are in identical off-bridge (towards atop) sites, and the S atoms above are in atop sites. In a study
performed on the S/Cu(1oo) system, however, Kitajima et al. [52] were able to determine, using
polarization-dependent SEXAFS results, the surface structure as (/7x/7)R14°. Measurements were
collected, at three incident angles, in the fluorescence yield mode, and surface coverage was estimated to
be - 112 ML. The S-Cu bond length was 2.33±O.03 A. Using the combined results from the SEXAFS
and LEED measurements, Kitajima et al. proposed a model for surface reconstruction involving clockwise
and counterclockwise rotational displacements of Cu atoms relative to the S adatoms of 0.59 A.

Recently, Atrei and coworkers [53] conducted a SEXAFS study of sulfur adsorption on Cu(llO).
Polarization-dependent measurements were taken using the EAY technique at varying S coverage. In
conjunction with LEED results, the authors reported a c(2x2) surface structure at low S coverage, while
ruling out recotistruction or multiple adsorption sites at higher coverage in favor of an expansion of the
fIrst Cu interlayer distance. . The S atom was found to occupy the twofold hollow site, with the Cu-S bond
length of 2.37±O.03 A, throughout the coverage range studied.

CIICu(l00) and Ag(100). The study of this system by Citrin et al. [54] was stimulated by conflicting
results for the c(2x2) CIon Ag(100) structure from LEED measurements and from comparison of
calculated and measured photoemission spectra. Copper was chosen because its photoemission peaks did
not interfere with the EAY signal. The adsorption site was identified as the fourfold hollow site of the
c(2x2)O on a Ag(100) structure with a CI-Cu bond length of 2.37±O.02 A. The polarization-dependent
SEXAFS data showed an anisotropy in the higher shells due to an averaging of four third-nearest-neighbor
atoms in the second layer and eight fourth-nearest-neighbor atoms in the first layer. The structural
parameters obtained from the Citrin et al. study were used to calculate the photoemission spectra for
CIICu(l00) and were found to have excellent agreement with experimentally measured spectra. In this
way, the importance of providing experimentally-deduced structural results was established. Although
difficult, studies have been carried out on the CIIAg(loo) system [55]. The system had to be studied in
1EY mode, due to photoemission peak interference for EAY detection, and at 100 K, due to anharmonic
distortions of the SEXAFS spectra being greater at room temperature. Coverages of 2/3 and 1/3 ML of
CI were studied: a weak LEED pattern consistent with the (.f3x.f3)R30° structure was observed for
2/3 ML 0 coverage, while no LEED pattern was observed for the 1/3 ML coverage. Fitting of the data
was used to obtain distances, and a threefold hollow absorption site was proposed for both coverages but
not identified due to insufficient polarization-dependent data.

Te/Cu(111) and Cu(1 (0). Comin et al. [56] made a SEXAFS study of both systems using 1EY and AEY
techniques. They identified the 114 ML p(2x2)Te on Cu(100) structure (nearest neighbor distance
Rl = 2.62±0.04 A) and the 1/3 ML (2.f3x.f3)R30° Te on Cu(111) structure (Rl = 2.69±O.06 A), the latter
having a novel sixfold quasisubstitutional site for which Te substitutes for Cu in the surface layer. The
complete understanding of the nature of chemisorption for the low symmetry site is of interest in view
of the experimental fmdings. The fact that Te has a relatively large atomic size and low reactivity is
thought to play a role.

Xe/Cu(lll). A temperature-dependent SEXAFS study on this system [57] has recently been reported.
The authors revealed that at 77 K. the Xe adatoms form a commensurate (.f3x.f3)R30° structure, in which

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the Xe atom sets in the threefold hollow site, while between 18 and 47 K, they form an incommensurate
structure because the Xe-Xe spacing is different than the distance between threefold hollow sites on the
Cu(1ll) surface.

2. Gas-Semiconductor Reactions

Gas-semiconductor reaction systems are generally more complex and not as well understood as
gas-metal systems. Early studies of oxygen chemisorption on GaAs(1lO) [58] and Si(III)2xl [59] helped
establish PAY as a viable technique but gave inconclusive results due to the low quality of the data. The
fIrst substantially quantitative study [60] of this nature was conducted cn the Te and I on Si(111 )7x7 and
Ge(111)2x8. For about 1 ML coverage and data collected using the my mode, I on both surfaces was
found to occupy the onefold atop site, while the twofold bridge site was identifIed for Te/Si(lll) and the
threefold h.c.p. hollow site for Te/Ge(III). The I1Si(111), I1Ge(111), and Te/Si(lll) results fit tJ:le pattern
for which either the monovalent I or divalent Te uses up the dangling bonds and thus prevents the surface
from undergoing reconstruction while Te/Ge(111) does not. A later study [61] of Te/Si(111) was
motivated by the desire to determine how the unusual Te twofold bridge site occupation changed as a
function of surface coverage. For about 114 ML coverage, the authors reported a l00Si(111)
(.f3x.f3)R300-Te structure. The Te atoms were determined to reside in the twofold bridge site again, but
the fIrst- and second-neighbor distances were found to be longer than those for - 1 ML coverage. A
possible explanation offered for the distance lengthening was a slight tilting of the Te atoms relative to
the surface. The CIISi(111) and Ge(111) systems were studied in a separate work, showing that CI
occupied the onefold atop site on annealed Si(I11)7x7, annealed Ge(111)2x8, anti quenched
Si(111)(.f19x.f19) surfaces. These data agreed with the chemisorption geometry inferred from earlier
photoemission results for the Si(111) surface but not for the Ge(111) surface. In a recent SEXAFS study
[62] made on the Si(I11)7x7-CI system, using the ion desorption technique, results were reported that
which are in very good agreement with the previous study made using EAY. The CI-Si bond length was
determined to be 2.00±0.02 A.

The first reliable study [65] of oxygen on a Si substrate was done on Si(I00). Polarization-
dependent 0 K-edge spectra were collected in the my mode for - 1 ML coverage of 0 on Si(100). It
was determined from LEED that at 1 ML coverage, the (2xl) reconstruction at the surface was lost. The
authors found evidence for two types of bridge site occupations: between Si atoms in the first layer and
between Si atoms in the other topmost layers. The O-Si bond length was found to be 1.65 A, and the
Si-O-Si bond angle was - 120°.

3. Molecule-Solid Reactions

The first application of SEXAFS to the study of chemisorbed molecules was made on the formate
(HOCO) on Cu(I00) system [66]. The data was collected using the PAY mode above the 0 K-edge.
Fo~ate is a planar molecule, which in this study was determined to be positioned on the Cu(100) surface
so that the 0 atoms nearly occupied the fourfold hollow sites, with the molecular plane straddling the Cu-
Cu bridge site. This determination was challenged, however, in a later study [67], in which it was shown
that the molecule occupied the "diagonal-atop" site where the C atom is situated directly over the Cu atom
and the molecular plane is positioned along the diagonal of two Cu(tOO) squares. The site assignment
was similar for the Cu(110) surface, but in this case, the molecular plane was aligned with the ridge of
contiguous Cu surface atoms [68]. It was suggested by Crapper and coworkers that the error in the fIrst
study could be attributed to improper Fourier filtering of the data so that insufficient isolation of first and
second shell data was carried out. A recent study [69] using photoelectron diffraction and reassessment
of previous results showed that the site occupancy of formate on both Cu(I00) and Cu(110) is nearly

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identical and of the "aligned-bridge" type in which the 0 atoms are in the atop positions. The Cu-O bond
length was 1.98±O.04 A.

B. Liquid-Solid Reactions

AIthough limited in quantity, EXAFS studies of liquid-solid reactions at surfaces have shown some
of the possibilities in this and related subject areas. Most studies in this subject area have dealt with
aqueous metal sorption on oxides. One of the earliest such studies involved Co K-edge fluorescence yield
EXAFS measurements of CO(N03)2 solutions on reaction with ,,(-AI20 3 and TI02 surfaces [70] to test how
different oxides may affect the sorption process. The sample was prepared by exposing the surface of the
oxides to a modified solution of CO(N03)2' adjusted so that pH values selected would prevent precipitation,
followed by centrifuging the samples on equilibration to remove excess solution. The experiment was
performed at atmospheric pressure in closed vials to prevent loss of liquid. Coverage was estimated to
be - 0.1 ML for C02+ ions. The authors were able to determine that Co was in fact adsorbed on the
surface and not in precipitate form. EXAFS results indicated formation of multinuclear Co complexes on
the oxides: on "(-~03' each Co was found to have six 0 at 2.08 A in the first shell, four Co at 3.12 A
in the second shell, one AI third neighbor at 3.20 A. and a distant Co neighbor at 6.1 A. On TI02• each
Co was determined to have about one Co (at 3.36 A) and one TI (at 3.31 A) in the second shell and no
distant neighbors. The conclusion reached was that Co was bonded to the surfaces of the oxides without
significant precipitation of Co-hydroxide or diffusion of Co into the oxides. The difference in the local
structure of Co adsorbed on the surfaces was interpreted to mean that ,,(-AI20 3 promoted formation of
greater polymerized Co complexes on its surface than of TI02 on its surface. A more recent study of Co
complexes formed on "(-AI203 surfaces as a function of sorption-density [71] showed that as the sorption
density decreases, highly polymerized Co complexes become less important in favor of monomeric
species. A similar study was carried out on Pb complexes formed on ,,(-AI20 3[72] for which the Pb atom
was determined to have one 0 at 2.23 A and two at 2.46 A in the disordered first shell, and one Pb at
3.55 A and one AI -at 3.77 A in the second shell, suggesting that the reaction on the aluminum oxide
surface resulted in the formation of inner-sphere Pb complexes that are less polymerized than Co
complexes on the same surface.

C. Solid-Solid Interfaces

Solid-solid interfaces involve some of the most interesting and complicated problems studied using
SEXAFS, many having direct relevance to technological problems facing us today. Examples include
Schottky barrier formation, clustering. epitaxial growth, compound formation, and solid solution formation.
This are:). of study is divided into three subsections: metal-metal, metal-semiconductor, and semi-
conductor-semiconductor interfaces.

1. Metal-Metal Interfaces

One of the earliest studies on metal-metal interfaces was on the Co on Cu(III) system [73]. The
system was studied for - 1 ML and - 113 ML Co evaporated on Cu(III). The polarization-dependent
SEXAFS results were used to determine that at 1 ML coverage, a two-dimensional monolayer of Co was
formed with each Co atom having 6 nearest neighbors at the same distances as in bulk Co. The Co-Cu
distance was reported to be 0.04 A shorter than the CO-CO distance. It was determined that small, three-
dimensional Co clusters formed at 113 ML coverage. The coordination number was - 3 for Co in this
case, with distances the same as those for bulk Co. This study demonstrated that the extent to which a
s~ace undergoes wetting is a direct function of coverage. A glancing-angle fluorescence EXAFS study
on a 0.01 ML coverage of Hf on a PtlC multilayer [74] (with Hf covered by 10 Aof amorphous carbon)
demonstrated in dramatic fashion the level of sensitivity of the technique. In a recent in situ study of a

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ML coverage of Cu on polycrystalline Pt [75], important to the underStanding of electroplating and
corrosion, the authors collected glancing-angle fluorescence EXAFS data with the sample in the presence
of an electrolyte and an applied voltage. Tentative results suggested up to 4 oxygen atoms at - 1.98 A
in the first shell with the type of second shell atoms undetermined.

2. Metal-Semiconductor Interfaces

One of the first studies of its kind, the SEXAFS study of Ag on Si(111)7x7 [76] was performed
for several coverages. The authors reported that at 1 ML and greater coverage, coexistence of the ordered
and disordered phases occur. However, measurements collected for 0.6 ML coverage indicate a uniform
ordered phase so that complications due to Ag clustering were eliminated. A (f3x.f3)AglSi(111) surface
structure was reported with the Ag atoms located in the interstitial adsorption site. An anisotropy was
determined in the Ag-Si distance, at 2.48±O.04 Aalong the surface normal and 2.46±O.04 Aat 65° relative
to the surface normal. SEXAFS has also been used to study the Pt/Si(111)7x7 system [77], for which it
was also reported (for 0.8 ML coverage) that the metal atom was located in the sixfold interstitial lying
midway between the top and second Si layers. Careful consideration of their results allowed the authors
to make a determination of the relaxation of the Si atoms surrounding the Pt atoms in response to the
interstitial site occupation. It was reported that the top Si layer was lifted by 0.58 Aand that the six Si
atoms moved 0.15 A outward from the Pt atom. Increasing the Pt coverage was reported to promote
intermixing in the top two Si layers, followed by, most likely, nucleation of Pt2Si coordinated clusters.
The authors in a recent study of the CslSi(111)7x7 system [78] attempted to determine the nature of
bonding of the adsorbed atom as a function of coverage, ranging from 0.4 ML to greater than 1 ML. The
nature of bonding at 1 ML coverage is inferred to be covalent and at 0.4 ML is inferred to be ionic, due
to an increase in bond length at lower coverage. There have also been several recent studies of Sb on Si
surfaces: the Si(100)2x1-Sb system studied by Richter and coworkers [79] and the Sb on Si(111) system
studied by Woicik et al. [80] In the first study, SEXAFS and STM were used to determine that Sb
occupied a modified bridge site having the Sb-Sb near-neighbor distance of 2.88±O.03 A. Each Sb atom
is bonded to two Si atoms with a bond length equal to 2.63±O.04 A. In the second study, it was
determined using SEXAFSin conjunction with X-ray standing wave measurements that Sb atoms occupy
threefold atop sites where each Sb atom is bonded to one Si atom. The X-ray standing wave results
indicated that Sb atoms reside 2.53±O.1 A above the Si top layer in clear support of the pyramidal
occupation site model.

3. Semiconductor-Semiconductor Interfaces

Local structure studies of semiconductor-semiconductor interfaces have obvious technological

importance in device applications. Understanding the role of strain and adatom-adatom and adatom-
substrate chemical interactions on the determination of structure at the interface is of great interest. There
have been several studies made on the Ge/Si interface system. In an earlier work, SEXAFS and other
surface techniques were used to study the onset of epitaxy of the SilGe(111) system [81]. A thin Si film
(- 5 A) was grown by solid phase epitaxy on Ge(lll) at room temperature. SEXAFS spectra were
measured, using EAY, as the sample was annealed from 370°C to 800°C. The Si-Si first shell distance
was found to increase from 2.35 A (at room temperature) to 2.44 A (at 800°C), the same as the Ge-Ge
distance, indicating strained Si-Ge bonding. The degree of intermixing (monitored from the Si-Ge signal)
increased with annealing temperature. A faint 1x1 'LEED pattern was observed after the 800°C anneal,
indicating that a pseudomorphic Si-Ge alloy had formed that had a lattice constant of bulk Ge [82]. In
a related study, Comin et al. [83] determined the interface local structure of- 1 ML of Ge on Si(111)7x7
using SEXAFS. The Ge atoms were determined to adsorb in the atop site and bond together to form
chains running parallel to the surface; these chains were bridged together with similar Si chains to

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 terminate the structure. The Ge-Si bond was strongly compressed to 2.38±0.02 A, while the Ge-Ge bond
was found to be unchanged from the bulk value.

D. Buried Interfaces

One of the best applications of the total reflection EXAFS has been for studying buried interfaces .
. The idea behind total reflection EXAFS is simple enough: the angle of incidence is kept below the critical
angle for the substrate layer so that most of the X-ray radiation is reflected off the interface and a small
portion penetrates the substrate layer (typically < 30 A). The fIrst detailed measurements using total
reflection EXAFS were carried out by Martens and Rabe [84] for the K-edge of a copper metal thin fIlm.
The authors pointed out that total reflection EXAFS is generally not directly proportional to the absorption
EXAFS because of a phase and amplitude contribution from the real part of the refractive index to the
signal, whereas the absorption EXAFS is only proportional to the imaginary part. This was deemed to
be a severe drawback for the technique; however, Heald and coworkers [85] demonstrated that, in
conjunction with X-ray reflectivity as a function of incident angle data, a simple analytic correction
scheme can be used to make determinative studies of interfaces using total reflection EXAFS. The
correction involves isolating the real and imaginary part contributions to the collected spectra and
normalizing out the real part. For this study Heald et al. chose the AVCu bilayer system and reported that
the interface was made up of a thin region containing interdiffused Cu and AI and a CuAI2 alloyed phase.
Total reflection EXAFS was used to study the GaN/GaAs(111) interface [86], formed after passivating
GaAs with 200 A of Si3N4 • The authors found that the Ga-N bond lengths at the interface were larger
(2.2 A) than those for bulk GaN (1.94 A). Fourier transforms of their data revealed negligible mixing of
GaAs and GaN. Tan et al. have made an interesting study of ion-beam induced reactions at the AVNb
buried interface [87]. The ion-beam mixing was accomplished with bombardment by 50 keY Ar ions on
the sputtered AVNb sample. Results revealed that the interface was rougher as a result of the ion-beam
mixing and that compound formation and interatomic diffusion were small. Two separable regions were
identified at the interface: a Nb rich layer, having at least short-range order;is immediately below the AI
layer and a relatively disordered AI rich layer is just below the Nb-rich layer. The influence of annealing
on the NilC interface, for Ni-C multilayers, were recently studied using total reflection EXAFS [88].
Annealing at 450°C resulted in the crystallization of the Ni layers from the amorphous phase, as deduced
from the identification of four Ni shells (at 2.45 A, 3.42 A, 4.25 A, and 4.9 A) similar to those of
polycrystallioe Ni foil. The Ni-C bond length was reported at 1.92 A. Evidence from X-ray reflectivity
was seen for increased interface roughness at high teII)peratures, inferred to be due to rearrangement of
atoms at the interface and not to interdiffusion.

VI. FUTURE PERSPECTIVE

One drawback to SEXAFS studies has been the relatively low signal-to-noise ratio due to the small
area of surface exposure and the selection of signal collected. Just as the first generation of dedicated
synchrotron facilities played an important role in 'establishing SE.XAFS as a viable surface technique, the
second generation will be instrumental in bringing improvements in the quality of its data. For example,
the Advanced Photon Source being built at Argonne National Laboratory will provide a synchrotron
radiation flux several orders of magnitude greater (for a small diameter beam suitable for surface studies)
than existing facilities can currently provide. The increase in flux will also enable time-resolved studies,
which are of great interest for studies involving reactions at surfaces, relaxation and reconstruction
processes, and interdiffusion of atoms over time scales presently incompatible with data collection times.

Recently, the trend in SEXAFS research has been to study more complicated surface problems
as our understanding of surfaces increases. Advances in instrumentation, measurement techniques, and
analysis methods have also contributed to this trend. In particular, the theoretical work being done to

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advance the understanding of the EXAFS process has excellent potential in providing a method of fitting
data in r-space that could simplify and shorten data analysis considerably. -

A relatively unexplored area of research related to surface science has been the study of buried
interfaces using total reflection EXAFS. A bothersome complication involving crystalline systems are the
Bragg peaks that complicate the data. As improvements are made in ways to circumvent the problem, this
subject area should attract more interest because of its natural applicability to many technologically related
topics.

ACKNOWLEDGMENT

The author thanks the Department of Physics at the University of Notre Dame for its support while
he was .preparing this manuscript

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70. CJ. Chisholm-Brause, G.E. Brown, Jr., and G.A. Parks, Physica B, 158,646 (1989).

71. CJ. Chisholm-Brause, G.E. Brown, Jr., and G.A Parks, in S.S. Hasnian, Ed., X-ray Absorption Fine
Structure, Ellis Horwood, London, United Kingdom, 1991, p. 263.

72. C.J. Chisholm-Brause, AL. Roe, K.F. Hayes, G.E. Brown, Jr., G.A Parks, and J.O. Lackie,
Physica B, 158. 674 (1989).

73. D. Chandesris, P. Roubin, G. Rossi, and J. Lecante, Surf. Sci., 169, 57 (1986).

74. T.W. Barbee and J. Wong, PhysiCa B, 158. 670 (1989).

75. T.M. Hayes, W. Li, G. Liang, C.M. Lo, T.E. Furtak, E.A Creek, P.Samanta, and L. Wang, in
S.S. Hasnian, Ed, X-ray Absorption Fine Structure, Ellis Horwood, London, United Kingdom, 1991,
p.229.

76. J. Stohr, R. Jaeger, G. Rossi, T. Kendelewicz, and I. Lindau, Surf. Sci., 134. 813 (1983).

77. G. Rossi, D. Chandesris, P. Roubin, and J. Lecante, 1 Physique C, £, 521 (1986).

78. D.R. Batchelor and D.A King, in S.S. Hasnian, Ed., X-ray Absorption Fine Structure, Ellis Horwood,
London, United Kingdom, 1991, p. 200.

79. M. Richter, J.C. Woicik, J. Nogami, P. Pianetta, K.E. Miyano, AA Baski, T. Kendelewicz,
C.E. Bouldin, W.E. Spicer, C.P. Quate, and I. Lindau, Phys. Rev. Lett,.Q2., 3417 (1990).

80. lC. Woicik, T. Kendelewicz, K.E. Miyano, PL. Cowan, C.E. Bouldin, B.A Karlin, P. Pianetta, and
W.E. Spicer, Phys. Rev. B, ~ 3475 (1991).

81. J.C. Woicik, R.S. List, B.B. Pate, and P. Pianetta, J. Physique C, £, 497 (1986).

82. For details of a similar recent study, please see J.C. Woicik, C.E. Bouldin, M.I. Bell, 10. Cross,
D.J. Tweet, B.D. Swanson, T.M. Zhang, L.B. Sorenson, C.A King, lL. Hoyt, P. Pianetta, and
J.P. Gibbons, Phys. Rev. B, ~ 2419 (1991).

83. F. Comin, S. Paolone, and G. Rossi, Surf. Sci., 2111212. 511 (1989).

84. G. Martens and P. Rabe, Phys. Status Solidi A, ~ 415 (1980): G. Martens and P. Rabe, J. Physique
C, H. 1523 (1981).

85. S.M. Heald, H. Chen, and 1M. Tranquada, Phys. Rev. B, ~ 1016 (1988).

86. E. Dartyge, A Fontaine, G. Tourillon, J.F. Peray, R. Joubard, and P. AInot, Physica B, 158. 679
(1989).

87. Z. Tan, J.I. Budnick, Y. Bruynseraede, W. Sevenhans, S.M. Heald, and J.M. Tranquada, Physica B,
158.686 (1989).

88. G.E. van Dorssen, EJ. Puik, P. Mackle, and H.A. Padmore, in S.S. Hasnian, Ed., X-ray Absorption
Fine Structure, Ellis Horwood, London, United Kingdom, 1991, p. 245.

7-20
 "
- - : : ... .
,

"0 "
.- - '
, ..
.

Figure 1. Illustration of outgoing photoelectron wave (solid line) and the portion of the wave scattered
from the surrounding atoms (dashed line).

B
Figure 2. Schematic of adatom A in a three-fold hollow site configuration with substrate atoms B. E is
the X-ray electric field vector, R is the near neighbor distance, and a and 8 are the angles made
by E and RAj relative to the surface normal, respectively.

7-21
 PHOTO- PHOTO- AUGER
ELECTRON ELECTRON ELECTRON

----+---~~~-- 2P3~
~---J---_---eH--- 2P I~
----+---~~__f_-- 2S

Ku,FLUORESCENT
PHOTON
------1__- - - 8 - - IS
IS

Figure 3. Schematic of the photoemission of a K shell core electron due to the absorption olan X-ray
photon and the annihilation of the resulting core hole by two mechanisms: (a) Ku tIuorescence
and (b) Auger electron emission.

,,
++
Binding Energy 0'
E~".-Ev . Kinetic Energy
__-,-----'-- photoemission I ~,
hv

VB '

A B 1.1"I'-\'i",~.U'" Auger
partial Auger

total yield

Figure 4. Schematic showing the photoemission spectra and a simplified three-level system associated
with the profile. An electron is photoemitted from core level A. B. or the valence band (VB)
after the absorption of an X-ray photon with energy hv. The energy zero is chosen at the
Fermi level (Ep). which is separated from the vacuum level (By) by the work function ~.The
energy window settings used with the various detection modes are shown below ' the
photoemission spectra. Adapted from Reference 1.

7-22
 8. HIGH RESOLUTION ELECTRON ENERGY LOSS SPECTROSCOPIC
CHARACIERIZATION OF INSULATORS FOR Si TECHNOLOGY

M.Uebr
. IBM Research Division
Thomas 1. Watson Research Center
P. O. Box 218
Yorktown Heights, NY 10598

P. A. Thiry
Laboratoire LISE
Facultes N.D. de la Paix
61, Rue de Bruxelles
B5000 Namur, Belgium

ABSTRACT

High resolution electron energy loss spectroscopy (HREELS) in conjunction with a number of
other surface analytical techniques has been applied to study semiconductor and insulator surfaces and
interfaces of technological importance. Results are presented for HREELS applied to characterize single-
crystalline Si02 surfaces, CaF/Si(111) interfaces, as well as thin-film SiO/Si(100) grown in situ by
thermal oxidation or by chemical vapor deposition. Interface phonons can be identified for thin epitaxial
insulator films and thin film properties (dielectric function) can be obtained for thin amorphous films. The
mechanisms of hydrocarbon removal from Si wafers by HF and ultraviolet-ozone cleaning, processes
crucial for Si technology, are revealed.

The complete article is published in J. Electron Spectros. ReI. Phenomena, 54/55. 1013-1032
(1990) (41 references). .

8-1
 9. SURFACE MODIFICATION TECHNIQUES: A SUMMARY REPORT

Kash Mittal
IBM US Technical Education
500 Columbus Avenue
Thornwood, NY 10594

I. INTRODUCTION

Surface modification of materials is of tremendous significance in a legion of technological

applications. As a matter of fact, surface modification offers the best of both worlds: one can modify
the surface to attain desired surface characteristics without altering the bulk properties. Both inorganic
(metals, ceramics, glass) and organic (polymeric) materials are modified for many and varied reasons or
purposes (decorative, functional, protective), and a large number of techniques exist to modify surfaces.
The choice of the proper technique for surface modification in a given situation depends on a host of
reasons, e.g., nature of substrate material, intended purpose of surface modification, and economic
considerations.

This Summary Report covers the following: various reasons for modifying both inorganic and
organic surfaces, general surface modification techniques, separate catalogs of modification techniques
specific or suitable to inorganic and organic materials, and research needs.

The field of surface modification is very dynamic and vibrant; much has been accomplished, but
much more needs to be done and understood.

II. INORGANIC (METALS, CERAMICS, GLASS) SURFACES MAY BE MODIFIED TO

• Make them more adhesionable

• Increase their adhesion durability
• Improve tribological behavior
• Improve corrosion resistance
• Reduce degradation due to environment
• Improve mechanical properties
• Alter surface electrical characteristics.

m. POLYMER SURFACES MAY BE MODIFIED TO

• Make polymer surfaces more adhesionable

• Increase their printability
• Make polymer surfaces more wettable
• Make polymer surfaces hydrophobic (low energy, less wettable, nonsticky)
• Provide an enclosing layer
• Improve tribological behavior
• Prepare polymer surfaces for metal plating
• Provide enzyme immobilization
• Provide flame resistance
• Provide luster
• Provide antistatic properties
• Control permeation/diffusion

9-1
• Alter surface conductivity
• Improve abrasion/scratch resi~tance
• Reduce electrostatic charging problem
• Control surface electrical characteristics
• Alter optical characteristics
• Reduce/prevent degradation by deleterious environment

IV. SURFACE MODIFICATION 1ECHNIQUES ARE USED FOR

Inorganic Materials (metals, alloys, ceramics, glass) and organic materials (polymers).

A. Broad Approaches to Surface Modification

The objective is to obtain a surface with desirable topography, chemical moieties, or

mechanical/metallurgical characteristics.

1. Chemical

• Creation of new surface chemical groups (surface restricted, deep)

• Deposition of a discrete layer (coupling agent, grafting, Langmuir-Blodgett [LB] film, metal layer)
• . Removal of some surface material (contamination, plasticizers, additives).

2. Physical

3. Mechanical

4. Metallurgical

Note: The surface modification techniques can also be broadly classified into two categories: wet and
dry.

B. General Surface Modification Techniques

• Chemical
• Physical
• Mechanical
• Metallurgical
• Microbial
• Vacuum evaporation (removal oflow molecular weight [mol. wt] materials)
• Pressure (removal of weak boundary layers)

1. Chemical Surface Modification

• Chemical reactions (oxidation, sulfonation, ozonation, phosphatization, chromate conversion,

amination, .. .)
• Grafting
• Selective etching
• Deposition of LB monolayers
• Deposition of coupling agents, e.g., sHanes (also silane deposition followed by plasma treatment)
• Surfactant adsorption

9-2
• Photochemical, using proper photoactive compounds
• Solvent (surface swelling) .
• Dissolution (proper second phase in contact, which can dissolve undesirable low mol. Wt. materials)
• Prevention of diffusion of low mol. wt. materials to the surface
• Electroless metal deposition.

2. Physical Surface Modification

• Plasma • UV sensitized • Ion bombardment

- Radio frequency (RF) • Ozone • Ion implantation
- Microwave • UV/Ozone • Ion plating
• Corona • X-ray • 1bin metal layer
• Flame • Laser deposition
• Ultraviolet (UV) • Electron •

3. Mechanical Surface Modification

• Blasting or abnision in air

• Surface texturing (lithographic technique)
• SABRA (Surface Activation Beneath Reactive Adhesive)
• Casting against other materials (e.g., polymers against Pt, Hg)
• Rubbing against other materials.

4. Metallurgical Surface Modification

Metallurgical techniques include those that modify the mechanical (tribological, abrasion) or
corrosion characteristics.

• Ion implantation
• Ion plating
• Cladding
• Laser
•

v. RESEARCH NEEDS

A. Organic (polymeric) Surfaces

• Cross-compare various modification techniques (plasma, corona, flame, etc.).

• Understand the deactivation of the treated surface, both mechanistic and kinetic aspects.
• Explore further the laser surface modification technique.
• Understand the mechanism of photochemical modification approach.
• Investigate the relative chemical versus mechanical contributions to adhesion to polymer surfaces.
• Characterize acid-base relationships by two or three different techniques and cross-compare; also,
compile a comprehensive data base relative to acid-base characteristics.
• Explore in detail the relation between acid-base functionalities on the surface and their adhesion to
a variety of overcoats, including metals.
• Understand the mechanism of silanes as adhesion promoters on polymeric surfaces. Also, other
adhesion promoters should be investigated on organic substrates.
• Understand metal-polymer interactions in d.etail.

9-3
B. Inorganic (Metals, Ceramics, Glass) Surfaces

• Investigate the relative chemical versus mechanical contributions to adhesion to such surfaces.
• Understand the mechanism of the photochemical modification approach.
• Cross-compare acid-base characteristics derived by different methods.
• Understand interactions of sHanes (adhesion promoters) with inorganic substrates using acid-base
concepts.
• Explore in detail the relevance of acid-base functionalities on the surface and their ·adhesion to a
variety of overcoats.
• Explore further the mechanism by which plasma polymerized sHanes function as adhesion promoters.

9-4
 10. ELECTROCHEMICAL DEPOSmON lECHNIQUES

Peter C. Searson
Department of Materials Science and Engineering
The Johns Hopkins University
Baltimore, MD 21218

I. INTRODUCTION

Historically, electrochemical techniques have been used for the deposition of metals and alloys
to improve the corrosion resistance or specific physical or mechanical properties. Traditional applications
have been in the aerospace, automotive, oil and gas, and chemical processing industries. However, recent
advances in electrochemical processing of materials and the development of novel deposition techniques
have expanded the use of electrodeposition methods in these and other industries. In many cases, these
advances have been related to applications in the electronics industry.

Novel materials processing has included the development of techniques for the electrodeposition
of semiconductors, superconducting oxides, and conducting polymers, as well as composite films
combining the properties of these materials. Electrodeposition techniques are now being used to provide
specific magnetic, electrical, and electromagnetic properties; chemical and electrochemical properties,
including corrosion resistance and catalytically active surfaces; and optical properties such as reflectivity
and absorptivity.

1b.is article highlights some of the novel materials and structures processed by electrochemical
methods. In addition, examples of new techniques for electrodeposition are also described. Specific
procedures for the electrodeposition of metals and alloys are not reviewed, but are available [1,2].

n. ELECTRODEPOSmON OF METALS

In the electronics industry, electrodeposition and autocatalytic (electroless) deposition are used in
the fabrication of a wide range of components. Advances in autocatalytic deposition have resulted in the
development of techniques for many applications, and commercial processes are in use for the
autocatalytic deposition of nickel, copper, and gold. Electroless nickel is used in a wide range of
engineering and electronics applications, and electroless copper is used in the fabrication of printed circuit
boards and mirrors (as well as electroless silver). Composite coatings of electroless copper or nickel on
plastic substrates have been proposed for electromagnetic interference shielding [3].

'The metallization of circuit boards is carried out by additive electrodeposition techniques [4].
Typically, lithographic techniques are used in conjunction with electroless copper deposition catalyzed by
a noble metal addition. Metallization has been achieved using both negative and positive resist techniques
[5]. Recently, photoselective deposition of a gold catalyst has been used for the fabrication of patterned
copper metallization [6], eliminating the need for a resist and reducing the number of steps required to
create a patterned deposit In related work, tin chloride has been used for the photoselective deposition
of palladium as a catalyst for electroless deposition [7-9]. In integrated circuit fabrication, selective
electroless deposition of Ni, Pd, and Cu has been used for contact filling, via holes, and conductor patterns
[10,11].

Electroless gold is routinely used in the electronics industry for contacts, connectors, printed circuit
boards, and lead frames [12] as a result of its high conductivity and corrosion resistance. Small

10-1
concentrations of nickel or cobalt are commonly added to electroless gold for wear-resistant applications
such as sliding contacts. Electroless gold deposits can be obtained by displacement of a less noble metal
substrate, although the films are relatively thin « 0.25 J.Ull), because the process stops when the substrate
is completely covered. More commonly, autocatalytic deposition is used for thicker and more uniform
fIlms [13].

Electroless deposition of cobalt-based alloys is used for magnetic media applications. Thin-film
rigid memory disks are commercially fabricated using either electroless deposition- or sputtering [14].
Typically, a magnetic cobalt-based alloy of 50-100 nm in thickness is autocatalytically deposited onto .an
electroless nickel-phosphorus film on an aluminum substrate. The cobalt-based alloys are gerierally
deposited from buffered amino acid solutions with a sodium hypophosphite reducing agent producing
highly uniform films with crystallite sizes on the order of SO nm. .

Another important application of electrodeposition in the electronics industry is the fabrication of

ohmic contacts to semiconductor materials. For example, ohmic contacts for InP in transistor and laser
applications are usually made by a vacuum process. Ohmic contacts have been formed by electroless
deposition of Ni-Zn-Au on p-type InP [15] and Au-Pd on n-type InP [16]. Similarly, electroless deposits
of Au-in-Pd have been used to produce ohmic contacts on GaAs.

Many industrially important metals with low equilibrium potentials, such as aluminum, titanium,
and molybdenum have been electrodeposited from nonaqueous solutions. It is well known that aluminum
can be electrodeposited from organic solvents (e.g., AlBr3 + KBr in toluene [17,18] or AlCl3 + LiAlH3
in tetrahydrofurone[19]) or molten salts (e.g., AlCI/NaCI [20,21]), and commercial processes are in use.
Recently, supercritical organic electrolytes have also been used to electrodeposit aluminum ftlms [22].

New developments in techniques for electrodeposition for microelectronics applications have been
related to patterned deposition or the ability to deposit selectively onto a substrate. Lithographic
techniques and photoselective deposition of catalysts.for electroless deposition have been described above.
In other work, laser-induced deposition has been used to deposit copper and gold on both metallic and
semiconductor substrates. This technique is an open-circuit process and can be used to fabricate patterned
deposits without a mask [23-26]. In this case, temperature is used to modify the position of the
equilibrium potential in a localized region so that electrodeposition is driven by the potential difference
between this region and the nonirradiated regions. In a further modification of this technique, laser-
enhanced jet plating has been used to fabricate high-density and pore-free gold deposits [27]. High-purity
gold tracks have also been deposited on silicon and SiOl using the photoelectrochemical reduction of
gaseous methyl(triethylphosphine) gold (I) [28] in which l5-60-J.Ull-wide tracks 30-70-nm thick were
deposited at a rate of 35 J.1II1/s.

In the automobile industry, examples of recent developments include the increased use of
electrodeposition of stainless steels and the fabrication of composites of electrodeposited aluminum and
plastic [29]. Electrodeposition of zinc and zinc-nickel alloys is widely used for corrosion resistance, and
autocatalytic deposition of nickel is used in the fabrication of a number of engine components. Novel
applications for autocatalytic deposition include surface modification of plastics, e.g., conducting contacts
on plastic components.

m. ELECTRODEPOSITION OF SEMICONDUcrORS

Electrochemical methods for the fabrication of semiconducting materials have received only
limited attention in the literature. Most work in this area has been related to the electrodeposition of metal
chalcogenides for solar energy applications. At present, there have been no techniques developed for the

10-2
electrodeposition of gallium arsenide, although silicon has been deposited in small quantities from molten
salts and from nonaqueous solvents with high impurity concentrations. In contrast, high-quality thin films
of germanium have been prepared using relatively straightforward techniques.

A wide range of metal chalcogenide compounds has been prepared by electrodeposition. One of
the first successful techniques for the deposition of compounds such as CdS and Bi2S3 involved anodic
oxidation of the metal in an electrolyte-containing sulfide, selenite, or telluride [30,31]. Subsequently,
CdSe and CdTe were deposited by reduction of the metallic ion in acidic solutions of Se02 and Te02,
respectively [32-35]. However, the reduction of the chalcogenide X4+ to X:. (where X = S, Se, Te) usually
resulted in a significant fraction of the elemental form in the films. More recently [36], CdSe, CdTe, and
CdSexTel .X have been prepared from cyanide solutions containing SeO and TeO resulting in thin films with
negligible concentrations of the elemental chalcogenide. High-quality polycrystalline CdS films have been
prepared by the reduction of cadmium in nonaqueous sulfide solutions [37,38]. A combination of
electrodeposition and reaction annealing in HzSe has been used to prepare CuInS~ solar cells with 10%-
11 % efficiency [39]. More recently, photoanodes of this ternary chalcogenide have been prepared by
direct electrodeposition without. any subsequent heat treatment [40,41]. ZnS films have been
electrodeposited from aqueous ZnS04 and NazS203 solutions buffered to alkaline pH with NaOH [42].
Zinc reduction was suppressed by complexing with EDTA (ethylanediamene tetraacetic acid)

Of the IV-VI compounds, techniques have been developed for the electrochemical deposition of
SnSe [43] and SnS [44]. Thin films of p-type snS were electrodeposited from solutions of SnCl2 and
tartaric acid in ethylene glycol saturated with elemental sulfur.

In addition to the metal chalcogenides described above, a number of oxides, including TI20 3, IrQ2'
Mo03, W03, and Pb02, have been prepared by electrodeposition techniques. Thermodynamically, the
oxide ~03 is stable at potentials positive to the domain of stability of the soluble ion TI+ at certain pH
values [45]. As a result, the solid oxide can be deposited by the direct electro-oxidation of the soluble
ion onto a suitable substrate. Switzer et al. [46] developed a technique for photocatalytic deposition of
~03 on silicon substrates by oxidation from alkaline TI+ solutions. Thin fIlms of iridium oxide have been
electrodeposited by both anodic and cathodic deposition from IrCl4 in an alkaline electrolyte of hydrogen
peroxide, oxalic acid and KC03 [47]. The deposited films were amorphous, but changed to crystalline
after heat treatment at 500°C. For electrochromic applications, techniques have been developed for the
electrodeposition of Mo0 3 [48] and W03 [49] from solutions containing the dissolved metal. Doped
B-Pb02 thin-film electrodes for electrocatalytic applications have been fabricated by electrodeposition from
acidic Pb(N03)2 solutions onto noble metal substrates [50-52].

The conditions for the electrochemical deposition of germanium were established over 40 years
ago [53-55]. High-qUality thin films of germanium have been prepared from GeC14 and GeI4 in
nonaqueous solvents such as glycols and polyalcohols [56,57].

Silicon deposition has been reported from both molten salts and nonaqueous solvents. Feigelson
and coworkers have reported on the electrodeposition of silicon from ~SiF6 [58] and BaOlSi02IBaF2 [59]
melts. In the molten ~SiF6 electrolyte, polycrystalline films up to 3-mm thick were formed with a grain
size of about'l00 1JIIl. At potentials close to the equilibrium potential, total impurity levels as low as
10 ppm were obtained. Deposition from the BaO/SiOiBaF2 melt was analogous to the Hall process used
in aluminum production. Deposition rates in excess of 100 mA/cml,were used to deposit 2-mm-diameter
particles at a current efficiency of about 20%. These authors reported a purity of 99.97% with a room-
temperature resistivity of 0.2 .a cm, corresponding to an impurity concentration of about 1018 em·3•

10-3
 A number of groups have reported on electrodeposition of silicon from nonaqueous solvents
[60-63]. Relatively smooth, uniform films up to 200-nm thick have been deposited from SiHCIs in
tetrahydrofuran [60]. However, the bulk concentration of impurities in these films was on the order of
18 at %, much higher than that for the films deposited from the molten salts.

In the last few years, gallium arsenide solar cells have achieved relatively high energy conversion
efficiencies; however, attempts to electrodeposit GaAs have been unsuccessful to date. Gallium may be
electrochemically deposited from acidic or alkaline solutions when the oxide G~03 is not stable. In the
literature, there are reports of gallium deposition from acidic sulfate solutions and alkaline gallate solutions
from more than 50 years ago [64-66]. In contrast, the domain of stability of elemental As is only about
0.5 V due to the formation of gaseous arsine, AsH3, at low potentials. Despite this limited domain of
stability across the pH range, As has been electrochemically deposited in acidic, neutral, and alkaline
aqueous solutions under a variety of conditions [67,68]. In general, these deposits were formed at ambient
temperatures and were typically 0.1-1O.0-mm thick. Arsenic has been deposited under conditions of
constant current from solutions of ~03 dissolved in concentrated HCI [69,70]. In alkaline conditions,
As has been deposited from ~03 dissolved in NaOH and in KCl/N~C03 solutions [67]. Neutral solu-
tions of ~03 dissolved in KCN have also been used to electrochemically deposit As. High-quality As
films over l00-mm thick have been prepared from nonaqueous solutions of AsCl3 dissolved in acetone
(70). The same authors have also reported preparing even thicker ftlms using dimethyl acetone as the
solvent, although high temperatures (1()()0C) and high cell voltages (over 2()() V at 0.1 Ncm2) were
required.

On the basis of equilibrium thermodynamic data for Ga and As [45] and taking the Gibbs free
energy of formation of GaAs as -77.4 kllmol, a limited domain of thermodynamic stability for GaAs is
predicted, corresponding closely to the domain of the stability of arsenic [71]. Although recent attempts
at GaAs deposition from aqueous solutions were not successful [72], there have been no comprehensive
studies using nonaqueous solvents. Poly'crystalline GaSb films have been prepared by sequential
deposition of Ga and Sb from aqueous solutions followed by annealing at I()()OC [73].

IV. SUPERCONDUCTING OXIDES AND PEROVSKITES

Since the discovery of superconducting oxides with transition temperatures above the liquid
nitrogen temperature, there has been considerable interest in the chemistry of the IIA and IlIA elements
Y, Ca, Ba, and Sr. There have been a few reports of direct electrodeposition of a number of super-
conducting oxide precursors from nonaqueous solvents [74-76], however, in all cases, the deposited
precursors required a high-temperature oxygen anneal after the deposition step. Bhattacharya et al. [74,75]
reported on the electrodeposition of - 3-fJII1 thick TI-Ba-Ca-Cu-O and Y-Ba-Cu-O precursors on sm03
and MgO substrates using DMSO (dimethylsulfoxide) as the solvent After annealing, these authors
reported transition temperatures of 102 K for TI-Ba-Ca-Cu-O and 76 K for Y-Ba-Cu-O films. Maxfield
et al. [76] electrOdeposited Bi-Sr-Ca-Cu-O and Pb-Bi-Sr-Ca-Cu-O precursors from DMSO. The post-
annealed films exhibited zero resistance at 70 K and 40 K, respectively.

In an alternative approach, Zurawski et al. [77] have reported on preliminary results involving the
oxidation of copper in barium hydroxide solution to form a copper oxide containing 20% barium. Konno
et al. [78] have reported on the electrodeposition' of La1•xC3xCr03 precursors from chromate solutions
containing La(N03)3 and Ca(N03h. The precursors were converted to perovskite oxides after heat
treatment above 700°C in air. Rosamilia and Miller [79] have reported on electrodeposition of sliver,
copper, lead, and tin on Y-Ba-Cu-O superconducting oxides from acetonitrile. Such metallic films provide
both corrosion resistance and low resistance contacts in device fabrication.

10-4
v. REFRACTORY COMPOUNDS

Recently there has been interest in the electrodeposition of refractory compounds.

Electrodeposition of M~C from molten salts has been reported by a number of authors [80,81]. Recent
work has reported on the deposition of dense, pore-free films on nickel-plated steel substrate from an
alkali molten salt of LiFlNaF/KF and ~C03 with the addition of N~Mo04 [80].

VI. ELECTRODEPOSmON OF CONDUCTING POLYMERS

Many aromatic'heterocyclic compounds can be electrochemically oxidized at an electrode surface

to form an electrically conducting polymer film. Comprehensive summaries of the fabrication and
properties of cOnducting polymers are available [82-84]. At the present time, the main applications of
research in this area are rechargeable polymer batteries, electrochromic devices, electrocatalysis, and host
materials for enzymatic biosensors.

Conducting polymers can be deposited by electrochemical polymerization of the monomer under

oxidizing conditions. Electrochemical polymerization has the advantage that thin-film structures can be
fabricated directly onto a suitable substrate. Examples of conducting polymers that have been
electrochemically synthesized include polypyrrole, polythiophene, polyacetylene, and polyaniline.

There have been a number of reports of incorporation of catalysts into thin polymer films [85,86].
These modified electrodes have been shown to exhibit higher efficiencies and durability than adsorbed
monolayers. The polymer ftlm provides a host material of high conductivity, and the catalyst is
incorporated at the electrode surface in relatively high concentrations.

VII. COMPOSllE MATERIALS

A. Multilayer Structures

Thin-film multilayer structures represent a new class of materials" many of which exhibit unique
optical, electrical, magnetic, and mechanical properties. Electrodeposition has been used to fabricate
compositionally modulated metallic multilayer structures of Cu-Ni, Cu-Co, Cu-Pd, Ag-Cu, Ag-Pd, and
Au-Ni [87-89]. These materials are of interest for their mechanical and magnetic properties. Recently,
Switzer et al. [90] have reported preliminary results on the electrodeposition of compositionally modulated
TI.Pl\Oc structures with modulation wavelengths on the order of 5 om.

A schematic diagram of this type of structure is shown in Fig. la. The two components, A and
B, are deposited sequentially, either by sputtering or electrodeposition, to form a multilayer structure with
a characteristic wavelength, A.

B. One-Dimensional Structures

Composite structures consisting of a metal wire within an inert host material have been used for
applications such as magnetic recording media [91-94] and grid-type micropolarizers [95]. These
structures are shown schematically in Fig. lb. An effective method for producing such structures is by
electrodeposition of the metal or alloy into a porous material. Several groups have reported fabricating
magnetic recording med,ia by electrodeposition of iron [91-93] and cobalt alloys [94] into 3-4-J.UIl-thick
porous anodized aluminum oxide.

10-5
 Encapsulated wire electrodes are routinely used as microelectrodes for applications in
electroanalytical chemistry. In many cases, single disk electrodes are fabricated by electrodeposition of
a metal such as gold or platinum into a glass capillary of 1-10-JIDl diameter [96]. In related work, Penner
.and Martin [97] have reported on the electrodeposition of platinum into 200-nm-diameter pores in
polycarbonate membranes (Nuclepore, Inc.). Similar techniques have been used to fabricate wires of
conducting polymers, as described in the next section.

C. Composite Polymer Films

Several researchers have reported on electropolymerization of conducting polymers into

microporous materials. Penner and Martin [98] electrodeposited polypyrrole into I-J.1IIl-diameter
cylindrical pores in polycarbonate membranes. The conductivity of these highly oriented polymer fibers
was reported to be as much as an order of magnitude larger than that of a thin film of the same thickness.

There have been a number of reports of electropolymerization of polyaniline in insulating

. polymeric host materials [99,100]. Similar results have been achieved by chemical polymerization of a
conducting polymer in a host material [101]. Crata and Buttry [99] electropolymerized polyaniline in a
solution-cast Nation (E. I. DuPont de Nemours and Co.) film. These composite films were fabricated by
solution-casting Nation and aniline in an appropriate solvent followed by electropolymerization of the
aniline to form an interconnected network of the conducting polymer through the host matrix. These
composite films are reported to have higher conductivities and faster switching rates due to enhanced
proton transport. This type of composite structure is shown schematically in Fig. lc.

Bard and coworkers [102] have reported on the deposition of silver and copper in a thin film of
an ionic conductor using a scanning tunneling microscope (STM). The S1M tip was used as a counter
electrode with a metallic substrate serving as a working electrode. A Nation film was used as the
electrolyte and soaked in solution of silver or copper ions prior to deposition. The metal ions in the'film
were reduced under conditions of constant potential, and tracks about O.I-JIDl wide could be written into
the Nation film by using the translational stage of the STM.

D. Particulate Composites

The fabrication of particulate composite materials can be achieved through electrodeposition of

the metallic host in an electrolyte containing the second phase particulate material. This technique has
been developed commercially in the last few years for the fabrication of wear-resistant coatings by
incorporation of relatively large-diameter particles (on the order of 1-10 JIDl). These structures are shown
schematically in Fig. Id.

For the electrodeposition of particulate composites, the only requirement is that the second phase
can form a stable suspension in the electrolyte. Examples of the particulates include carbides [103-105],
oxides [104,106], and diamond [107]. For electrodeposited composites of relatively large particle size
(> 1 J.1IIl), volume fractions of the particulate in the range of 0%-30% have been repOrted.

Autocatalytic deposition of nickel has also been used to fabricate composite Nilpolytetrafluoro-
ethylene (PIFE) films using - l-JIDl PTFE particles [108,109]. Indeed, NiIPTFE composites are used
commercially in a number of aerospace, electronics, and automotive applications due to their enhanced
wear resistance and relatively low cost Composite NilCr3~ films have been fabricated by autocatalytic
deposition of nickel from an electrolyte containing Cr3~ particles 2-3 JIDl in diameter [110].

10-6
 In addition to research into composites with relatively large particles (> 1 1JIIl), there has been
some work directed toward composites with submicron particles. Fpr example, Auf Alz03 composites have
been electrodeposited using 50-nm alumina particles [11 Il.

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10-8
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10-10
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10-11
A Ie.
metallic layers
B ~}~%'f:%t®'t.&'Mt?K:'$gK¥i?t.K (a) Metallic Multilayers
A (compositionally

t wavelength. }.
modulated alloys)

(b) One-Dimensional
Structures

deposition into intercoMected

~B ,_"""",1_)
network of pores (e.g. metal.
(,) Fib..... S'm"'"
matrix (e.g. polymer. glass)

... ...
-..-
paniculare (e.g. ceramic•
•• • • polymer. metal) (d) Particulate Composites
matrix (e.g. metal. alloy.
conducting polymer.
semiconductor)

Figure 1. E1~ochemically processed composite structures

10-12
 11. PLASMA-AIDED MANUFACTURING

I. Leon Shohet
Enginee~g Research Center for Plasma-Aided Manufacturing
University of Wisconsin-Madison
Madison, WI 53706

ABSTRACT

Plasma-aided manufacturing, the use of electrically charged particles in the manuf~cturing process,
is used for producing new materials with unusual and superior properties, developing new chemical
compounds and processes, machining, and altering and refining materials and surfaces. It has direct
applications to semiconductor fabrication, materials synthesis, welding, lighting, polymers, anti-corrosion
coatings, machine tools, metallurgy, electrical and electronics devices, hazardous waste removal, high-
performance ceramics, and many other items in both high-technology and the more "traditional" industries.
This .paper describes the nature of plasma-aided manufacturing and how it applies to materials coating.

I. INTRODUCTION

Plasma-aided manufacturing, which we define as the use of electrically charged particles in the
manufacturing process, is an emerging field that will greatly enhance the international competitiveness of
American industry. Plasma-aided manufacturing is used for producing new materials with unusual and
superior properties, for developing new chemical compounds and processes, for machining, and for altering
and refining materials and surfaces.

In order for plasma technology to be utilized in manufacturing, it is necessary that the processing
result be unattainable by other methods, superior products results, or the plasma technology be more
economical. Plasma-aided manufacturing is nowata critical point in its development In the past, it has
been possible to produce "industrial" plasmas for use in plasma-aided manufacturing with limited
knowledge of the plasmas, their chemistry, their specific process control, quality and productivity
improvement, and sophisticated production techniques. Now our industrial colleagues tell us that, without
an in-depth understanding of the variety of phenomena taking place and their application to the industrial
environment, advances in this technology, and its efficient use, will occur at a diminishing rate.
Specifically, our partners have expressed concerns about yields, end-point detection, reliability, processing
rate, aging, and the feasibility of using various plasma processes. Our partners believe that significant
progress demands a cross-disciplinary effort beyond the capability of any single existing U.S. industrial
or university research group.

An illustrative diagram of the various reactions taking place in a plasma processing reactor is
shown in Fig. 1.

Every plasma reactor incorporates the following processes:

• Electron impact ionization and dissociation

• Gas phase chemical reactions

• Surface phase chemical reactions.

11-1
 To maintain the discharge, ionization must occur to sustain the plasma. Electrons are needed to
dissociate the feedstock gases to produce fragmented neutrals that are chemically active (free radicals).
In addition, the ions are often needed, either by themselves or in conjunction with other species in the
plasma, to produce the needed chemical reactions, either in the plasma itself or on the surface of the
material to be processed. Often, the gas-phase chemical reactions tend to be a loss mechanism for the free
radicals produced, serving much as do the recombination processes for charged particles. On the surface
itself, very complex processes occur that are often difficult to quantify; in these processes. the free
radicals, ions; and other particles impinge on the surface causing implantation, sputtering, or etching, or
a combination of a number .of these processes.

When plasmas are utilized in manufacturing, the application and character of the processes
involved are governed by the operating pressure of the system. Typical reactors cover operating pressures
from below lQ4 Torr to greater than atmospheric pressure. Figure 2 shows the types of processes used
in manufacturing as a function of the operating pressure of the reactor. At low pressures, physical rather
than chemical effects dominate. This is the case in plasma source ion implantation, for example. As the
pressure increases, sputtering occurs, and then chemical effects, such as etching, begin to become
significant At higher pressures, deposition effects tend to dominate, and at the highest pressures, as in
thermal plasma spraying, chemical vapor deposition (CVD), and arc-spray coating, the plasma tends to
be utilized primarily as a heat (thermal) source. Viewed in this way, it can be seen that there are many
connections that occur between the various processes. Each of them, for example, has surface and
materials issues. Each process needs to know the gas and surface temperatures and the densities of the
various species making up the plasma. Each needs to develop a modeling capability that can predict the
properties of the materials being processed. .

Accordingly, the relationship between the "external" process variables, such as radio frequency
(RF) power, gas pressure, gas flow rate, etc., which are variables that can be set externally to the reactor,
and the "internal" process variables, such as charged particles, free radical and ' neutral particle
concentrations, and fluxes, need to be determined. An example of how plasma deposition might be treated
in this way is shown in Fig. 3.

II. COATING TECHNOLOGIES

For plasma-aided manufacturing to have an impact on present and future requirements of industry,
new processes, diagnostics, sensors, modeling, and statistical and control strategies need to be developed.
In addition, new studies in basic science and engineering are also needed

Advances in the research base will contribute new insight for the long-term improvement of
plasma-aided manufacturing. In connection with monitoring and control of the manufacturing processes,
for example, four important plasma diagnostics have not routinely been used in industry for control and
mOnitoring. They are: laser-induced fluorescence [1], infrared diode laser absorption [2], vacuum
ultraviolet (VUV) emission as well as Fourier transform infrared spectroscopy, and in situ ellipsometry.

Advances must also be made toward a better understanding of nucleation, growth, surface
diffusion, interfacial roughness, stress, and surface chemistry of plasma-deposited fllms. The influence
of plasma processing parameters on these properties may be determined by using a variety of these in situ
diagnostics. Particular attention will be directed toward understanding the plasma chemistry. Efforts will
be directed toward modeling of fllm growth in the plasma environment based on statistical design
techniques. Specifically, the influence of (1) film thickness, density, and stress on optical properties,
(2) plasma modification of surfaces, and (3) growth of external polymeric surfaces needs to be determined.

11-2
 Problems in the current technology associated with plasma-aided manufacturing are: the lack of
process reliability and optimization, the lack of an engineering base with which to develop process control
and transfer the technology to industry, and a limited knowledge to further expand the applications of the
processes.

The research goal for plasma-aided manufacturing is to develop the diagnostics, modeling~ and
control techniques necessary to utilize these processes effectively in industry. We believe that the
techniques will have applications to a wide variety of plasma deposition processes in one laboratory. It
is necessary to emphasize only a nominal number of processes because there are a very large number of
potential applications~ Following is a brief discussion of a number of plasma coating processes and
current research efforts in the Engineering Research Center (ERC) for Plasma-Aided Manufacturing.

A. Plasma Polymerization

In the ERC, a parallel-plate 13 MHz reactor called P4 (parallel-plate plasma polymerization) is

an engineering test bed for plasma polymerization. P4 is shown in Fig. 4. It has been designed to ensure
compatibility with the various diagnostic tools being develo~d in the ~RC. It is also computer-controlled
to facilitate the real-time control of the deposition process and the acquisition of diagnostic data. The
current material under test in this system is polymethylmethacrylate (PMMA). This material is deposited
on silicon substrates that can either be coated with a conducting or insulating film or can be uncoated.
The deposition pressure is approximately 100 mTorr. Subsequent modifications to the reactor will include
the.use of electron cyclotron resonance (ECR), RF.induction, and/or magnetically-confined plasma sources.

P4 is outfitted with a personal computer (pc)-based controller so that automated deposition

processes are possible. This facilitates statistical experiments and the use of statistical process control.
Diagnostics include Langmuir probes, optical emission spectroscopy, laser-induced fluorescence, and mass.
spectrometry, and they allow the determinatio·n of electron temperatures and densities, reactive species
present, and their concentrations and plasma potential. These data will be used in conjunction with plasma
modeling to help understand the plasma kinetics and the surface and growth kinetics of the plasma
polymer. The modeling effort uses a particle-in-cell approach to model plasma kinetics. Statistical
techniques will be used to determine how the plasma process parameters (such as power, flow rate, and
pressure) are related to the internal plasma parameters (such as electron density and temperature) and how
the plasma process parameters are related to the desired materials properties (such as refractive index,
dielectric behavior, and residual stress). Given this information, it will be possible to tailor the material
properties of the deposited polymer films [3]. In particular, we plan to fabricate polymer channel
waveguides with graded indices of refraction for waveshaping applications in photonics. To achieve this
goal, we need to deposit films on the order of 5-10-1JlD thick. This will require that the deposited films
have minimal residual stress. A major research goal is to utilize statistics, diagnostics, and modeling tools
to develop a mechanistic model for residual stress in PPMMA films.

B. ECR Deposition

This activity is a collaborative effort between the ERC and several industrial partners. We are
optimizing the deposition using ECR plasmas to ensure the desired materials properties of the deposited
films. The materials systems of interest are alternate vapor sources for the deposition of silicon
compounds. The source most frequently used now, silane, presents safety hazards because it is exposed
. to ambient air. ECR has a number of promising advantages for deposition, and we expect to determine ·
and optimize its effectiveness by using the diagnostics and modeling methods made available through the
ERC.

11-3
 One industrial partner will provide the ERC with a number of novel liquid vapor sources to use
as silane gas substitutes in the ECR deposition of silicon nitride; this is.of great interest to semiconductor
manufacturers. The ERC diagnostics will be used to develop an understanding of the nitride deposition
process. In particular, as the chemical kinetics are understood, we expect to interact with our industrial
colleagues to design more advanced molecules that will minimize unwanted free-radical composition. The
deposited films will be characterized using facilities available on campus. The chemical composition will
be investigated using Auger electron spectroscopy and electron spectroscopy for chemical analysis
(ESCA). The refractive index in the visible will be measured with 'a three-color ellipsometer, and the
dielectric b~havior will be characterized using a capacitance-voltage system.

C. Plasma-Deposited Barrier Coatings

Several industrial partners have expressed an interest in developing plasma-deposited sources and
processes for surface-selective deposition of barrier coatings in or on forms of varying shape and scale.
Barrier coatings are required on certain containers to prevent the permeation of gases such as oxygen
through container walls or to prevent the escape of vapors out of the container. In certain cases, plasma-
deposited coatings have either a processing or a performance advantage over conventional methods such
as co-extrusion and wet or gas chemical deposition. As an example, plasma-deposited polymer coatings
are highly cross-linked, and the deposition process does not produce substantial amounts of chemical
waste, as does a wet chemistry process. Unfortunately, however, many plasma source systems do not
physically deposit coatings that conform to the odd shapes of tubes, bottles, and other hollow and re-
entrant forms.

We are investigating plasma deposition of barrier coatings with several RF capacitive and
inductive plasma sources. Working with our industrial partners, we will apply our expertise in plasma
engineering to design sources and processes directed toward a number of contemporary manufacturing
goals. Our activities will draw from nearly every facility and support group within the ERC. Plasma
source design and construction will require RF electromagnetic field modeling, two-dimensional (2-D)
plasma modeling, and much of the Center's plasma diagnostic capabilities, such as electric probes, optical-
emission spectroscopy, infrarede (IR) spectroscopy, and mass spectrometry. Process development will
require film characterization studies, statistical experimental design, and testing of surface-barrier aging
and performance. By placing the source design directly within the context of our partners' industrial
applications, we will ensure the transfer of technology and engineering advances.

D. Plasma Modification of Fibrous Material

The goal of this work is to modify the surface characteristics of textiles and composites, while
leaving their bulk properties and appearance unaffected By controlling the composition of the plasma,
the surface of the polymer can be tailored for a specific end use. Previous work has been done to improve
the interfacial bonding properties of carbon, Kevlar®, glass, polyethylene, polyester, and other
thermoplastic fibers.

The primary direction to be followed here is to improve the surface characteristics of fibrous
materials (textile materials and composites) for wettability (both hydrophilicity and hydrophobicity), static
and soil resistance, printing, and dyeability. Comp3.red to other treatments, plasma processing offers the
following potential advantages: lower cost, lower total energy consumption, less required space, more
rapid treatment, a decrease in process liquids, higher reproducibility, and less toxicity.

The research will compare the properties of plasma, chemically treated, and untreated materials.
Their surface and chemical and aging properties will be measured and compared using the diagnostics

11-4
available in the ERC. Engineering statistics will be used to optimize the plasma process. The common
plasma diagnostics and modeling developed for all of the projects in the deposition and polymerization
area will be employed to determine the plasma properties required for effective treatment. Subsequently,
we will examine the feasibility of scaling up the process to a manufacturing environment.

E. Plasma Spraying

A three-pronged approach will be followed by advancing the knowledge base through diagnostics
and modeling of the plasma-particle interaction and of the dependence of plasma jet fluid dynamics on
the spray nozzle design, enhancing the technology base by obtaining empirical correlations between
coating characteristics and spray process parameters using statistical experimental design methodology,
and making use of any advances in our understanding through the testing of equipment and/or process
improvements. Figure 5 shows a diagram of the ERC-developed Hot Anode Gas Shielded (HAGS) [4]
plasma torch, which has a higher power efficiency than a conventional DC torch of a similar design. Full
implementation of the HAGS torch will result in more efficient use of electrical power, improved coating
quality, and more rapid coating deposition rates.

F. Thermal Plasma CVD

Thermal Plasma CVD is particularly useful for materials that do not have a liquid phase. Our
focus in this new technology is on obtaining a detailed understanding of selected processes that have both
immediate industrial interest and specific diagnostic value. We are particularly interested in high-rate
deposition of diamond film, high Tc superconducting films [5], and nonoxide ceramic films such as SiC
and BN. lhree parallel efforts are being pursued: a combination of diagnostics and modeling to clarify
the mass transport across the nonequilibrium boundary layer between plasma and substrate and the
nucleation on the substrate surface, a statistical experimental design approach for obtaining correlations
between coating characteristics and operating parameters, and a materials characterization study of the
interface between coating and substrate that will link the defects in the film with deposition parameters.

G. Plasma Modification of Materials

The goal of this activity is the development of new, cost-effective ion implantation techniques fOI
improving the surface properties of materials, called plasma source ion implantation [6] (pSll), a patented
non-line-of-sight technique for ion implantation of surfaces to improve the wear, corrosion, hardness, anc
fatigue properties of materials. A diagram of a PSII reactor is shown in Fig. 6.

_Two areas for developing methods for the plasma modification of materials are important:
(1) surface hardening and wear resistance and (2) corrosion and oxidation resistance. Preliminary testing
has demonstrated that implantation of nitrogen ions by PSII can substantially improve the surface hardness
and wear resistance of certain materials in certain environments, but the applications are quite limited.
Nitrogen ion implantation is generally effective in increasing the surface hardness and wear resistance for
steels with high chromium content in wear applications at low to moderate temperatures. Thus, although
some of the material problems of industrial interest are amenable to nitrogen implantation with the present
PSII facility, the facility is unable to produce implantation processes that address applications such as
(1) the surface hardness and wear resistance of low chromium steels, (2) the surface hardness and wear
resistance of ceramics and other nonsteels, (3) the hardness and wear in high-temperature environments,
(4) corrosion resistance, and (5) oxidation resistance. For these broader applications, ion species such as
titanium, carbon, chromium, etc., will be required. To address these problems, we are extending the psn
process to operate in a molecular ion species mode and modes similar to the mED (Ion Beam Enhanced
Deposition) or ion beam mixing techniques that have been developed using conventional technology. In

11-5
these latter techniques, a thin layer of a desired nongaseous implant species such as titanium is deposited
onto the target (for example, from sputtering or by physical vapor deposition), and then bombarded witJ1
energetic ions (for example, nitrogen or noble gas ions).

We treat three classes of targets: laboratory test coupon specimens, manufactured components,
and manufacturing tools. The test coupons are characterized by Auger electron spectroscopy (AES),
transmission electron microscopy (lEM), scanning electron microscopy (SEM), scanning Auger
microscopy (SAM), Rutherford backscattering spectroscopy (RBS), and X-ray photoelectron spectroscopy
(XPS) or ESC A, as well as optical microscopy, microhardness, and pin-on-disk tribology tests for relative
wear resistance. The manufactured components and manufacturing tools that are sent out for field testing
are often either too large or otherwise unsuitable for detailed surface characterization, but as a minimum
we try to characterize at least the microhardness of the components before and after implantation.

Both the laboratory tests and the industrial field tests are necessary. The work on laboratory test
coupons represents the development of the knowledge base of the PSII process, whereas the field test work
contributes to the technology base. The test coupon experiments are crucially important in our long-range
strategic development plans for developing new industrial processes. The field test experiments are
important because they validate the test coupon "experiments and ensure that the test coupon experiments
are leading to valid industrial processes.

An important aspect of the development activity is the modeling activity that supports the
experimental work. The modeling is done in three areas: plasma physics studies of the PSII sheath
scaling, Monte-Carlo calculations of the resulting ion-materials interactions, and tribological modeling of
ion-implanted specimens.

Plasma modification of materials depends crucially on the interaction of a broad spectrum of

disciplines including plasma physics, mechanical and microstructural properties of materials, tribology,
corrosion chemistry, radiation interaction with matter, and manufacturing systems analysis. These
disciplines are tightly interwoven; the results of plasma physics modeling codes are used as input to the
ion-materials interaction modeling codes that we use to predict implanted ion profiles. The implanted
specimens are then characterized by a variety of surface analytical and tribological techniques. Finally,
tribological modeling is used to close the loop.

A major obstacle that currently hampers the progress of plasma modeling of the PSII process is
the lack of diagnostics to measure the composition of the ion species in the PSII plasmas. The species
composition must be known to provide input data to the modeling codes for the ion-materials interaction
studies. Rough estimates of the speCies composition can be obtained from other experiments and from
indirect measurements of the Auger profile distributions of implanted ions. For example, in nitrogen
plasmas, modeling gives the best agreement with the Auger profiles for a species mix of approximately
65 % N; and 35% N+, but the error bars are very large, and a better understanding will be required for
the IBED development Another diagnostic need is a noninvasive technique to complement the probe
measurements of sheath propagation. To address these needs, the ion species composition of the PSII
plasma species must be measured, and we have chosen the laser-induced fluorescence (LIF) diagnostic on
the new psn system as an initial step in this direction.

Besides continuing analytic modeling, we also continue the development of detailed plasma
simulation codes. One code being developed uses the propagator (or Green's function) solution of the
plasma kinetic equation. The program includes all the relevant atomic physics as well as electron emission
at the target and the chamber wall. The first implementation of the program will probably be for a helium
plasma, followed by versions for nitrogen and other plasmas.

11-6
 Another code is now capable of predicting the energy spectrum of bombarding ions. We will
compare these predictions with experimental measurements of two types: indirectly, by ex situ Auger
profiling of silicon wafer test coupons, and directly, using a telemetered energy analyzer inside a model
target. Two-dimensional (2-D) as well as three-dimensional (3-D) codes are needed to model the PSII
treatment of targets. As these codes evolve, they will be compared with 2-D and 3-D. measurements that
are just now beginning to yield results.

H. Semiconductor Applications of PSII

Although PSII was originally conceived as an ion implantation process for nonsemiconductor
applications, it has been demonstrated that there are many very good applications ofPSII in semiconductor
processing. PSII achieves in a bell jar type of environment the same ion implantation treatment previously
available only with beamline accelerator technology. This opens up the possibility of incorporating the
ion implantation process into other processes, e.g., to do in a single chamber both ion implantation and
plasma etching. PSII has particular advantages in the intermediate energy range from 1 ke V to 20 ke V;
these energies are not well suited to either plasma etching processes at. the low end or to beamline
implanters at the high end. Specific examples of PSII applications that might be attractive include
backside impurity gettering, shallow implants, ion implantation with rapid thermal annealing, and
formation of insulating layers of AlN.

ACKNOWLEDGMENTS

This work was supported by the National Science Foundation under Grant ECD-8721545.

REFERENCES

1. E.A. Den Hartog, H. Persing, and R.C. Woods, Appl. Phys. Lett, R 661 (1990).

2. R.C. Woods, R.L. McClain, L.J. Mahoney, E.A. Den Hartog, H. Persing, and 1.S. Hamers, Proc. 1991
SPIE Conference.

3. J.A. Tobin and D.O. Denton, Proc. 3rd IntI. Vacuum Microelectronics Conference. Monterey, CA.
1990.

4. S. Malmberg, S. Russ, 1. Heberlein, and E. Pfender, Proc. National Thermal Spray Conference,
Pittsburgh, PA, 1991.

5. S.L. Girshick and W. Yu, Plasma Chern. & Plasma Proc., 1Q, 515 (1990).

6. J.R. Conrad, J.L. Radtke, R.A. Dodd, and F. 1. Worzala, Proc. AIME Fall Meeting, 1988.

11-7
 Neutral ,.rtlcle Fr.. RMtlcaia
"" Electron ActlvatlOn/ ~
e+®_~+O+e
Input Gas Flow _ Output Gas Flow _
Gas Phase Reacllons F,MRadlc81

Substrate Electrode

Figure 1. Processes occurring in a plasma reactor

+3

+2

+1

..
'C'

e
0
0

!
••=
•..
CL
·1

en
oS!
·2

Pluma Source
Ion Implantation:

Type of Plasma Process

Figure 2. Types of plasma processes. As the pressure increases, the nature of the processes tends to
change from physical to chemical to thermal, but in general, each process occurs in a varying
degree.

11-8
 Internal vs. External
Paral11eters

Substrate Temperature
Reactor Geometry
Ellipsometry
Pressure n Thickness

-
~
Flow Rate f{e)
e Film Bulk

Substrate-Film
ESCA

Gases N
-+ Interface
FTIR
Power Film Surface
t res ESR
Pumping Speed Application Based
Analysis
Substrate Potential

Figure 3. Relation between internal and external process variables

 Chamber Design

...§!idID9 Seal
1.5" Conflat

@P c(@ -~
--
I
4.5" Con at 18"
0
@P C® l

6" Conflat Sliding Seal

Chamber Is Stainless Steel

Figure 4. The P4 polymerization reactor

 Figure 5. The HAGS plasma torch

Infra Red Chart

Pyrometer Recorder

Discharge
Bias langmuir
Vacuum Probe
Chamber
---4-----1 Curve
Tracer
Filament
Supply
Working Gas

Ionization
Gauge
Subllmatorl Target Stage
Evaporator ~_---J
Current
To Pulse
Vacuum Modulator
Pump

Figure 6. PSII system

11-11
 12. ATOMISTIC INORGANIC FILM FORMATION BY REACTIVE
AND NONREACTIVE PVD lECHNIQUES

Donald M. Mattox
IP Industries
440 Live Oak Loop
Albuquerque, NM 87122

I. INTRODUCTION

Physical Vapor Deposition (PVD) is defined as an atomistic deposition process in which atoms
(sometimes molecules) are transported from a solid or liquid surface (source) to condense on another
surface (substrate) without gas phase nucleation or reaction. Generally the source for depositing atoms
is thermal vaporization or physical sputtering. Figure 1 depicts the various forms of PVD processing
techniques.

II. PVD lECHNIQUES

A. Vacuum Deposition

Vacuum deposition (evaporation) is typically defined as a deposition process in which the atoms
(or particles) from a thermal vaporization source reach the substrate without collisions with residual gas
molecules. This normally requires a vacuum of better than about 1<r Torr (1.3 x 1O-2 Pa). This definition
does not address the effects of generally undesirable concurrent bombardment of the substrate by residual
reactive gases, the avoidance of which often requires high (10-7 Torr) or ultrahigh (10-9 Torr) vacuum
depending on the deposition rate, the reactivity of the species, and the impurity level of the desired
deposit. Ultrahigh vacuum (UHV) conditions are used in the molecular beam epitaxy (MBE) deposition
of semiconductor materials whereas high or even a poor vacuum condition can be used for evaporation
processing in which contamination is not a major problem either because of the materials involved, the
high rate of deposition, or the materials requirements.

The adatoms that impinge on the substrate surface have a line-of-sight direction from the source
and thermal energies. When alloys are vaporized, the materials vaporize in proportion to their vapor
pressures, which may differ greatly with materials and which are strongly dependent on the source
temperature. When compounds are vaporized, there is often a loss of one constituent on condensation.

The advantages of vacuum deposition are that the

• Techniques and equipment are relatively simple

• Source material may be relatively inexpensive

• Contamination level may be made very low

• Environment may be easily monitored

• Deposition rates may be easily monitored

• Deposition rate is high

12-1
• Shutters may be used to advantage in the system.

The disadvantages of vacuum deposition are that the

• Line-of-sight deposition gives geometrical shadowing of surface features

• Point source for deposition ~an make deposition uniformity a problem

• Films are often not fully dense and may have high residual tensile stresses

• Compounds and alloys are difficult to deposit with a controlled composition

• Deposition rate may be highly variable during a "run" or from run to run

• In situ substrate cleaning is not common but can be done by plasma techniques

• Technique is often used with poorly trained personnel and marginal equipment

B. Sputter Deposition

Sputter deposition, which is often called sputtering and is a poorly chosen term, is the deposition
of particles whose origin is a surface ("target") being sputtered, usually by accelerated ions. One of the
major advantages of sputter deposition is that the deposition rate is rather constant and reproducible ·and
can be sustained over a long period of time. The sputtering process allows alloys to be easily deposited
from an alloy source and compounds to be deposited using a reactive plasma deposition environment or
a reactive plasma or ion beam to give concurrent bombardment of the target material. There are a number
of different sputtering techniques and configurations amenable to sputter deposition. A problem with
many of the sputter deposition configurations is Qbtaining a uniform deposit over large areas, which
requires a uniform plasma that is difficult to attain in many sputtering configurations, particularly
magnetron sputtering. .

Sputtering may be done in a "high pressure" plasma in which the sputtered particles are
thermalized by gas phase collisions before they reach the substrate, in a "low pressure" plasma in which
thermalization does not occur because the sputtered particles reach the substrate with their sputter-ejection
energies that are much higher than thermal or in a vacuum (using ion guns for sputtering) in which gas-
phase collisions do not occur. In the case of "low pressure" and vacuum deposition environments, high-
energy reflected neutrals from the target may concurrently bombard the depositing :film. This high-energy
reflected neutral bombardment is often poorly controlled.

If a reactive gas (deliberate or contaminant) is present in the plasma, it is chemically "activated"

(radicals and ions) by fragmentation to be more reactive with the depositing material. This allows
"reactive deposition" of compounds. The most desirable case is one in which of the constituents is
condensible and the other is gaseous (Ti + N => TiN). In many cases of reactive deposition, it has been
difficult to obtain fully reacted material so that the compounds are substoichiometric (e.g., TINt_x). In
reactive sputter deposition, plasma uniformity and reactive species availability are very important for
obtaining a uniform film.

Sputter-deposited fIlms are often not fully dense. Film density may be increased and the
stoichiometry controlled by concurrent bombardment during deposition. See Section C.

12-2
The advantages of sputter deposition are having a

• Long-term, stable vaporization source

• Large-area source with some configurations (direct current [DC] diode)

• Unique source with some configurations (parallel ·line sources for planar magnetron and rotatable
tubular sources)

• Source of materials that may be easily deposited as alloys

• Reactive deposition capability that allows the deposition of compounds

• Scheme for easy in situ substrate cleaning and surface preparation.

The disadvantages of sputter deposition are that

• Films are often not fully dense

• Reactively deposited fllms may not be fully reacted (sub stoichiometric)

• Sputter-deposited films may have a high residual tensile or compressive stress

• Many process variables need to be controlled

• Most of process energy goes into heating the target

• Plasma contamination is often a process variable .that is difficult to control

• Sputtering sources are expensive

• Deposition rates are generally slower than for vacuum evaporation.

c. Ion Plating

Ion plating is a generic term for deposition processes in which concurrent energetic particle
bombardment during deposition is used to modify the cOmposition, morphology, microstructure, and
properties of the deposited material. The source of depositing species may come from thermal
vaporization, sputtering, or chemical vapor precursor species.

There are two basic vetsions of the ion plating process. In plasma-based ion plating, the substrate
is in contact with a plasma, and the ions are accelerated from the plasma and arrive at the surface with
a spectrum of energies. In addition, the surface is exposed to an activated species from the plasma.
adsorption of gaseous species, high electron concentrations, and radiation from the plasma. In the
vacuum-based ion plating often called "Ion Assisted Deposition" (lAD), "Ion Beam Assisted Deposition"
(mAD) or "Ion Beam Enhanced Deposition" (IBED), the bombardment is from a beam of ions formed
in an ion gun and accelerated to the surface with a more specific and controlled energy distribution often
accompanied by an undefined bombardment by high-energy reflected neutrals when a sputtering source
is used. Many of the surface effects of the two versions are the same, but there are also important
differences to be expected, particularly in reactive deposition and surface coverage.

12-3
 The most common sources for energetic bombarding particles at gas (plasma) pressures above
which there is thermalization of energetic particles between the vaporization source and the substrate are

• Ions from a DC, radio frequency (RF), plasma arc, or laser-induced plasma being accelerated to the
surface under an applied bias or "self-bi~"

• High-energy neutrals originating from charge exchange processes in a gas.

When the pressure is low enough to assure little or no thermalization between the source and the
substrate, additional sources of energetic particles are

• Reflected high-energy neutrals that arise from energetic ions reflecting from a surface as neutrals, e.g.;
low-pressure magnetron sputtering and ion beam sputtering

• Acceleration of ions from the vacuum arc vapor source due to a space charge

• Acceleration of negative ions (e.g., 0-) away from a negatively biased sputtering·surface

• Energetic neutral sputtered species

• Ion guns in which ions are extracted from a confined p:asma using a grid system.

The flux and energy of the bombarding species are very important. High-energy particles are
incorporated into the lattice and may precipitate to form voids (lower density). The high-energy parj cles
also tend to give high residual compressive stresses in the films by excessive "recoil implantatic l" of
surface atoms. In order to obtain dense, low-stress fIlms, :he bombardment energies should be an und
100-250 eV with a flux ratio (energetic particles to depositing atoms) of about 1:10.

Important ion plating depoSition parameters are: energetic particle to depositing particle ratio,
energy of the bombarding particles, ambient gas/plasma pressure and composition, deposition temper~ture,
and the materials involved. In reactive ion plating, in which a compound film material is formed, the
bombardment and deposition parameters affect the reactioli kinetics and degree of reaction, phas and
stoichiometry of the compound, crystallographic orienttion, and inclusion of unreacted sp des.
Additional factors affecting the surface reactions include: cl· ~mical state of depositing, ambient and 'om-
barding particles, surface heating, defect production, surface adsorption, implantation, nucleation de nsity
of depositing species, secondary electron emission, and preferential sputtering and desorption of surface
material.

The advantages of ion plating include obtaining

• Control of film properties such as density and stress by controlled bombardment

• Bombardment-enhanced chemical reactions and removal of unreacted species

• Good surface coverage

• Good adhesion and interface formation

• High deposition rates using thermal vaporization sources.

12-4
The disadvantages of the ion plating process include the

• Many process parameters

• Inclusion of bombarding species in the film if uncontrolled

• High compressive film stresses if uncontrolled

• Poor understanding of surface processes in ion plating.

More detail on applications of mAD is given in Chapter 16, this volume.

Ill. FILM FORMATION

A. Nonreactive Film Formation

In PVD, film formation and growth are determined by the nucleation of adatoms on a surface, and
the parameter of nucleation density is important A high nucleation density is generally desirable for good
adhesion and a dense film. Nucleation density (and adatom surface mobility) is controlled by a number
of factors including:

• Surf~ chemistry and chemical reactions

• Preferential nucleation sites

• . Charge centers, steps, defects, grain boundaries

• Adsorbed species.

The nucleation density may be modified by

• Controlling the surface chemistry by cleaning or surface modification such as AI20 3 on AI

• Substrate heating

• Generation of nucleation sites, e.g., defects, steps

• Adsorption of reactive species, e.g., 0 (OJ on oxides

• Concurrent energetic particle bombardment prior to and during ·deposition by introducing defects,
recoil implantation of species, and physically implanting species.

B. Reactive Film Deposition

Reactive deposition of materials may be used to form compounds by reacting the depositing
species with a codepositing reactive species or with an adsorbed reactive surface species to form a non-
volatile compound. For example, a mixture of TI and C may not have any TIC, may be partially TIC and
the rest unreacted TI and C in solution, may be substoichiometric TIC1•x, or may be TIC with excess TI
or C-all of which will have different properties. Generally, for low-temperature deposition, the best
situation for reactive deposition is one in which one of the reaction species is condensible and the other

12-5
is gaseous (e.g., TI + N). If both species are condensible, the best deposition condition is to have a high
substrate temperature to promote reaction or to use postdeposition heat treatment

There are a number of techniques for performing reactive atomistic film deposition. The simplest
way is to evaporate the material thermally in a partial pressure of a reactive gas (reactive evaporation).
'This generally gives poor quality films, because the materials are not completely reacted, and the high gas
pressures result in gas-phase collisions and n1l:cleation of the depositing material, giving a low density
deposit.

In another general process, the gaseous reactive species may be "activated" by fonning excited
species, radicals, and ions in a plasma. The reactivity of the species can be increased by adding internal
energy (excited species), by fragmenting the species to form radicals (uncharged species of 0, N, F) or
ions (charged species of O+, 0-, N+, Cu+, Cu2+). or by forming more reactive species (Le .• 0 3 from
O2 + 0). 'This is most often done in a plasma. in an arc. or by radiation absorption such as can be done
with a mercury vapor lamp or an excimer laser. In the case of the activated species, the reaction
probability with the adsorbed adatoms is increased over that of the molecular reactive species. Activated
species may also be produced in a separate source to produce a reactive plasma beam or reactive ion
beam.

Reactive deposition may be performed in a low- or high-pressure plasma or in a vacuum. In the

absence of a good vacuum. gaseous species from the ambient impinge on the surface and adsorb to some
degree. For an ambient pressure of to-3 Torr. gaseous particles will impinge on the surface at about
1<Y monolayer (ML)/s (compared to a typical deposition rate of about to MLls). The adsorption
probability and adsorbed film thickness will depend on a number of factors such as the impinging species
(Le., plasma parameters), the nature of the surface. the adsorption sites, etc. For instance, it has been
shown that atomic oxygen on silicon will adsorb with a higher probability and to a greater ML thickness
than will molecular oxygen and that ozone is strongly adsorbed on ~03.

In the case of a plasma environment in which the species are activated. the adsorption may be
higher than in an environment in which there is no activation. and this, in turn. influences surface reactions
and recoil implantation into the surface. In vacuum. one expects adsorption to be low, and physical
penetration of the bombarding species into the surface will be the more important effect. The effects of
adsorption on reactive deposition have not been studied to any extent [1].

The composition of the reactively deposited material may be controlled by controlling the
availability of the reactive species. 'This allows the gradation of composition from an elemental phase to
the compound phase. For example. TI to TIN to enhance adhesion of the deposited TIN material.

The reactivity can be further increased by using concurrent energetic particle bombardment either
by the depositing/reacting species or by a species that does not enter into the reaction (inert ion
bombardment). Generally these energetic species are obtained by charging (ionizing) a species and
accelerating the ions in a electric field, but the energetic species may also be neutral, such as those formed
by charge exchange processes or neutralization and reflection of energetic ions from surfaces. 'This
bombardment enhances compound formation by introducing heat into the surface, adding kinetic energy
to the adsorbed species, disassociating adsorbed molecular species ("surface activation"). producing
secondary electrons that assist chemical reactions. and selectively desorbing or sputtering unreacted or
weakly bound species. Concurrent bombardment effects can be enhanced by mixing a heavy inert gas
with a light reactive gas to give bombardment by both species.

12-6
 Periodic bombardment of a depositing species by an energetic reactive species can accomplish
many of the same effects. For example, one can deposit several monolayers of aluminum, bombard them
with energetic oxygen ions, and then deposit more aluminum, etc. This proCess has been termed
alternating ion plating.

Concurrent energetic particle bombardment during atomistic film deposition has been shown to
have a substantial effect on the composition, structure, and properties of compound films. In general, the
bombardment allows

• Chemical reactions to occur at low substrate temperatures

• Formation of more stoichiometric materials

• Decreased incorporation of unreacted species

• Formation of higher density films

• Better surface coverage.

Plasma deposition environments may give a reactive deposition process that is not normally
expected. For instance, the sputter deposition of gold on oxide surfaces in;m oxygen-containing plasma
gives rise to very adherent gold films by giving a high nucleation density, and recently this deposition
condition has been shown to result in gold-oxygen bonds being formed, whereas gold oxide has only been
formed previously by electrochemical techniques.

Reaction (rate and degree) of particles in contact with each other depends on a number of factors
including the

• Degree of previous reaction

• Reactivity of the species (including "activation")

• Energetics of the reactive species (internal and kinetic)

• Concurrent ion bombardment (energetic, secondary electrons, resputtering)

• Temperature of the substrate

• Reactive species availability (adsorbed on surface or impinging)

• Residence time of reactive species

• Presence of free electrons near the surface.

The probability that an adsorbed species will react with a surface depends on the nature of the
species and the degree of reaction that has already occurred at the surface. For instance, oxygen molecules
will react with a pure aluminum fIlm, but nitrogen molecules will not The probability that the oxygen .
molecule will react with the aluminum decreases as the aluminum reacts with the oxygen molecules (i.e.,
the coverage increases). In the case of atomic oxygen, the reaction probability will decrease with
coverage. In the case of atomic oxygen on silicon surfaces, the reaction probability decreases

12-7
monotonically with coverage through several ML coverages. If the material can form a series of
compounds (e.g., TiN, Ti2N) the probability of reaction is further decreased as the degree of reaction
increases and· it will be more difficult to form the higher compound. In may cases, a reaction occurs ftrst
at active sites on the surface providing a nonhomogeneous growth (or etching) mode.

The degree of reaction of codepositing species depends on the availability of the species and the
time of contact, as well as the reaction probability. Obviously, if the species are not available to react,
the reaction will not proceed to the desired extent. 1bis gives rise to the "loading factor" that means' a
relationship exists between the surface area for reaction (deposited film area) and the amount of reaction
gas necessary. If one of these is changed, that will probably necessitate changing the other.

IV. HYDROGEN EFFECTS ON FILM GROWTH

Hydrogen seems to play a very unusual role in the growth of some materials. In the case of
silicon deposition from the silane (SiH4) precursor gas in chemical vapor deposition (CVD), the incomplete
decomposition of the precursor results in the deposition of amorphous silicon that can contain more than
20 at % hydrogen. The hydrogen prevents Si-Si bonding. The amorphous silicon seems to deposit much
like a polymer, giving very good surface replication and low void density in film growth. The growth
seems to be controlled by the adsorption of species formed in the plasma [2~]. Other materials such as
boron and carbon show similar growth of an amorphous phase when hydrogen is present.

In the case of carbon, a diamond ("diamond-like") structure may be grown in the presence of
hydrogen. In this case, the C-H bond on the surface seems to stabilize a high temperature/pressure
diamond structure of the carbon until the deposition of another C-H causes the desorption of the original
hydrogen atom. These diamond fIlms may then show properties approaching natural diamond and
diamond grown under high pressure-high temperature conditions. A problem with this type of growth is
that the surface is relatively rough compared to that of diamond fIlms formed by ionized deposition
techniques. These diamond (hydrogen) fIlms have. been grown by a number of techniques and under a
variety of deposition conditions.

V. SURFACES IN PVD: RESEARCH AND ANALYTICAL INTERESTS

For studying the nucleation density of adatoms on a surface, methods and techrJques that have
been used include optical (and other radiation) extinction during deposition. ::-r:: y photoelectron
spectroscopy (XPS) signal extinction with deposition (a function of ML depoe:: :c: . function changes
with deposition, and in situ transmission electron microscopy (TEM). , ._~s are needed on
engineering systems in which the nucleation studies are combined with studies on surface chemistry,
surface preparation, adhesion. and fIlm properties. Other needed research includes studies of the

• Structure and properties of the material formed on the surface during deposition that later becomes
the "interphase" material found in the interfacial region between the film and substrate [5]

• Concurrent and prior energetic particle bombardment on nucleation density of the adatoms

• Adsorption of reactive species on a surface, the effect of molecular species on adsorption, and the
production of unique species in the plasma

• Concurrent bombardment on chemical bond formation at surfaces, the formation of substoichiometric

reaction layers, and .enhanced reaction completeness

12-8
• Concurrent bombardment on chemical reaction kinetics on surfaces including synergistic effects of
energetic inert species and molecular reactive species, and effects of secondary electrons, coverage,
dissociation, recoil implantation, and the ratio of bombarding species to depositing species

• Concurrent bombardment on crystal growth on surfaces and the relationship among surface adatom
mobilities, crystallographic orientation,· and defect formation.

REFERENCES

1. D. M. Mattox, Appl. Surf. Sci., 48/49. 540 (1991).

2. S. Veprek and M. Heintz, Plasma Chem. Proc., 10(1),3 (1990).

3. S. Veprek ~d M. G. J. Veprek-Heijman, Appl. Phys. Lett, 56(18), 1766 (1990).

4. S. Veprek, F.-A. Sarrott, S. Rambert, and E. Taglauer, 1. Vac. Sci. Technol., A7(4), 2614 (1989).

5. Opportunities and Research Needs in Adhesion Science and Technology, Proceedings of the
Workshop held October 14-16, 1987, sponsored by the National Science Foundation, HITEX, 1988.

APPENDIX

"Surface Effects in Reactive Ion Plating" by D. M. Mattox.

ABSTRACT

Ion plating is a generic term for deposition processes (vacuum-based and plasma-based) in which
concurrent or periodic energetic heavy particle bombardment during deposition is used to modify the
composition, morphology, microstructure, and properties of the deposited material. The beneficial effects
of controlled bombardment are well documented in reactive deposition (and etching) processes; however,
the mechanisms involved and their relative importance are poorly defmed and understood. This paper
reviews some of the possible mechanisms important in reactive ion plating and how they may vary with
deposition conditions. The complete text is given in Appl. Surf. Sci., 48/49. 540 (1991).

12-9
 13. PARTICLE BOMBARDMENT EFFECTS ON TIllN-FILM DEPOSmON: A REVIEW

D. M. Mattox
Surface and Interface Technology Division
Sandia National Laboratories
Albuquerque, NM 87185

ABSTRACT

In many atomistic film deposition processes, concurrent energetic particle bombardment (ions,
atoms, molecules, atom clusters) may occur inadvertently and uncontrollably or bombardment may be used
to deliberately modify film properties. These energetic particles can arise from (i) the acceleration of
charged particles, (ii) high-energy neutrals from reflection from bombarded surfaces, or (iii) charge
exchange processes. Particle bombardment effects that can affect film formation and growth include
(a) modifying the substrate surface (cleaning, defect formation), (b) momentum transfer processes in the
surface region (sputtering, desorption, recoil implantation, defect formation), (c) addition of heat to the
surface region, and (d) formation of secondary electrons that can affect chemical reactions. These in turn
affect film properties such as adhesion, residual film stress, fIlm morphology, density, grain size and
orientation, surface coverage, pinhole density, and surface area. The understanding of these effects and
how to use them advantageously is important to 1:bose utilizing processes where concurrent energetic
particle bombardment is occurring or can be made to occur.

The complete article is published in 1. Vac. Sci. Technol., A7(3), 1105-1114 (May/June 1989)
(104 references).

13-1
 -
14. . SOL-GEL COATINGS FQR ENERGY-RELA'IED MA'IERIALS

Alan J. Hurd
Sandia National Laboratories
Albuquerque, NM 87185-5800

ABSTRACT

'Through sol-gel processing, the full flexibility of solution chemistry can be exploited to make
films with fmely controlled compositional characteristics; no less important is the possibility of exploiting
colloid and polymer physics in general ways to achieve desired film properties. The advantages,
disadvantages, and applications of sol-gel films are discussed with an emphasis on those properties that
are unique to sol-gel processing.

I. INTRODUCTION: A LOW-COST SOLAR CELL

O'Regan and Gditzel reported [1] in late October 1991 that they had succeeded in fabricating a
photo voltaic cell based on commercially realistic technologies. One of the enabling technologies in their
device is a sol-gel coating. Although this cell may not be the answer to mankind's energy problems, it
serves to illustrate some of the advantages of sol-gel coatings. .

The cell is based on a porous Ti02 (anatase) coating impregnated with a charge-transfer dye, a
ruthenium-pyridine complex. Electrical contact "is made throughout the porous film by an iodide
electrolyte. Solar photons are efficiently absorbed by the film-46% of the solar flux at all wavelengths
"is harvested-and their energy is converted, at efficiencies exceeding 80%, to electrons injected into the
conduction band of the Ti02 semiconductor. After the collected current was sent through test loads and
back into the electrolyte to regenerate the dye, overall efficiencies between 7% and 12% were found,
depending on illumination. The authors reported exceptional stability for their cell with respect to
decomposition under constant use. Owing to the low cost of materials, they feel that practical applications
are feasible.

The success of this solar cell derives from a high quantum efficiency for charge injection as well
as the substantial overlap between the absorption spectrum of the dye and the solar spectrum. However,
neither of these attributes could be exploited unless a sufficient amount of dye could be illuminated while
maintaining electrical contact with both a semiconductor substrate and a regenerative electrolyte. Thus,
the porosity of the titania film is a decisive advantage.

The film was deposited from a colloidal suspension of 10-om Ti02 particles prepared by the
hydrolysis of titanium tetraisopropoxide. A "paint" of these particles was spread onto a conductive glass
slide and allowed to dry into a 100mm film. After lightly sintering the film at 450°C to ensure electrical
contact, a high surface area semiconducting support resulted with pores large enough to accept dye
molecules; the surface area of the cell was increased 780-fold!

Aside from the porosity, other factors contribute to the economic potential of the, solar cell. The
purity of the titania is important, and, through the purity of the liquid reagents, it is attained. The
relatively low-tech method of film fabrication requires minimal investment in equipment, yet retains wide
flexibility to coat large areas or complex shapes. The thermal treatment is low in energy cost in
comparison with most ceramic processing. Finally, in addition to chemical control, the manufacturer has

14-1
physical control of the film precursors-the colloid-and the way they are deposited. which allows
optimization of the cell performance via porosity.

II. SOL-GEL FILMS: DEFINITION AND mSTORY

No universal definition of sol-gel film processing exists. Perhaps the most general qualification
is any film deposited from a liquid phase. Although necessary, this qualification would be perceived to
be too general by the current sol-gel community. Sol-geJ films are defined largely by processing:

"A sol-gel film is a coating or free-standing film that is formed from a sol through
continuous stages of increasing concentration of a solid precursor."

11lis definition comes closest to modern usage [2]. Precipitations, such as common gold or silver
metallizations on glass, are excluded because such a film grows essentially at final density from the
substrate into the liquid On the other hand, precipitates that form in the bulk liquid and are then
concentrated on a surface by settling, electrophoresis, or evaporation form a true sol-gel film by the above
definition. A schematic of the sol-gel processing field, of which films are only a part, is shown in Fig. 1.

Typically, the sol is a solution of polymeric species or a suspension of "oligomers" including,

possibly, particles in the colloidal size range. The liquid carrier must be volatile or, at least, volatilizable
through heat treatment. During deposition through states of increasing solids concentiation, this sol might
gel, as in bulk sol-gel processing, however, the gel state is often afl~eting ·transient that quickly empties
of liquid. Nevertheless, the structures formed during this stage, with varying amounts of porosity,
influence the structure of the final film.

By the above definition, printing and painting are sol-gel film processes. Thus, sol-gel films are
easily the oldest surface modifications invented by man, dating back tens of thousands of years. The first
modem sol-gel films, according to the early, defini~ve review by H. Schroeder [3] of Schott Glaswerke,
were Langmuir-Blodgett (LB) monomolecular layers, which by 1935 had been developed to the point of
making antireflection coatings. LB films are formed by the slow withdrawal of a substrate through a
molecular surface layer that is lifted from the liquid surface onto the substrate; they continue to be
developed as a means of depositing very thin, high-molecular-weight layers, and they are considered to
be a research discipline in their own right, separate from mainstream sol-gel technology.

Schroeder reports that the first oxide films (Si02) were made in Germany shortly before World
War II by spin coating silicic acid onto glass. During the War, this process was used industrially,
presumably as optical coatings, but the first products did not appear on the market unti11953 [4]. Large-
scale production of automotive mirrors coated by sol-gel techniques began in 1959. Original patents on
the chemical basis of sol-gel oxide films were filed simultaneously by the Schott chemists [5] and by
Levene and Thomas (Owens-Dlinois, Int.) in 1969 [6]; the process itself was known through German
patents to Schott and Leitz as early as 1939 [7]. The early Schott workers nicknamed sol-gels "glass from
the bottle" [4].

Dislich [8] predicts that the future of sol-gel processing will be .based on its strengths: high
compositional and homogeneity control at low temperatures. Sayer and Sreenivas favor sol-gel processing
as a way to evaluate new compounds quickly and cheaply [9]. In comparison with vacuum and chemical
vapor deposition (CVD) techniques, sol-gel coating is not equipment-intensive or directional. For optical
applications, the ability to coat both sides of an element simultaneously is a potential advantage [3].
Indeed, for any given application, sol-gel fIlms may offer unique advantages.

14-2
Ill. ME1HODS OF FABRICATION

Sayer and Sreenivas [9] classify all ceramic thin-film fabrication into physical techniques,
including vacuum evaporation, sputtering, and ablation, and chemical techniques, such as CVD and sol-gel
processing. Part of the flexibility of sol-gel processing is the option of using physical mechanisms in
conjunction with chemical reactions to achieve a desired result. For example, it is now common to trap
colloidal particles inside a fine sol-gel matrix to render a fIlm antireflective [10] or colored [3]. lhis
hybridization of chemical and physical aspects accounts for much of the recent explosion of interest in
sol-gel films.

The first step in sol-gel fIlm fabrication is to meter a well-defined quantity of sol uniformly over
the substrate; this can be accomplished in several ways discusSed below. Second, the liquid phase is
allowed to dry; often the evaponition is spontaneous and nearly instantaneous. The film density is strongly
affected by capillary forces at this stage. Finally, the film can be heated to remove traces of liquid,
improve adhesion, crystallize, or sinter the material. The heating step is optional since, for many
applications, the dry fIlm emerging from the second stage is robust enough. Indeed, the ability to fabricate
ceramic and organic films exclusively by room temperature processing may prove to be a great advantage
for bioactive films.

Sol-gel processing is simple and economical, but, as Guglielmi points out [11], it remains largely
empirical in practice: sol-gel·science is a recent invention [2].· The outlook is bright. Since 1982, more
than 500 papers have been published in scholarly journals on sol-gel films.

A. Dip Coating

Nothing could be simpler than dipping a component or piece into a sol and withdrawing it.
Figure 2 shows a side view of the process. Historically the technique of choice for optical films, this
typically low-tech process allows great flexibility in part size and shape with a minimal equipment
investment However, the simplicity of dip coating masks the complexity of the physics and chemistry
behind it.

The coating of photographic fIlm with a gelatinous emulsion motivated early studies of the
hydrodynamic entrainment of a liquid film by a withdrawing body. The first correct treatment; by Landau
and Levich [12], predicted that the entrained fIlm thickness A. (Fig. 3) scales with the withdrawal velocity
uo as uo213 (in the absence of evaporation) assuming simple, Newtonian viscosity. Guglielmi [13] cites a
number of authors who have reported behaviors ranging from Do213 down to u oO. 1, demonstrating, perhaps,
that viscosities are not always simple or that surface-tension gradients are sometimes important. In any
case, the interplay of gravity, surface tension, and fluid viscosity determines the amount of liquid metered
onto the surface in dip coating in contrast to slot and roller coating, in which the liquid volume is
dispensed by externally controlled pressure (see below).

Most sol-gel coating is done with a volatile liquid, such as short-chain alcohols; dip coating is no
exception. Evaporation during withdrawal gives rise to an astonishing phenomenon: the entrained film
rapidly approaches a steady-state thickness profile for a constant withdrawal velocity. A signature of this
process is the presence of a "drying line" above which little or no free liquid is observed and below which
the entrained liquid fIlm tapers smoothly to the reservoir. The recession rate of this drying line is a
function of its height above the reservoir, and the entrained film will rapidly grow to a length at which
the recession rate matches the withdrawal rate. Typically, withdrawal speeds are of the order of
millimeters per second, and the drying line stabilizes at a height of a few millimeters.

14-3
 -
. The steady nature of dip c<?ating with volatile solvents engenders optical studies of the process.
In Fig. 4, Schroeder shows how interference fringes in the fIlm can be used to assess coating uniformity
[3]. Since 1988 [14], Hurd and coworkers have been developing imaging ellipsometry to assess coating
uniformity, in which images of the steady-state fIlm through an ellipsometer yield thickness and index
maps. The index maps reveal a measure of the local solids concentration, while the thickness maps relate
directly to the evaporation behavior. At the drying line, which represents a sharp edge in the evaporation
and vapor diffusion problem, we have shown that the sol concentrates very rapidly because of the
precipitous loss of solvent [15]. This accelerated evaporation sets an unavoidable time limit on the
gelation, aggregation, polymerization, or other chemistries occurring in the film, as Fig. 3 illustrates.

Surface tensions are usually fmely balanced during dip coating, as the liquid surface radius of
curvature usually exceeds 1 kID except in the gravitational meniscus region [16]; this point can be
appreciated by the difference in scales for the measured profile h(x) in Fig. 5. Surface tension is such an
overwhelmingly large force, however, that dramatic things can happen when this balance is upset. The
dipping of solvent mixtures having differing volatilities can lead to surface-tension gradients when one
component is depleted from the mixture by differential evaporation, as shown in Fig. 6. The resulting
surface-driven flows produce extraordinarily high shear rates, of the order of IO"ls, that can be used for
fIlm structure control via, for example, shear-induced ordering [17].

The uniformity of dip-coated films is surprisingly good, given the fact that the sol is self-metered.
Vibrations and air currents are easily and necessarily avoided; "edge-bead thickening" ap~ars to be
unavoidable [11]; good wetting is. a prerequisite; phase separation in multicomponent systems can be a
problem [18]. .

B. Spin Coating

Because of the burgeoning microelectronics and magnetic disk industries, spin coating of sol-gel
films may now be the most important fabrication technique. A sol is dispensed onto a stationary,
nominally flat substrate, which is then accelerated rapidly to spin about an axis normal to the surface. A
portion of the sol is ejected by centrifugal force. Emslie et al. [19] showed that, remarkably, the film
thickness becomes uniform regardless of its initial distribution. Meyerhofer frrst considered evaporation
in the process [20] and predicted that the film thickness should scale with the angular velocity 0 as 0-lf2,
a result confirmed recently by Lawrence [21]. However, the effects of nonNewtonian viscosity can alter
this scaling [21]. Unlike dip coating, the distribution of sol occurs more rapidly than variations in sol
properties from evaporation [11].

Shear rates in spin coating can be large enough (> l<Yls) to effect structural changes in the film
[22]. The refractive index of silica films deposited from polysilicate sols shows an increasing trend with .
0; intuitively consistent with the idea of shear-induced ordering, this phenomenon remains largely
unexplained.

C. Electrophoresis

Possibly the only way to produce a uniform, conformal coating on complex shapes is to use
electrophoretic deposition [23]. The part must be 'conductive, and the sol must contain contain charged
species. The latter criterion can almost always be met by judicious use of emulsification or surfacta:ncy.
When the part is held in the sol at a moderate potential with respect to an inert counterelectrode and where ·
the choice of positive or negative potential signs depends on the particle charge, the electric field causes
the particles to migrate and adhere to the surface. Thus the fIlm passes through states of increasing solids

14-4
concentration. The coating can be built up to large thicknesses in comparison to dip and spin coating, but,
if the particles are insulating, the coating itself will choke off the electric field.

A major advantage to electrophoretic coating is its self-healing nature. Pinholes are filled
preferentially, owing to their high field strength. Similarly, edges and protruberances acquire greater
thickness than flat areas. These attributes make electrophoresis attractive for microelectronic coatings [23].

D. Free-Standing Structures

A growing body of sol-gel literature deals' with fibers and free- standing films of glass:-forming
oxides. The major part of the effort has centered in Japan, beginning in the early 1980s. While not
strictly a part of surface modification, this phenomenology deserves mention because of its intrinsic
interest and the many aspects of structure formation it shares with deposited films. In fact, the coating
of wires and fibers has a closer resemblance to this section than to the foregoing sections.

Sol-gel fibers were first reported by Sakka and Kamiya [24] in 1982. They allowed an alkoxide
solution nearly to gel, then touched a glass rod to the surface and pulled up. By a process called spinning,
a long, uniform fiber was created that became a dense glass fiber after heating. Diameters of a few
microns to tens or even hundreds of microns are possible. The amount of material metered into the fiber
by the gravitational meniscus has, to this author's knowledge, not been treated, although it appears to be
a straightforward extension of the Landau-Levich treatment for films [12].

The characteristic ot'spinnability has remained a mystery. Sakka and Kozuka showed [25] that
spinnable sols remain Newtonian at high viscosities and that they contain long, polymeric species as
opposed to compact particles.

The same Japanese group pioneered free-standing film formation. Reviews by Sakka and
coworkers in 1984 [26] and 1988 [27] treat the phenomenology. Commoruy called "sheets," free-standing
films have been produced in three basic ways: sheets have been drawn from spionable solutions using
wire frames, they have been extruded through slots, and they have been coated onto substrates from which
they could be separated. Typical films are tens of microns thick. Huling and Messing reported an
interesting variation [28] in 1988 in which they spin coated camphor disks with various sol-gels and then
allowed the camphor to sublime. After firing, they produced very thin sheets, down to I-mm thick, of
crystalline aluminosilicates.

E. Other Coating Methods

Traditional high-speed, continuous coating is accomplished by premetering the sol onto a moving
substrate using slots and rollers. The extensive literature on this subject has been reviewed by Scriven [29].
Although not normally considered to be in the sol-gel domain, these techniques promise to gain in
importance as industrial applications are found. A recent research example that crosses the boundary into
recognizable sol-gel processing is the study of "doctor- blading" by Casanova et al. [30]. Also called tape
casting, the doctor blade forms a variable slit opening through which the substrate travels and the sol is
dispensed.

Although spray coating, painting, printing, and many other techniques fit the definition of sol-gel
films adopted here, they fall beyond the scope of this paper.

14-5
IV. DRYING AND HEATING

As pointed out by Scherer [31], the removal of liquid from bulk sol-gels is particularly
. troublesome due to the tendency of gels to crack or warp 'under drying stresses. Thick fIlms and
multilayer films suffer essentially the same problems as bulk gels. Very thin fIlms, such as those formed
by dip-coating (h < 0.2 mm), tend to be below the critical thickness at which cracking occurs. In any
event, capillary forces can dramatically influence the structure and porosity of sol- gel films.

A. Capillary Collapse

Stress arises as soon as a gel no longer "fits" inside its host liquid volume. In dip coating, for
example, the rapid loss of liquid near the drying line creates menisci in the pores of the gel that set up
tension in the liquid. The Young-Laplace equation shows that this pressure is inversely proportional to
the radius of curvature of an adjacent meniscus [31]. Further evaporation is impeded by liquid transport
through the gel to the gas-liquid interface, a regime called the "constant-rate period" by Scherer. For most
materials, the reactive force to this tension, exerted by the interface on the gel, causes the network to
collapse until a point at which the gel can collapse no longer. Suiface pores then emerge from the liquid
as it recedes into the gel; this period is called the "falling-rate period."

A sobering calculation shows that, if the pores in the film are comparable in size to the precursor
particles, then the menisci give rise to tens or even hundreds of atmospheres of tensile pressure. Whether
actual pressures exceed 100 atmospheres is debatable, given the range of applicability of the
Young-Laplace equation and the (meta)stability of the overexpanded liquid [17] . . Nevertheless, Brinker
has shown that the film compacts to a density that is proportional to the particle size as a result of
capillary collapse [22].

To and Drake' [32] discuss the heat and mass transfer during a drying process without
consideration of capillary phenomena. They propose that during the constant- and falling-rate
periods-called the diffusion-limited regime in their paper-not only is the transport of liquid to the
evaporating interface important but also the transport of heat In very thin films (not explicitly defined
by the authors), of course, thermal transport is not limiting. '

B. Stresses and Multiple Coats

Schroeder [3] identifies three stresses that can develop in sol- gel films. Intrinsic stresses are
typically tensile and arise from the tendency of gels to shrink as they dry. Adhesion stresses arise in this
situation because the gel is pinned to a substrate. Finally, thermal stress is important for materials that
aren't well matched in thermal expansion coefficients.

Thermal stress is often the limiting factor in the extent to which multiple coats can be deposited.
Of particular interest in this arena is the use of multiple layers to create interference optics that might meet
with high temperatures. Schroeder [3] cites titania on soda-lime glass as a good thermal match-the
difference in thermal expansion coefficients is less than 30%-in which repeated coats are viable. Silica,
on the other hand, is not easily multicoated because its difference in thermal expansion coefficient exceeds
90%. Brautigam and coworkers [33] have only been successful with silica using a full thermal treatment
between layers.

The measurements of stress in sol-gel films is a science in its infancy. Schroeder usedthe
deflection of a thin disk coated on one side to study titania films [3]. Cerqua and Hayden have applied
modulated transmission ellipsometry [34] to assess residual stress as a function of various processing

14-6
parameters. They found that even compressive stresses are possible depending on the age (extent of
aggregation/polymerization) -of the sol.

. V. COMPLEX COMPOSmONS

Although a large number of possibilities exist for single-component sol-gel fIlms, multicomponent
formulations offer even more numerous possibilities. A few examples are cited, but special applications,
such as ferroelectric and superconducting films, will be treated separately in Section VI.

Colloidal inclusions have already been noted [3,10] as a means to modify optical properties. The
use of metal and semimetal colloids or clusters remains a promising route, especially in view of recent
activity with quantum-size effects in silicon.

Molecular mixtures can have equally profound optical and electronic effects. Cobalt oxide [3] was
a pigment used in early research, and mixtures oftitania and silica were used industrially [4] to adjust the
refractive index. · Cadmium stannate fIlms were synthesized as a transparent semiconductor in initial
research work.

The greatest effort appears to have gone into glass ceramic films. Dislicnand Hinz [4] reported
an eight-component formulation in their seminal patent [5]. An example of the extremely wide range of
compositions possible by sol-gel processing is given by Puyan6 and Gonz~ez-Oliver (35], who studied
binary, ternary, and quaternary oxides of silicon, titanium, aluminum, tin, indium, germanium, yttrium,
and zirconium. .

VI. APPLICAnONS

A. Electronic

There has been an explosion of papers in sol-gel processing of superconducting ceramics over the
past few years, especially in Japan. The YBCO phase has been formulated [36], and Sakka's group has
recently gotten involved [37]. Although reasonable critical currents (e.g., 13,000 A1cm2) have been
obtained, the quality of sol-gel processed films lags behind films prepared using physical deposition.
Nevertheless, the ease and simplicity of the sol-gel process lends itself well to a wide range of
stoichiometries [38].

Ferroelectric films of the lead titanate family are under investigation in a number of laboratories
using sol-gel technology. Phase purity is a recurring problem, as the lead-poor pyrochlore phase tends
to form at low temperatures. Uhlmann and coworkers have compared these sol-gel developments,
including barium and strontium titanates, to physically deposited films [39]. In general, finer
stoichiometric control was possible with sol-gel as compared to sputtering, but microstructural
characterization is lacking.

B. Abrasion and Wear Resistance; Strengthening

Schroeder [3] relates a curious fact The wear and abrasion resistance of a part can be enhanced
by a sol-gel coating but only if the coating is very thin (a few nanometers). A similar observation was
made recently by Maddalena et al. [40], who found that the strength of soda-lime glass rods could be
enhanced by thin silica coatings. In fact, they found that, if the coating is too thick (h > 0.2 mm), the
strength of the rod decreases. Apparently the well-known smoothing action of conformal sol-gel coatings
works to repair surface defects that might otherwise nucleate a crack or abrasion.

14-7
C. Membranes

Ceramic membranes find application in food, chemical, and pharmaceutical separations for gases,
liquids, and molten metals. Recently, membranes have been developed through sol-gel processing [41].
The sol-gel advantage is the control over porosity one has by controlling the size and ramification of
precursors. The inclusion of zeolites in a dense sol-gel matrix provides a second route toward. well-
defined pores, as reported by Bein and coworkers [42].

D. Solar

Solar applications have been focused on the economical preparation of solar mirrors [43], except
for the photo voltaic cell example described in Section I [1]. Coatings have been used to convert optically
rough surfaces into flatter and smoother ones for later coating with a reflective layer [44]. Similar
coatings have been used as protective films on solar mirrors [45] and as antireflective films [46].

VII. CONCLUSIONS

Surf~ce modification by sol-gel films is a growing area of research for several good reasons.
Sol-gel processing provides the flexibility and stoichiometric accuracy of solution chemistry while
requiring relatively little or no heating and minimal capital equipment The high cost of pure liquid
reagents usually is not important in making thin fIlms, but the necessity to filter reagents in critical
applications cou~d become a limitation.

No attempt was made to provide a comprehensive review. Rather, the examples were chosen to
be illustrative. To those authors whose work was left unmentioned, the author extends his apologies in
advance.

This work was supported by Sandia National Laboratories under DOE Contract No.
DE-AC04-76-DPOO789.

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14-8
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and Qrganometallic Polymers, Chapter 28, ACS Symp. Sec., 390. 345 (1988).

28. 1. C. Huling and G. L. Messing, 1. Am. Ceram. Soc., 11 C-222 (1988).

29. L. E. Scriven, in C. J. Brinker, D. E. Clark, and D. R. Ulrich, Eds., Better Ceramics Through
Chemistry Ill, Mat. Res. Soc. Symp. Proc., 121. 717 (1988).

30. J.-C. Casanova, C. Camoin, J.-L. Bouillot, and R. Blanc, J. Phys. III France, 1.. 1437 (1991).

31. G. W. Scherer, J. Am. Ceram. Soc.,,113 (1990).

14-9
32. Y.-O Tu ~d R. L. Drake, J. Colloid and Interface Sci., 135,562 (1990).

33. U. Brautigam, H. BUrger, and W. Vogel, 1. Non-Crystalline Solids, 110. 163 (1989).

34. K. A. Cerqua and 1. E. Hayden, J. Non-Crystalline Solids, 100, 471 (1988).

35. R. Puyane and C. 1. R. Gonzalez-Oliver, Proc. SPIE, 401, 307 (1983).

36. Y. Masuda, T. Tateishi, K. Matsubara, R. Ogawa, and Y.Kawate, Jpn. J. Appl. Phys. Part 1, Mb
1390 '(1991).

37. T. Monde, H. Kozuka, and S. Sakka, Chem. Lett. b 287 (1988).

38. C. Barbe and T. A. Ring, in B. J. 1. Zelinski, C. J. Brinker, D. E. Clark, and D. R. Ulrich, Eds.,
Better Ceramics Through Chemistry IV Mat. Res. Soc. Symp. Proc., 180. 883 (1990).

39. D. R. Uhlmann, G. Teowee, J. M Boulton, and B. 1. J. Zelinski, in B. J. J. Zelinski, C. 1. Brinker,

D. E. Clark, and D. R. Ulrich, Eds., Better Ceramics Through Chemistry IV, Mat. Res. Soc. Symp.
Proc., 180. 645 (1990). .

40. A. Maddelena, M. Guglielmi, A. Raccanelli, and P. Colombo, 1. Non-Crystalline Solids, 100,461

(1988).

41. Q. XU and M. A. Anderson, J. Mater. Res., Q, 1073 (1991).

42. T. Bein, K. Brown, P. Enzel, and C. 1. Brinker, in C. J. Brinker, D. E. Clark, and D. R. Ulrich, Eds.,
Better Ceramics Through Chemistry III, Mat. Res. Soc. Symp. Proc., 121, 761 (1988).

43. R. B. Pettit and C. J. Brinker, Sol. Energy Mater., Ji, 269 (1986).

44. C. S. Ashley and S. T. Reed, in C. 1. Brinker, D. E. Clark, and D. R. Ulrich, Eds., Better Ceramics
Through Chemistry ill Mat Res. Soc. Symp. Proc., 121,635 (1988).

45. S. T. Reed and C. S. Ashley, in C. 1. Brinker, D. E. Clark, and D. R. Ulrich, Eds., Better Ceramics
Through Chemistry III, Mat. Res. Soc. Symp. Proc., 121, 631 (1988).

46. C. S. Ashley and S. T. Reed, in C. J. Brinker, D. E. Cleark, and D. R. Ulrich, Eds., Better Ceramics
Through Chemistry ill, Mat. Res. Soc. Symp. Proc., 11 671 (1986).

14-10
 SOL-GEL-PROCESSING

SOLVENT
EXTRACTION

SOL SOL GEL AEROGEL

FIBERS
•
--
t-
••••••••
••••••••
••••••••
••••••••
ORDERED ARRAYS OF
UNIFORM PARTICLES
I
GELAnON
EVAPORAnON
EVAPORATION
OF SOLVENT
•

STRUCTURALCERAM;-.J's
XEROGEL
• ~ ••••e! .~ •••
;;; -j••••••
) J /
..-•• ij.

0
DRY HEAT!
XEROGEL FILM
SENSOR GLASS CERAMICS )
.... OPTICAL SEALING GLASSES .....
COATINGS CATALYTIC CATALYST SUPPORTS GLASSES

5))))).
DENSE GLASS FILM
1DIELECTRIC
PROTEcnVE
FIBEROPnC PREFORMS
CONTROLLED PORE GLASS

DENSE GLASS

Figure 1. Sol-gel processing road map (courtesy of Jeff Brinker). Film formation is one possible
branch; porous (xerogel) films have wide application even when only lightly heat-treated.
 stagnation pOint
\

Figure 2. Dip-coating schematic. In general, the substrate can be inclined at an angle a in order to vary
the· amount of gravitational draining.· Above the "stagnation point" all streamlines, and
therefore all solids, are entrained The "drying line" is defmed as x = o.

DEPOSITED FILM

X=O
FILM COLLAPSE ANDIOR
PORE FORMATION

GELATION

@FINALSTAGE {
OF DRYING

GRAVITATIONAL
DRAINING
® CONCENTRATION ALCOHOLIWATER
+
EVAPORATION
EVAPORATION

® ENTRAINMENT ENTRAINED DILUTE SOL

- - - RESERVOIR
SURFACE

DILUTE SOL

Figure 3. Stages of film formation in dip coating. In other types of coatings. many of these same stages
occur, but not simultaneously.

14-12
Figure 4. Interference fringes in an entrained film of ethanol being drawn from a beaker (bottom). The
height of the film is a few centimeters.

. .
o
E
3

o
o
o 1 2 3 4
x (mm)

Figure 5. Thickness profile of dip-coating film of pure alcohol. The parabolic shape is a consequence
of evaporation effects.

14-13
 propo noll water (50:50)
L[)
N I ,

0
0
0 0
N
0
0
0
0
~ L[)
(j) 0
""D 0
~

0 0
(j) 0
Ol 0
C
~
0 0
'+-
0
0
0
0
0 -
0
0
0
0
I ~ I
0

x2 x1

Figure 6. Thickness profile of a propanol/water mixture. The more volatile alcohol is essentially
completely evaporated by x = x2 , while the water lasts until Xl'

14-14
 15. HIGH-ENERGY ION IMPLANTATION OF MA1ERIALS

J. M. Williams
Solid State Division
Oak Ridge National Laboratory
P. O. Box 2008
Oak Ridge, TN 37831-6057

ABSTRACT

High-energy ion implantation is a very flexible type of surface treatment technique, because it
offers the possibility of treating almost any type of target material or product with ions of almost any
chemical species or combinations of chemical species. In addition, ion implantations can be combined
with variations in temperature during or after ion implantation. As a result, the possibility of approaching
a wide variety of surface-related material problems exists with ion implantation. This paper will outline
factors pertinent to the application of high-energy ion implantation to surface engineering problems. These
factors include fundamental advantages and limitations, economic considerations, present and future
equipment, and aspects of materials science.

I. INTRODUCTION

This paper will emphasize the technique of simple, direct high-energy ion bombardmerit of
materials for improvement or tailoring of near-surface properties. The energy range of interest is from
about 25 keY to about 400 keY. Thus, the technique can be contrasted with lower energy processing
techniques such as ion plating, chemical vapor deposition (CVD), or ion nitriding. The related, but more
complex, technique of high-energy ion beam assisted deposition (lBAD) will be treated in a separate
paper [1].

Development of high-energy ion implantation can be credited partly to the early nuclear industry,
in which ion production, acceleration, and mass separation were expanded into a sizable technology for
isotopes separation. From the materials science standpoint, ionization of the atoms per se usually plays
little to no role in the practical outcome, in comparison with, hypothetically, bombardment with fast
neutral atoms of the same energy. Ionization facilitates acceleration, mass separation, and dosimetry for
the bombarding ions.

Ion implantation is currently most widely used in the solid state electronics industry, in which the
technique is used for introduction of dopants in carefully controlled quantities into elements of integrated
circuits. Over 1000 ion implanters are in use for this purpose in the economically advanced nations. In
part because of this success, research is now directed toward the constructive modification of practically
every surface-related property in all classes of materials using high-energy ion bombardment Goals
include the construction of insulating layers on (or buried in) conductors and semiconductors; the
construction of conducting layers on (or buried in) insulators; the modification of virtually all possible
surface optical properties; improvements in corrosion, catalysis, or other electrochemical properties;
improvements in wear and brittle failure; and fabrication of thin single-crystal films of artificial diamond,
for example. Moreover, there are already a few other commercial successes for ion implantation, besides
solid state electronics. These are mostly in the areas of biomedical materials, aerospace and defense ·
materials, and certain production tooling.

15-1
 In the following sections of this chapter, factors pertaining to the use of direct ion implantation
for surface engineering of materials will be identified and discussed. Examples of materials science
results, applications, and pOssible· applications will be given.

II. FUNDAMENTAL ASPECTS

As far as particle-solid interactions are concerned, there are four important issues to consider for
any experiment or process design. Fortunately, the applicable physics is now rather advanced, and results
can be predicted with fair to good accuracy with quick, easy-to-use computer codes. The most widely
used code is TRIM [2], which is available for personal computers free of charge.

A. Range and Energy of Energetic Atoms

When energetic atoms penetrate into a solid, much of the energy loss is caused by elastic
collisions with target atoms of the solid. As a result, atoms in a beam, incident at a given energy, are
statistically scattered laterally and longitudinally as they slow down. The resulting depth distribution over
which the implanted atoms come to rest is typically somewhat Gaussian in form, but the distribution may
also be skewed, depending on beam and target parameters. Figure I shows a typical ion implantation
distribution for ions incident at a single energy, compared with a TRIM calculation.

B. Radiation Damage

Because of the atomic collisions involved in the slowing process, many target atoms (typically
about 1000 atoms per incident ion) are displaced from their normal lattice sites in the target material. This
large energy deposition in the product is a unique aspect of high-energy ion implantation as a materials
processing technique. The process is called radiation damage because target atoms are displaced. In fact,
the results are as often beneficial as they are deleterious. The damage can result in homogenization,
refinement of microstructures, improved adhesion of ion-treated layers, and amorphization. Numbers of
displaced atoms are also calculable by TRIM. Ultimately, most of the vacancies and interstitials
recombine to produce considerable healing.

C. Sputtering

Sputtering is another aspect of radiation damage in which knocked-on atoms near the surface are
ejected from the surface. Sputtering yields (Y) are typically 0.2 to 10.0 target atoms per iilcident ion,
depending on beam/target parameters. Thus, there is often no net addition of material to a target due to
ion implantation, and many times there will be a net loss. One effect of sputtering is to limit the
concentration of the dopant that can be introduced by ion implantation. Because of erosion, the outer
surface is a moving interface that moves into the previously implanted volume. The resulting maximum
concentration of the dopant at saturation at the surface is about IIY. Other aspects of sputtering include
angular dependence of sputtering from each element of topography on the surface, angular dependence
for shaped products in ion beams, and dependence on crystallite orientation. Distinctive surface textures
can result from combinations of these factors (Fig. 2).

D. Heat

The high energy of the process eventually appears as by-product heat deposited directly in the
target. One of the frequently claimed advantages of ion implantation is that it is a low-temperature
process. The claim is true, because heat is not needed to achieve penetration. By-product heat must be
managed, however. This is usually achievable by some combination of cooling and rate control for the

15-2
implantation. Ion implantations can be performed over a range of temperatures from cryogenic to quite
high values, depending on product requirements.

Ill. GENERAL ARGUMENTS

A. High Energy, Chemical Flexibility, and Metastable States

Ultimately, the more impactive contributions of ion implantation may result from the fact that, in
principle, the high energy of the process means that almost any chemical species· can be injected into
almost any' target-plastic, metallic, ceramic, or semiconducting-regardless of ordinary chemical
reactivity. This means that a large variety of presently unknown metastable states, with potentially
beneficial properties, could be created by ion implantation. Radiation damage also causes or aids in
producing metastabilities, e.g., amorphization of many materials. Moreover, known chemical reactions
can be employed in new and creative ways by using ion implantation. Buried, insulating oxide layers such
as Si and AI are examples (ion implantation of oxygen). Reactive ion etching or polishing (ion
implantation of F or CI) is another. Together with temperature variation during and after processing, ion
implantation allows a wider range of parameterization than is possible with most other types of surface
treatments. A disadvantage is that considerable R&D is often required for development of a single product
or process. Predicting engineering performance in advance of testing is difficult. Therefore, rapid
economic advancement is not necessarily assured.

B. Thickness of Ion Treated Layers

The depths of ion treated layers in solid materials are generally less than 1 J.llll (Fig. 1). This is
typically only about 10% of the depth of various coatings that are in competition for wear and corrosion
protection. Thus, mechanical fragility is a possible problem, and perhaps to a greater extent, a perceived
problem in the marketing of ion implantation products and services. Actually, ion implanted layers can
be more rugged than many suspect. For certain applications such as pure corrosion protection, without
too much mechanical stress, ion implantation is more effective than many coatings because of extremely
good lateral uniformity. In particular, this means the absence of pores where corrosion events can
nucleate. For cases in which ion implantation has won markets in improved production tooling, tolerance
has often been the key factor, together with difficulty in hardening the tool by competitive methods
without loss of tolerance. Clearly ion implantation will nearly always be one of the last steps in the
manufacture of any product to which it is applied.

C. Cost

High cost is a major disadvantage of ion implantation if treatment of large areas is contemplated.
Consider an ion dose of 3 x 1017/cml, which is typical of what might be needed for corrosion protection
or wear improvement of a metal product. The lowest cost that could be projected for processing materials·
to that dose in the United States is perhaps about $4OO/ml, with single modules of equipment of the type
described below. This estimate already takes into account some possible economies of scale. Further
improvement in costs may result from future equipment developments (see below), and very large scaling
could presumably reduce costs a great deal. At present, ion implantation costs can be born by products
such as nuclear fuel clad, hip joints, or other specialty products of high value. Even some industrial tools
can bear such costs, but many products cannot. For large areas, costs per unit area will be approximately
linear with dose. One avenue to cost reduction might be more optimal designs from the materials science
standpoint, which might result in important dose reductions.

15-3
D. Environmental Factors

Ion implantation is regarded as one of the most, if not the most, environmentally acceptable
surface treatments. One reason is that the process achieves excellent economy in use of feed material
because of very effective application. For the dose of 3 x to 17/cm2 mentioned above (a rather high dose),
about 1 lb of Cr would be required to treat 1 acre of surface, or about 3.7 lb of the precious metal Ir
would be required for the same number of Ir atoms as for 1 Ib of Cr. Process discharges are
correspondingly small and generally benign.

E. Other Factors

It is nearly impossible for an ion treated layer to spall froin a surface. 'This feature is of possible
importance for performance, environmental, and safety reasons. Very precise dosimetry is possible, as
in semiconductor doping, for example. Often there is no change in the appearance of a surface due to ion
implantation. 'This has been both an advantage and a disadvantage, depending on the application.

IV. EQUIPMENT

A. Present Equipment

There are currently five types of commercial ion implantation equipmen~ available. Concepts,
intended purposes, advantages, and disadvantages will be presented: Four of the implanters are ion beam
devices, but one is a plasma device that involves different concepts.

1. Magnetically Analyzed Plus Postacceleration Ion Beam Implanter

'This type of ion implanter, having emerged as the industry standard for solid state electronics, is
by far the most widely used at present. Therefore, it provides a logical reference point for discussing
competitive features. Figure 3 is a schematic layout of such an implanter: The ion source part of the
implanter is usually a type of plasma source known as a Freeman source, .but such a source may also be
modified to allow for sputter ejection of ions into the plasma By using such a source in conjunction with
suitable recipes, ions of most chemical species can be generated. Ions from the source pass through an
extraction/pre acceleration stage, which brings the beam up to about 30 ke V for magnetic analysis. The
magnetic analysis stage reduces the beam to a single charge state of a single element (and generally a
single isotope of that element), that is delivered to the mass analyzing slit Thereafter, the beam is further
accelerated in the postacceleration stage up to an accelerator potential of about 200 kV. If the charge state
is 2 instead of 1. the particle energy will be doubled (e.g .• 400 keV instead of 200 keY). Typically there
is a large sacrifice in beam intensity to achieve charge states higher than 1. After the beam passes through
the accelerating column, beam optical devices allow delivery and rastering of the beam to sizable targets
in the vacuum end station, as desired.

The ion implanter of the type shown in Fig. 3 provides several advantages but also provides the
most expensive process of any of the implanters. The ion source. in conjunction with the magnetic
analysis. provides the most chemical flexibility. The device provides the best overall quality control.
including beam uniformity and dosimetry (on a flat area). Because of the two acceleration stages, a wider
energy range is provided than is usually found on competing implanters. Currents (of about to rnA) are
lower than for the other implanters. In addition to use in the solid state electronics industry, this type of
implanter has found general use. A disadvantage of all beam implanters is that shaped (not flat) surfaces
must be manipulated in the beam to achieve uniform doses. A variety of fixturing devices are available
to perform these operations in vacuum.

15-4
 -
2. Unanaly~ed Beam Gas Ion Implanters

Because of the costs associated with the analyzed beam process, a simplified design has been
developed that is known as the unanalyzed, broad beam gas ion implanter (Figs. 4 and 5). This type of
equipment is intended primarily for ~mplantingmeta1lurgical products with nitrogen ions for corrosion
inhibition, wear inhibition, etc. Such an implanter can make use of more than one type of ion source, and
very large currents are possible. Capabilities of the sources themselves are not necessarily different from
those of analyzed beam implanters. But because ions of all constituents in the feed recipe are delivered
to the product, the chemical quality of the beam depends only on the purity of the feed material. Thus,
if a metal ion plasma were volatilized by use of a chlorination recipe, CI ions would also be delivered to
the target For this reason, unanalyzed beam implanters are regarded as most suitable for ions that can
be generated from pure gaseous material such as N. If there were sufficient reasons, inert gases could
also be used, and hydrogen-containing gases (methane, silane) could be used if the hydrogen were not a
problem to the product Capabilities of such implanters are as much as 100 rnA at 100 keV. Without
magnetic analysis, such an implanter delivers both multiple ionization states (e.g., N+ and N++) and singly
ionized atomic and molecular states (e.g., N+ and N;). Given that the. accelerator potential is fixed, either
effect amounts to particle energy dispersion, and therefore range dispersion, for delivered N atoms. The
molecular effect is the larger of the two for ion sources used in these implanters. For metallurgical
purposes, dispersion, instead of the more highly peaked implant distribution (Fig. 1), is often not a
disadvantage. Accurate dosimetry may be compromised.

It can be argued that an ultimate advantage to this big beam type of technology, compared with
plasmas that require magnetic confinement (see Section IV.A.5.), is "scalability." This means that' for
sufficiently large single modular targets, or for a sufficiently large total area treatment rate, economies of
scale are available for this technology, whereas for magnetically confined plasmas, even low energy ones,
scaling up to areas above a certain optimum may become quite costly.

3. Analyzed Beam Gas Ion Implanters

If silicon wafers (held at high temperatures) are bombarded with high energy 0 ions to very high
doses, the 0 precipitates as an insulating layer of Si02 in the subsurface of the Si, and the single-crystal
Si is retained at the surface on top of the insulating layer. This fact has given rise to advances in silicon-
on-insulator technology. In commercial application, the technique is known as the SIMOX process. For
execution of the process, good control of range and dosimetry is needed. Eaton Corporation has
developed a system for performance of the process. In concept, the layout is similar to that of Fig. 3,
because magnetic analysis is provided. Single atoms of 0 at single values of energy can be delivered.
The present system delivers 85 rnA at 180 keV, but expansion in capability is said to be imminent
Presumably such a system could be adapted for use with other gases if a process were needed

4. The Metal Vapor Vacuum Arc (MEVV A) Technology

The MEVV A technology makes use of a vacuum arc ion source to generate high ion currents of
metallic materials [4]. No gaseous plasmas are used in the source, and the only feed material needed is
solid metal of the desired species. Thus, the source provides excellent vacuum quality for the target
without using extensive differential pumping. The source generates metal ions with a range of ionization
states (but no molecular states), and the beam is delivered unanalyzed. Therefore, pertinent remarks given
above apply. The principle advantage of the system is economy in the ion implantation of metallic
species. The system is complementary in capability to the. unanalyzed gas ion implantation system
described above. The beam is simply a cone diverging from the source, also. 1he source is, in fact, a

15-5
rapidly pulsed source. At present, the time-averaged capability is about 50 mA of current at 100 keY of
accelerator potential.

5. The Pulsed Source Ion Implantation (pSII) Technology

The pulsed source ion implantation (psn) technology [5] is the only currently existing high-energy
system that is not a beam implanter. Thus, the ions are not in free flight when they impinge on the target.
Instead, the product is a field tenninal in the process. This technology is a derivative of fusion energy
technology. Ions in a large plasma, generated by electron cyclotron resonance (ECR) microwave or other
means, are extracted directly to the target (product) by a pulsed, high-voltage supply. Arcing to the
surface is prevented by the pulsing. This technology is the most competitive with the unanalyzed gas ion
type of implanter. As with that technology, the psn technology is intended primarily for use with gas
ions, particularly N, but its use with other gases is also possible. Hybridization or combination with other
coating techniques to achieve ion assisted deposition is also possible. The constitution of the ions
delivered is about the same as for the unanalyzed beam, in terms of molecular and ionization states. The
most important advantage of the system is cost, and this advantage results in good part from the fact that
the ions are incident at normal angles to essentially each surface element of the product This means that
manipulation of shaped products is not needed to achieve uniform treatment Also, if sputtering presents
a concentration limitation for beams, that concentration limit will be higher for normal incidence. Clearly
there will be some loss of flexibility for treatment of insulators, because such products would at least
require backing conductors of approximately the same shape.

B. Future Equipment

. Ion beam processing equipment for the 21st century is being developed most intensively in Japan.
A good fraction of the effort is under the auspices of a major joint government-industry initiative, and the
corresponding agency is known as the Advanced Material-Processing and Machining Technology Research
Association (AMMTRA). In addition to ion beam technologies, laser and other advanced materials
processing technologies are being developed. The government contribution to the ion beam technologies
is said to be more than $l00M. In addition to equipment development, materials science research is also
being supported. Competing industries, which are not a part of AMMTRA, are quite active also.

Table 1 summarizes the programs of AMMTRA in the area of ion beams [6]. Figure 6 is an
illustration of the sheet ion system being developed by UL VAC Japan, Ltd. Such a system will be capable .
of processing very large surface areas.

V. MATERIALS SCIENCE

Each problem that arises will likely require a specifically selected R&D approach and then a
correspondingly specific process design. The following general remarks and illustrations are intended to
provide ideas as to what might be possible. .

A. Amorphization

Ion bombardment results in amorphization of certain materials whose chemical makeup lends a
susceptibility towards amorphization. If this chemical predilection exists, amorphization results from
radiation damage alone and usually occurs at a rather small dose. Therefore, amorphization will usually
be quite inexpensive in any case in which it can be projected as having a practical benefit. If the target
does not have the suitable initial chemical character, it might be produced by high-dose ion bombardment.
Then amorphization should soon occur. This latter pathway will generally be more expensive, however.

15-6
 Table 1. Summary of AMMTRA R&D Projects [6]

Target Specifications
Main Issue of
Subject Development Mid (FY 1990) Fin (FY-1993)
Development of high- (1) High-current metal Metal ion AI, Si+
current metal ion beam ion source and ion 100 eV-l00 keY
system [Nissin Electric transport 100 mA (100 keY)
Co., Ltd.] (2) Ion beam tech- 100 keY (AI+) Modification area
_ nologies for surface ~ 100 cm2
modification Current density
1 mA/cm2
Integrated, high-current (1) High-energy, high- Sheet ion beam Sheet ion beam
ion beam system current ion beam 100 keY, 250-rnA 100 keY, 2A
[ULVAC Japan, Ltd.] system
(2) Low-energy ion Low-energy ion Low-energy ion beam
beam system beam ~ 100 eV, 5 rnA
(3) In situ beam ~ 1ooeV, 1 rnA
diagnostics
Ionized multiple beams (1) Cluster source with 200 mm diameter AI, Bi, Sr, Ca, Co ion
technology with high high deposition rate 0.3 ~min beams
deposition rate (2) Uniform ion current
[Mitsubishi Electric density on wide
Corporation] substrate
(3) Excited gas source 200-mm diameter
with high flux
(4) Compact designing 0.1 mmlmin
of ionized cluster beam
(ICB) source and gas
source
High-current focused (1) Gas-phase ion He+ He+ ion beam
gas-phase ion beam source Beam diameter
system [JEOL, Ltd.] S tOnm
(2) He gas recondenser 2 JJAlsr 2 JJAlsr
(3) Focusing column ~20K
for gas phase ion
source (GPIS) 25pA
(4) Microlithography ~ 2.66 x 7
to· Pa 100 keV
system
High-energy ion beam (1) Variable-frequency ~ 1 MeV 0.5-4.0 MeV
system [Hitachi Ltd.] radio frequency ~ 0.5 rnA (pulse) (variable)
quadrupole (RFQ) ~ 1 rnA
(2) Microwave ion
source for multiply
charged ion beam
(3) Me V ion implanter

15-7
 Table 1. Summary of AMMTRA R&D Projects [6] (Concluded)

Target Specifications
Main Issue of
Subject Development Mid (FY 1990) Fin (FY 1993)

Surface improvement (1) Improvement of Improvement time = Improvement time

technology by ion glass surface 1h 10 min
;5;
implantation [Nippon (2) Evaluation of Glass substrate Glass substrate
Sheet Glass Co., Ltd.] improved glass 050mm 0300 m.m
Modification of metal by (1) Improvement of Evaluation of mini- General corrosion rate
ion implantation corrosion resistance of sized sample 0.125 mm/yr
;5;
[Kobe Steel Ltd.] n and carbon steel
(2) linprovement of Vicker's hardness
wear resistance and ~ 1000
surface hardness
Deposition of high- .. (1) Design of optical Reflection ~ 20% Reflection ~ 20%
reflection X-ray mirror systems
[Japan Aviation (2) Ion beam sputter Incident angle ~ 5°, Incident angle
Electronics Industries, deposition A. = 1-30 run ~ 5°, A. = 1-30 run
Ltd.] (3) Ion beam deposition 25-mm diameter (100 riun x 100 nun)

The following chemical and other factors favor amorphization from the empirical point of view.

• Chemical bonding (in order)-covalent, ionic, metallic

• Complex equilibrium structure for the chemical composition at the bombardment condition
• Narrow compositional range for equilibrium phase field (e.g., intermetallic "line" compounds)
• More elements
• Two or more phases of differing crystal structure in chemical equilibrium at the bombardment
temperature
• Low melting point
• Low-temperature bombardment

Because bombardment temperature is a factor, .a design choice as to whether to produce

amorphization or not during ion implantation can sometimes be made. Amorphization can have varying
effects. Ironically it can reduce brittle effects, provide isotropic deformation modes, improve fracture
strength, and reduce the elastic modulus for ceramic materials, but it seems to make metallic materials
more glassy.

B. Effects in Polymers

At low doses, ion bombardment produces increased crOSS-linking, increased polymerization, and
increased ultraviolet (UV) absorption [7]. At higher doses, hydrogen gas evolution, densification, and
fmally carbonization occur. Beam pyrolysis of photoresists painted onto metal surfaces can result in hard
carbon coatings with excellent adhesion and properties [8].

15-8
C. Semiconductors

, In addition to the doping and SIMOX process already mentioned, it is possible to produce a
subsurface layer of cobalt silicide, which is fully metallic in conducting qualities [9]. Considerable
research continues in compound semiconductors such as SiC, CdTe, and GaAs for which amorphization
and epitaxial regrowth are special problems in comparison withSi. Ion implantation doping for solar cell
production has been considered, and a non-mass-analyzed system for ion implantation of P, using solid
metal feed material, was designed and evaluated [10]. The process is claimed to be economical and
environmentally benign.

D. Metallic Materials

A variety of surface engineering approaches are possible, depending on problem details and
economic factors. Simple nitrogen ion implantation often has very favorable effects on wear and fatigue
of metals and alloys high in Cr, 11, or AI. Nitrogen implantation usually does not result in improvement
in friction. Treatments that result in carbonaceous or carbide coatings are possible. Figure 7 illustrates
one successful case of salt-pitting corrosion protection for an aluminum alloy pillow block material for
helicopters [11]. The application actually involved fretting corrosion. Fretting is considered to be a
particularly favorable type of wear problem for approach by ion implantation because spalling is so
difficult The dopant that worked was Cr. Nitrogen ion implantation produces large increases in the
electrochemical salt pitting potential for aluminum, but corresponding increases in salt spray performance
were not observed, as they were for Cr.

E. Ceramics [12]

Certain effects due to amorphization were identified above. Figure 8 is a Weibull analysis for
engineering fracture stress of ~03. Two types ofion implantation have been done. In the first, a high
dose of Cr was used ·at room temperature. In the second, a low dose was Used at temperatures at which
amorphization occurred. For AI20 3, an implantation at 77 K was required to produce amorphization, but
for ceramics that are amorphizable at room temperature, the amorphization process would be quite
economical. For the amorphous case, the stress increases by a factor of nine for extrapolation to the
cumulative failure level of 0.2%. In addition, amorphization of ceramics might produce a variety of other
benefits. Projected Hertzian stresses and stress concentrations arising in tribological situations might be
reduced due to amorphization. Elastic and plastic compliance for adhesion to dissimilar materials might
be improved

For high-dose implantations, metallic dopants precipitate as metal particles in an ~03 matrix
provided that the postimplantation anneal is done in vacuum. For annealing in oxidizing atmospheres, .
metallic dopants are incorporated as oxide alloys. Buried conducting thin-metallic layers, analogous to
the planar buried conducting or insulating layers formed in silicon by ion implantation, have not been
formed in sapphire.

Low-dose ion implantations in graphitic and glassy carbon produce dramatic improvements in wear
[13].

VI. SUMMARY

On its pure technical merits, the surface processing technique of high-energy ion implantation
would appear to offer good prospects for improving technologies that will be applied in the future in the
transportation and utilities industries. The problem areas that seem most suitable for approach by ion

15-9
implantation include interfaces of dissimilar materi~s (metal-polymer or metal-ceramic interfaces),
corrosion and tribology in general and certain problems pertaining to ceramics (fracture, spalling of
bearings, etc.). For the near future, however, the high cost of ion implantation is likely to restrict its use.
Potential near-term applications for devices such as chemical sensors (oxygen, pH), ceramic bearings, cam
followers, and other smaller engine parts might be cost effective, assuming th~ ion implantation could
solve problems. In the longer term, more economical ion implantation technology, coupled with minimal
environmental impact, could make ion implantation attractive for wider use in basic economic areas such
as utilities and transportation.

ACKNOWLEDGMENT

1bis reSearch was sponsored by the Division of Materials Sciences, U.S. Department of Energy,
under Contract No. DE-AC05-840R21400 with Martin Marietta Energy Systems, Inc.

REFERENCES

1. G. Hubler, Chapter 16, this volume.

2. J. F. Zeigler, J. P. Biersack, and U. Littmark, The Stopping and Ranges of Ions in Solids, Pergamon,
New York, NY, 1984.

3. J. L. Whitton, in G. Kiriakidis, G. Carter, and J~ L. Whitton, Eds., Erosion and Growth of Solids
Stimulated by Atom and Ion Beams, Martinus Nijhoff, Dordreeht, Germany, 1986, 151.

4. J. R. Treglio, Nucl. Instr. and Metb., B40/41, 567 (1989).

5. J. R. Conrad, 1. L. Radtke, R. A. Dodd, Frank J. Worzala, and Ngoe C. Tran, 1. Appl. Phys., g,
4591 (1987).

6. I. Yamada, Nuel. Instr. and Meth., B59/60, 1467 (1991).

7. A. Licciardello, O. Puglisi, L. Calcagno, and G. Foti, Nuel. Instr. and Meth., B39, 769 (1989).

8. A. Kluge, H. Ryssel, B. H.-S. Javadi, R. Ochsner, and H. Ruoff, Proceedings of the 7th International
Conference on Surface Modification of Metals by Ion Beams, Washington, DC, July 15-19, 1991,
to be published.

9. A. E. White, K. C. Short, R. C. Dynes, R. Hull, and J. M. Vandenberg, Nucl. Instr.and Meth., B39,
253 (1989).

10. A. 1. Armini, S. N. Bunker, and R. Bricault, Nucl. Instr. and Meth.,!!2.. 94 (1985).

11. J. M. Williams, A. Gonzales, 1. Quintana, I.-S. Lee, R. A. Buchanan, F. C. Burns, R. J. Culbertson,

M. Levy, and 1 R. Treglio, Nuel. Instr. and Meth., B59/60. 845 (1991).

12. C. W. White, C. J. McHargue, P. S. Sklad, L. A. Boatner, and G. C. Farlow, Mater. Sci. Rpts., i,
41 (1989).

13. M. 1. Kenny, 1. T. A. Pollock, and L. S. Wielunski, Nuel. Instr.and Meth., B39. 704 (1989).

15-10
 280 keV Zr ONTO Ti

-en
~
c::
o EXPERIMENT
:J
~ - TRIM CALCULATION

-:ee
z-
as
o
~
a:
~
z
w
()
z
o
()

0.0 0.04 0.08 0.12 0.16 0.20 0.24

DEPTH (J.1 m)

Figure 1. Concentration versus depth for 280 keY Zr ions implanted into a Ti-6 wt % Al-4 wt % V
alloy. The experimental determination of the depth distribution by Rutherford backscattering
spectrometry has been compared with that derived from a TRIM calculation.

Figure 2. "Cones and pyramids" type of sputter texture produced on a copper surface by use of ~ huge
dose (1.5 x 1019/cm2) of Ar ions at 40 keY [3]. The breadth of the area is about 3 1JIIl.
Photograph courtesy of J. L. Whitton.

15-11
 ION ACCELERATION ELECTROSTATIC
MASS COLUMN SCANNING
ANALYZING
SLIT
.1

MAGNET

ENDSTATION

--
VI
I

N
ION EXTRACTION!
PREACCELERATION

T~
ION
SOURCE

1
Figure 3. Schematic representation of a postacceleration type of ion implantation system, with magnetic
mass separation of beam constituents. The target in the end station is intended to represent
an array of orthopedic knee joints that are being treated for improvement of wear performance.
Figure 4. Automotive crankshafts undergoing N-ion implantation. The beam diverges as a cone from
the source and is unanalyzed for mass, molecular, or charge content. This facility is at AEA
Industrial Technology: Harwell Laboratory, United Kingdom. (photograph courtesy of
G. Dearnaley.)

15-13
--
,
VI

Figure 5. View of an ion implantation system intended primarily for use in ion implantation of large
metallurgical products. TIlis system is manufactured by Leybold and has capabilities similar
to the system shown in Fig. 3.
 INTEGRATED, HIGH CURRENT ION BEAM TECHNOLOGY
TARGET: BEAM PROFILE OF 50 em x 5 mm

HIGH ENERGY
SHEET ION BEAM
100 keV, 2 A

--
VI
I

VI

LOW ENERGY
MULTI-ION BEAM GENERATOR
100 eV, 5 rnA

Figure 6. Schematic representation of the "sheet ion beam" type of ion implanter. Development of this
device is being done by ULVAC Japan, Ltd. as part of the AMMTRA program.
Figure 7. Photograph showing coupons of 2014 AI, new, after various ion implantation treatments and
salt fog testing (168 h), and as-tested with no ion implantation. Initially, the surfaces were
all mechanically polished. The ion implanted areas were 2 cm in diameter, and the implanted
samples were halved after testing. Cr ion implantation was very effective, reducing corrosion
to almost nil. Oxide patches on unimplanted areas were up 30 IJlll in thickness.

15-16
 99.9

90.0
~ 70.0
w 50.0
cr
::l 30.0
--1
<{
20.0
li..
10.0
w
> 5.0
--
VI
I

....:I
~
--1
::l
::E
2.0
1.0
IMPLANTED-CRYSTALLINE
IMPLANTED-AMORPHOUS
AS-POLISHED
::::>
u 0.5
0.2
0.1
2
10'
STRESS (MPa)

Fig. 8. Weibull analysis for fracture under four-point bending of an as-polished, implanted-
amorphous, and implanted-crystalline Al 20 3 specimen.
 16. SURFACE TREATMENTS WITH ION BEAM ASSIS1ED DEPOSITION

G. K. Hubler
U.S. Naval Research Laboratory
Code 4671
Washington, DC 20375

ABSTRACT

This contribution introduces ion beam assisted deposition (lBAD), reports on progress toward
obtaining an understanding of the physical and chemical processes that are active during mAD, and gives
examples of applications that are currently in use or that are projected to be in use in the near future.
Sufficient background is given that the reader should obtain a working knowledge of the technique,
understand the advantages and limitations, and have a good idea as to how it may be applied to specific
problems. In particular, a model is presented that includes the effects of sputtering, reflection of ions,
multiple species beams, charge exchange neutralization, and incorporation of ambient gas atoms. Good
agreement is found with data on several materials for the composition of fIlms as a function of the arrival
ratio of ions to evaporant atoms. Calculations based on a collision cascade simulation are reviewed that
predict the energy dependence of the critical arrival ratio to achieve low intrinsic stress in deposited films.
Factors that influence the choice of the geometry for beam assisted deposition systems, the choice of ion
beam energy, and applications of the films are discussed in detail.
...
I. INTRODUCTION

Ion beam assisted deposition (mAD) refers to the process in which evaporant atoms produced by
physical vapor depositiori (PVD) are simultaneously struck by a flux oflow energy ions [1]. The extra
energy imparted to the deposited atoms causes atomic displacements in the bulk and surface atom
migration. This can result in improved film properties [2,3] that include better adhesion and cohesion of
the film, modified residual stress, and higher density compared to similar films prepared by PVD [4,5].
When the ion beam or the evaporant is a reactive species, compounds such as refractory Si3N4 can be
synthesized at very low temperatures [6].

There are many excellent review articles on mAD films in the literature [1,7-11]. However, the
majority of these papers focus on the film properties, and little attention is given to the physical aspects
of film fabrication. In this article, the development of an understanding of the physical processes active
during IBAD is presented, as well as film properties and applications [12]. Models are presented for the
prediction of bulk physical properties of compound nitride films synthesized by mAD. The models
accurately predict the fIlm composition and thickness for nonreactive species and the amount of ambient
gas incorporated for reactive species. Applications are discussed in the areas of optical films, coatings
for oxidation and corrosion protection, and tribological coatings.

II. BACKGROUND

It is interesting to trace the development of mAD in the surface modification community. The
pioneering work that demonstrated the superior properties of mAD fIlms was done chiefly by researchers
in the field of optical thin fIlms during the late 1970s and early 1980s. Surface modification by ion
implantation at - 100 keV developed independently from the mAD technique. However, it was always
understood by the implantation community that the shallow depth of penetration was a major limitation
to the development of certain applications. The advantages of PVD are the formation of thick films, a

16-1
wider range of film composition, and lo~ cost. The advantages of ion implantation are high adhesion,
bulk density, low substrate temperature, good reproducibility and control, and absence of catastrophic
stress levels. Note that the advantages of PVD are exactly the disadvantages of ion implantation and vice
versa. The .connecting line shows that mAD combines the advantages of ion implantation and PVD and
discards the disadvantages. Table 1 identifies the reasons why many researchers in the ion implantation
community have expanded their interests to include the development of mAD.

Ill. EXPERIMENTAL CONDITIONS

Figure 1 shows the most common geometry used in mAD. Important details of the methods may
be found elsewhere [12-14]. Briefly, a broad beam from an ion source (Kaufman gun) impinges on a
substrate simultaneously with the deposited atoms. An electron beam source is the most common PVD
source, but thermal sources, e.g., a Knudsen cell, or a sputter target in the case of dual ion beam
sputtering, are also used. The most straightforward geometry for data interpretation and for the generation
of uniform films is a small angle « 30 degrees) between the vapor and ion sources. A 90-degree angle
is also used when the beam is generated by an ion implanter. In systems that use a Kaufman ion source,
the operating pressure is typically between 5 x 10-5 and 5 x 1<r Torr, whereas in systems that use an
extemalion source (e.g., an ion implanter), the pressure can be much lower in the deposition chamber.

Ion beam energies between - 30 eVand 100 keY have been investigated. The appropriate energy
is a matter of choice, often dictated by the equipment one has available to construct an IBAD system.
Although there is no general agreement on the best energy to use for mAD, some qualitative information

Table 1. Comparison of the advantages (+) and disadvantages (-) of ion implantation
and physical vapor deposition (PVD) ion beam assisted deposition in which mAD
combines the advantages of both processes

Feature Ion Implantation PVD

( -) (+)
Thickness 100 om Micrometers
Concentration < 40 at. % 0%-100%
Cost High Low
m
(+) (-)

Adhesion Excellent Poor

Density High (bulk) Low « bulk)
Stress Low High (delamination)
Substrate temperature Low High (for best film
properties)
Reproducibility Excellent Fair
Control Excellent Fair

16-2
is available. Both M. Iwaki [15] and G. Wolf [14] report that while the adhesion of IBAD films is
improved at low energies (500 e V to 3 ke V), the best adhesion is obtained at higher energies (20 to
40 keY). On the other hand, Martin [9], Gibson [1], and others report that the absorption in optical films
increases as the energy increases, due to a greater displacement damage, and they obtained their best
results at energies below 500 e V. Therefore, a tentative conclusion is that the beam energy should be .
chosen according to the application of the film. For fllms intended for environmental protection, wear
resistance, decorative coatings, etc., the high energy is suitable to obtain the best adhesion. Also, film
damage is less likely to affect the important properties of corrosion resistance and hardness. For films
intended for optical and microelectronic devices, low energy is preferred to minimize optical absorption
and the formation of electrically active defects.

IV. PHYSICAL PROCESSES

Figure 2 presents the physical processes to be considered by a simple phenomenological model

of the mAD process that is discussed in greater detail by Van Vechten et al. [13]. Referring to Fig. 2,
vapor atoms (indicated by V) impinge on the growth surface. The ions, which for the sake of discussion,
consist of both N; and N+, are either implanted beneath the surface or reflected with reflection coefficient
r. As a result of ion bombardment, some of the deposited atoms are sputtered from the surface with
sputtering coefficient S, and adsorbed ambient gas atoms (indicated by G) may be either desorbed or
stimulated to chemically react with the surface atoms. Finally, in passage through the ambient gas, some
of the ions are neutralized by charge exchange collisions, and therefore will not be counted by the charge
collection system.
..
A. Model For Film Composition

Simple models have been proposed in previous work [12,13) to predict the composition of IBAD
fllms in the synthesis of nitrides. A material system that particularly lends itself to quantitative study is
silicon nitride, in which Si is evaporated and nitrogen ions impinge on the surface. Alloys of any
composition Si1_xNx up to stoichiometric Si3N4 are produced, depending on the value of the ·arrival ratio,
R., of nitrogen atoms to silicon atoms .
. The alloy composition, Rr, defined as the nitrogen to silicon ratio in the film is given by
R f = R. (1 - <1'»/(1 - R. <S» (la)

where
(1b)

In Eq. 1a, <r> is the effective reflection coefficient of nitrogen ions and atoms (0.10), and <S> is the
effective sputtering coefficient of silicon (0.26). The parameter values were determined in previous work
for a 500-eV nitrogen beam and an operating pressure of 2 x 1(}' Torr [13]. In Eq. 1b, <a> is the
effective number of nitrogen atoms per .unit charge (1.89), l+Ji is the charge exchange correction factor
(1.52), 'Y is the ion beam tooling factor (1.05), IF is the ion current density (Alcm2), e is the electron
charge, NSi is the atomic density of Si, 'Ye is the tooling factor for the quartz crystal microbalance (1.05),
and Q is the deposition rate of Si from the quartz crystal microbalance (cm/s). All of the parameters in
=
Eq. 1b are independent of Ip and Q, so R. K IF/Q, where K is a constant

The film composition, Rr, is plotted in Fig. 3 versus Ip (bottom scale) and R. (top scale) for films
deposited in a pressure (N0 of 2 x 1()' Torr and at a deposition rate of 10 Als. The composition was
measured by Rutherford backscattering spectrometry (RBS). The curve in Fig. 3 is calculated from

16-3
Eqs. la and Ib for the indicated parameters values. The agreement between the experimental points and
the model is excellent Assumptions included in the model are (1) there is no ambient gas inCOrpOration,
(2) N atoms not reflected are implanted beneath the surface, and (3) there is no diffusion or sputtering of
N after coming to rest These assumptions are applicable because (a) the curve extrapolates to Rr = 0 at
o ion current, (b) one value of the. sputtering coefficient reproduces the data at all currents (e.g., the
surface binding energy is unchanged), and (c) all nitrogen is accounted for either by reflection or by
incorporation into the film (e.g., there is no loss of nitrogen from the t1lm).

Similar data for the boron nitride system [20] are plotted in Fig. 4. As was the case for Si, the
data extrapolate to the origin indicating no gas incorporation into the film. The curve is a fit to Eq. la
for the sputtering coefficient S where all the other parameters are fixed at the same values as for Si with
the exception of r (r = 0 for BN). The fitted value of S is 0.11 ± 0.1 where the large error results from
the limited amount of data obtained at high arrival ratios.

B. Model for Film Thickness

A model for the thickness of IBAD silicon nitride t1lms was proposed in an earlier paper [16].
A useful quantity for the fabrication of compound films is the ratio of the thickness of the film deposited
on the sample, D, to the thickness of silicon deposited on the quartz monitor, Q, which is called the
thickness correction factor, Te. It is expressed as

Tc = "it. Ns/N.[R.(1 - <r> - <S» + 1] (2a)

, .
where the alloy atomic density is

Na = pNM = [2.28 + (PSN - 2.28) Rcl1.33] N(28 - 6Rr ). (2b)

In Eq. 2b, P is the density of the alloy, A is Avogadro's number, M is the atomic weight of the alloy, and
PSN is the density of amorphous Si3N4 • Interpolation of density is linear in Rr. The Si density (2.28 glcm3)
and amorphous Si3N4 density (3.13 glcm3 ) are used at the end points of Rf = 0 and 1.33, respectively.

Experimental data for Te are plotted versus ion current density [13] in Fig. 5. The solid circles
are D/Qt where D was derived from fits to infrared reflection spectra. For the open circles, D values for
a different set of samples were obtained by surface profile measurements. There is good agreement
between the two methods. The solid curve is computed from Eqs. Ib and 2 with the parameters given
earlier in this paper. For ion currents greater than about 100 J.lAIcm2, the curve is in reasonable agreement
with the thickness data, with deviations averaging less than 2%. For smaller ion currents, departures are
much greater.

C. Incorporation of Ambient Gas Atoms

Materials that are amenable to the mAD process are nitrides, oxides, and carbides. Frequently,
a reaction will occur between the ambient gas (from the ion source or the backfilling of the chamber) and
the evaporant (from relaxation of the first criterion for applicability of the model described previously).
It is of basic interest to understand how the ion beam modifies and controls this reaction.

Figure 6 shows the composition ~ of titanium nitride films (closed circles) versus the arrival ratio
Nm for a 11 deposition rate of 10 Ns and a pressure of2 x lO's Torr [17]. At zero ion current (R. = 0),
~ of the film is about 0.4, which is in sharp contrast to similar data for silicon nitride (Fig. 3) where
Rr =0 at R. == O. At higher pressure (2 x 10'" Torr), ~ = 1.0 at R. =0, and at lower pressures, the data

16-4
collapses toward the solid curve that represents the calculated amount of nitrogen incorporated into the
film from the ion beam. TIlis must be true in the limit of very low pressures in which the amount of
nitrogen ambient gas arriving on the surface is much less than the contribution from the ion beam. The
triangles in Fig. 6 are obtained by subtraction of the curve from the data points and represent the amount
of nitrogen incorporated from the ambient. To perform this subtraction, assumption (2) in Section IllA
is used, Le., all of the nitrogen that is not reflected is incorporated into the films.

A useful way to analyze the .data is shown in Fig. 7 where Rgf, the amount of nitrogen
incorporated from the ambient, is plotted versus the pressure/deposition rate ratio in (TorrI Ns). Data for
two different Ra values are shown. TIlis method of data reduction has the advantage that the relative
fluxes of ions, evaporation, and ambient gas are evident in the plot. At R. =0 (filled squares), the amount
of gas incorporation changes from stoichiometric titanium nitride to pure titanium in a little over a two
order-of-magnitude decrease in gas pressure or increase in deposition rate. TIlis demonstrates the well-
known phenomenon that high deposition rates produce higher purity films by reducing the impurity
gas/evaporant impingement ratio. For R. = 0.25, the curve is altered, and two interesting points may be
noted. FIrst, the data retain the same shape but shift to lower pressure/deposition rate values. TIlis implies
that one effect of the ion beam is to increase the sticking coefficient of ambient N2 gas molecules to the
surface. Secondly, the saturation value at a high pressure or low deposition rate decreases from 1.0 to
about 0.86. TIlis can be explained by a decrease in the active absorption sites on the surface as a result
of ion bombardment or by desorption of adsorbed nitrogen.

A simple calculation was performed using a dynamic surface coverage model similar to one
proposed by Barbie et al. [18]. The model is preliminary and is intended to demonstrate qualitatively
which physical processes should be considered to explain the results. The model includes a'surface
coverage dependent sticking coefficient for physisorption and the concept of dynamic exposure time. The
solid line in FIg. 7 is the calculated Nm ratio assuming a sticking coefficient of 0.1, a fraction of active
surface absorption sites for N2 of 0.5 monolayers, and a negligibly small thermal desorption rate. The
curve is in reasonable agreement with the data fOf, R. =O. The line corresponding to R. =0.25 (short
dashes) is obtained by setting the sticking coefficient to 1.0 and reducing the surface active fraction of
adsorption sites to 0.42. Thus, it is possible to infer two effects of bombardment: (1) the sticking
coefficient for the N2 increases by a factor of about ren, and (2) the number of active adsorption sites
decreases approximately in proportion to R.. A more complete model would account for the sputtering
of surface adsorbed nitrogen, which could be part or all of the latter effect.

The expression used for the calculated curves in Fig. 7 has the form

q = ex(1 - O)E/(B - O/C) p/Q (3)

where ex is the sticking coefficient of nitrogen on a pure Ti surface, 0 is the fraction of the adsorption sites
filled, p is the pressure, E is a constant, and the constants Band C include the desorption rate (assumed
to be very small), surface migration rate (assumed to be very small), and rate of conversion from
physisorbed to chemisorbed states (- 0.1). The agreement of the model with the data is encouraging. It
may be anticipated that with further development, it will be possible to derive an expression for
composition that will have the form

where the first term is Eq. 1, and the second term is derived from Eq. 3.

16-5
V. Fll..M PROPERTIES

Some of the enhanced properties of IBAD coatings are listed in Table 2. The following section
gives examples that illustrate the differences between PVD fIlms and IBAD fIlms. .

A. Adhesion and Stress

Figure 8 shows a photograph of a 2-~-thick fIlm of Si deposited on Ta. The delaminated film
(hairy Si) on the left side of the photo was shielded from a 1000-eV nitrogen ion beam, while the right
side was bombarded at an arrival ratio of 0.2. The film is uniform and very adherent and does not
del~nate due to high internal stresses. This is one of the primary advantages of IBAD films-high
adhesion and reduced internal stresses.

Figure 9 shows the stress in W films [19] as a function of substrate temperature and arrival ratio
of Ar ions. Note that at each temperature, there exists an arrival ratio at which the stress is zero, and that
with no ion beam, the film contains high levels of residual internal stress. These data are quite typical
for IBAD films, e.g., stress can be reduced in most materials. High stress leads to rupture and
delamination above a critical thickness, and it is common for PVD films of dielectrics, semiconductors,
and refractory metals to have high stress. Therefore, mAD offers a means to control the stress that
facilitates the production of very thick films.

B. Densification: Theory and Experiment

The most important practical attribute of IBAD is the increase in film density over PVD fIlms.
PVD films typically contain voids or columnar structures that produce a 10% to 20% density deficit
relative to the bulk material [20,21]. This is especially true for covalently bonded semiconductors and
refractory metals. The densification mechanism is poorly understood. It is well established that the
energetic ion beam applied to the film in the IBAD process can eliminate the voids and produce bulk
density films. The mechanism for this densification may be related to atomic displacements in the
collision cascades, enhanced surface and bulk diffusion, recoil implantation, and ion mixing mechanisms.
A particularly revealing experiment has been performed by Hirsch and Varga regarding this issue [22].
Germanium was deposited with Ar ion assistance for Ar ion energies between 65 e V and 3000 eV. Hirsch
and Varga found an energy dependent critical arrival ratio of ions to atoms, R.:, above which the 2-J.lID-
thick films on Ge substrates did not spontaneously delaminate from the surface. Hirsch and Varga
suggested that if sufficient energy is provided to the growing film; internal stresses in the film are reduced

Table 2. Classification of the three modes of film formation for ion beam assisted deposition

Ion Assistance Reactive Ion Assistance

Ion Assistance (Compound Synthesis) (Gas Adsorption)
Vapor Ion* Film Vapor lon* Film Vapor Ion* Film
Ge Ar Ge Si N Si3N. TI N TIN
Ag Ar Ag B N BN TI Ar TIN
Ce02 0 Ce02 Si CH4 SiC Nb N NbN

Taz0 3 0 TazOs Cu 0 C~O AI 0 AI20 3

*The ions consist of both atomic and molecular ions and may be more than singly charged.

16-6
to a level that allows the growth of thick Ge films. The crosses in Fig. 10 show the data that Hirsch and
Varga. fit with the functional . fonn ~a E-3n.

Brighton and Hubler analyzed these data by means of the binary encounter approximation (BEA)
for the simulation of collision cascades [23]. They pointed out that the energy dependence of R.: could
be reproduced by assuming that the reduction in stress is directly related to the total energy lost to
displacement collisions. For reduced energy units of E < 0.1, the energy dependence of the nuclear energy
loss, dEJdx varies as Eln. If the 'reduced stress is caused by the total amount of energy expended in
displaceme~t collisions, then the total energy is obtained by integrating over the ion energy, or

R ~ fo ~ dE = E-3n
c JE dEJdx '

which was observed by Hirsch and Varga. If the reduction of stress were caused by enhanced surface
atom mobility from energy deposited at the surface, then the energy dependence

R a _1_ = E-1n
c dFJdx

would be expected. Thus, it is possible to distinguish between surface and bulk mechanisms by measuring
the energy dependence of R.: for a particular property of the film.

Brighton and Hubler also calibrated the BEA Monte-Carlo code MARLOWE [24] by adjusting
the input parameters to reproduce ion range and sputtering yield data for the Ar => Ge system at low
energies. Assuming that every deposited atom had to be involved at least once in a collision cascade at
the critical arrival ratio (similar to a radiation damage level of one displacement per atom), Brighton and
Hubler calculated the points in Fig. 10 represented by circles. This calculation contains no adjustable
parameters, and the absolute agreement with the data is quite good. This result supports the assumption
that reduction in stress occurs when every deposited atom is involved in a cascade.

The physical reason for reduction in stress was assumed to be caused by densification of the film
where the voids were eliminated by the collision cascade, but no analysis of the films was carried out by
Hirsch and Varga to confinn this. Recently, Yehoda et al. [21] have measured by means of transmission
electron microscopy (TEM) the arrival ratio of Ar ions to Ge atoms, which eliminated voids in PVD Ge
fllms. They found a 9% void density without bombardment and full bulk density with bombardment at
arrival ratios that match well with those of Hirsch and Varga. These experiments are convincing evidence
that the densification of Ge films grown with the IBAD process occurs during the collision cascade and
that the reduced stress is a result of that densification. This conclusion is also in accord with two-
dimensional molecular dynamic simulations carried out by K. H. Muller [25] that give a detailed picture
of the cascade events that produce densification.

It is interesting to note that the data of Hirsch and Varga and the analysis of the data can be used
to optimize the mAD process. One can choose an arrival ratio to increase :film density, yet minimize the
amount of incorporated Ar, which usually increases with increasing R

An experiment on the Ar => Cr system at higher energies (3-20 keV) by G. Wolf and his students
[14] indicates that the energy dependence of the critical arrival ratio to achieve zero stress in flIms is E"l.
This important work is only the second comprehensive study of its type (after Hirsch and Varga) and it
provides an important clue about the stress relief mechanism. Two important differences with the Hirsch

16-7
and Varga study are (1) higher energy and (2) a metallically bonded system as opposed to a covalently
bonded system. Both differences may be responsible for the different energy dependence. More
theoretical work is required to explain these results.

The above discussion shows microscopic evidence for densification induced by ion bombardment.
Figure 11 presents film density of Ze0 2 ftlms bombarded with 1200 eV O2 ions. This is a direct
measurement of the change in density of the film [26].

C. Microstructure

The effects of ion beams on the microstructure of films are numerous and complicated. For this
reason, only some general observations will be noted here, to give a flavor of the modifications that are
observed.

Most covalently bonded materials such as semiconductors and silicon nitride or silicon carbide
ceramics will be amorphous at room tem~rature. Silicon and germanium will be crystalline above the
temperature of - 0.4 Tm, the melting temperature in degrees Kelvin. Using ion beam deposition, the
temperature may be lowered by - 200 K because the atomic motion induced by the energetic atoms serves
the same purpose as high substrate temperature [7]. Metals and ionic materials tend to be polycrystal1ine.

In general, the ion beam decreases the grain size at low temperatures, but can increase grain size
at higher temperatures in which annealing effects overcome the damage caused by the ion beam [7]. This
small grain size is partly responsible for the general observation that IBAD ftlms are more ductile than
bulk materials with a larger grain size.

The orientation of ftlms can be altered so that textured films are commonplace. The degree of
texturing is dependent on beam energy, beam flux, and substrate temperature. In some cases, epitaxial
films can be induced to grow with ion assistance where they do not grow in the absence of ions. Ni and
AI on silicon are examples of this [7].

VI. APPLICAnONS

Applications are quite numerous in the optical thin-film industry, where the primary advantage
offered by IBAD is film densification. Refractive index stability and freedom from environmental
degradation are direct benefits of IBAD. Research in the area of wear-resistant and corrosion-resistant
coatings for metals and ceramics is just beginning. In general, there are three classes of IBAD, which are
summarized in Table 2. In each column are several examples of the material system deposited for one
of the three classes.

The first column shows a simple ion assistance type in which inert heavy ions such as Ar are used
to improve the properties of an elemental film or a compound film that undergoes congruent evaporation.
In this case, it is important to minimize the amount of Ar incorporated into the film; that amount increases
with R. and beam energy. Therefore, the lowest R. possible to obtain the desired film properties should
be used. An improved understanding of the critical arrival ratio to achieve improved films would be
helpful in this regard. This class also includes materials such as Ce02, which is slightly substoichiometric
when evaporated by PVD. Ion assistance with Ar can be used for densification only, or oxygen ions can
be used for densification and to restore stoichiometry.

The second column shows an ion assistance and compound synthesis group in which there is little
reaction probability of the ambient gas with the evaporant. The third class in column 3 covers compound .

16-8
synthesis of very reactive materials. It can operate with the gas associated with the ion beam (e.g., N2 for
TIN), or inert ions such as Ar can be used in conjunction with a secondary gas supply of N2 in which the
purpose of the ions is to activate and control surface chemical reactions. .

The models reviewed here potentially apply to all of these classes of mAD. The first industrial
application of mAD for wear or corrosion resistance appears to be the coating of electric razor screens
with TIN [15]. In this case, the choice ofmAD was dictated by the superior adhesion of the films over
other methods. Table 3 is a comprehensive compilation of materials that have been grown with IBAD
taken from the review by Smidt [7]; it has all the materials in the literature through 1989.

In order to place mAD in the proper context with respect to potential applications, the following
sections give examples of where IBAD is being used or where it is projected to be used in the near future.
In this way the reader will have a grasp of the kind of materials and problems in which mAD can
potentially be employed.

Table 3. Partial list of materials deposited by ion beam assisted deposition

Si Si3 N4
Ge AlN
a-Si:H AlON

'Ze°2 InSbBi SiON

Ce02 GaAsGe TIN
T~O~ GaSbSn TIC
Cr20 3 GeSn ZeN
V02 HfN
Hf02 BN
InSnO MoN
CuD NbNC

MgF2 Mo~

ZnS Diamond-like C
ZnSe WSi2
PbS YB~CU30d-8

16-9
 A. Optical Films

1. Densification of Optical Films

As already stated, the mAD technique was initially advanced by workers interested in optical thin
ftlms. There are two kinds of applications: (1) those in which densification is the primary concern and
(2) those in which graded refractive index profiles are required.

For the first kind of application, densification, low energy Ar or 0 ions are used to bombard the
optical thin films. Research has shown that the density is increased, in some cases up to that of bulk
. material. The primary a~ction is not necessarily that the refractive index is increased to near bulk
values, but that the index value is stable under humidity and temperature variations because there are no
voids or pores in the film that adsorb water vapor. This simplifies optical coating design and promotes
better control and reproducibility in the fabrication process. Another benefit of using low energy ions is
that adhesion to the substrate is improved, which also helps to increase production yields.

Figure 12 shows how the stability of ZrOz films is improved using mAD. The mAD fIlm is
completely immune from spectral shifts [26].

2. Graded Index Coatings

IBAD is beginning to be used to fabricate graded index coatings for antireflection coatings, reflec-
tion filters, and mirrors. Some of these devices can be tens of microns thick, so stress control becomes
very important.

Figure 13 shows the data of Dono:van et al. [27], in which the refractive index of silicon nitride
films is plotted versus the nitrogen fraction x. The index varies smoothly between 3.9 and 2.0. This large
and continuous change in index can be used to fabricate a new type of optical filter called a "Rugate
ftlter," in which the refractive index proftle varies sinusoidally in depth. This profile simulates a quarter
wave stack interference rejection filter, and similar mathematical formalism may be used to predict the
peak reflection frequency. The advantages of the Rugate filter versus the quarter wave stack are that
(1) no interfaces initiate delamination and scatter light and (2) side bands away from the design frequency
are minimized.

Figure 14a shows the deposition record for a Rugate film in which the N ion currentlSi deposition
rate ratio is plotted against the thickness. An increase of the ratio implies a reduction in the index. The
Si deposition rate is held constant while the ion current is varied to produce the modulated composition.
A computer controls the process by comparing the present ratio with a preprogrammed composition
proftle. This produces a modulated refractive index profile according to the data in Fig. 13. The solid
curve in Fig. 14b is the optical density of the same film versus wavelength, and the dashed curve is a
calculation directly from the deposition record. Agreement is very good above the absorption edge of the
silicon substrate, which is not included in the calculation. Reflectance at the design wavelength of 1.1 J.IIIl
is 99.5%. This is the flfSt report of continuous modulation of composition by means of the mAD
technique.
Graded index antireflection coatings and broad band mirrors can be deposited in a similar fashion.

16-10
3. Optical Absorption

Figure 15 shows the change in absorPtion coefficient in the visible as a function of the energy of
the Ar ion beam during deposition ofT~Os films [28]. As stated previously, lower energy beams reduce
the displacement damage in the films that can produce color centers. Therefore, in general, low energies
are desired 'for the deposition of optical films that operate in the visible.

It is difficult to assess how widespread the use of ion beams is in the optical fIlm industry because
the manufacturers have a need to protect proprietary methods.

B. Ion Beam Deposition .

Several groups are depositing diamond-like carbon (OLC) by direct ion beam deposition. Using
a Kaufmann ion source, methane is introduce into the plasma, and, at energies between 100 and 1000 eV,
DLC is deposited with rates from 1-10 Als. OLC provides a hard, protective coating for optics and
windscreens on vehicles. While DLC absorbs strongly in the visible, coatings from 200 to 2000 A in
thickness remain transparent enough to be used as protective transmission coatings. At least two
companies are set up to produce these coatings over reasonably large areas (20-cm diameter). Advantages
of these coatings are low porosity, high scratch hardness, and high adhesion to any substrate.

C. Corrosion

Because IBAD films are dense and have few pin-holes, they are attractive for corrosion protection
applications. Although only a few studies on corrosion have been done, the early results look promising.
Wolf has done IBAD Pt, TiC, TiN, B, DLC, CrN, BN, Cr20 3, and Si on metals with good success [14], .
and others have done AI, Ta, and W on carbon steel. Carbon steel is cheap and workable, and IBAD
films have good adhesion and high corrosion resistance. Thus, even though the process may be expensive,
use of inexpensive substrate material can obviate some of the processing cost.

Ceramic compound films such as ~03' Si3N4, and TiN also offer excellent corrosion resistance.
Takahashi in Japan [29] has set up a processing line that coats steel sheet continuously with AI, TiN, or
Al20 3• Figure 16 is a schematic of the apparatus. IBAD films are desirable, in part, because they are
adherent and more ductile than bulk materials due to their microcrystalline or amorphous structures.
Therefore, they can yield with the metal sheet so that some working of the metal is possible after
application of the coating. Figure 17 shows potentiostatic polarization data for Si3N4 IBAD coatings on
AI in a pitting solution [30]. The pitting potential of the coating is increased by 1000 mV, a very
impressive increase.

D. Oxidation

Work on oxidation protection is recent with only one result in the literature using IBAD coatings
of BN, Cr, or Si3N4 to protect Ti alloys. This seems to be a promising area for further research.

E. Catalysis

Ceyer has produced exciting increases in catalytic yields by bombarding a gas-catalyst surface with
energetic neutral atoms [31]. This is an interesting result that may result in the fundamental understanding ·
of gas-phase catalysis and perhaps in the design of new catalytic reactors.

16-11
F. Ion Induced Chemical Vapor Deposition

Several researchers have used class 3 of Table 3 for the production of unique hydrocarbon or
ceramic films. In this process, a gas is introduced into the chamber, the substrate is cooled to induce
condensation of the gas, and an ion beam strikes the surface. In this process, hydrocarbon bonds are
broken, volatile species are released, and a coating is produced. For silicone oil vapor, and depending on
the arrival ratio of ions to vapor-condensed atoms, the films can be very low friction solid lubricants to
very hard, corrosion-resistant SiO"Cy coatings [32]. This process is similar to chemical vapor deposition
(CVD), in which the high temperature of the substrate provides the energy to initiate chemical reactions
that are responsible for film formation. In the ion beam case, the same or similar reactions can be induced
at room temperature, opening the possibility of depositing CVD-like films . on polymers and other
temperature-sensitive substrates.

G. Friction and Wear

IBAD is being used to deposit solid lubricant coatings such as MoS:z. Advantages are that the
coatings adhere to the substrate and have a longer lifetime as a result of densification (better coherence).

The hardness of TiN coatings can be varied over a large range by microstructure control. Figure 18
shows the hardness as a function of arrival ratio for these films [33]. It is also true that the ductility of
these films; even for the highest hardness, is much larger than that for bulk material or CVD TiN films.
Boron Nitride, ZrN,and Si3N4 films have been investigated for wear .properties. BN works extremely
well on Si, but does not work particularly well on metals, and Si3N4 has good load bearing capability, but
has a high friction coefficient, and is not well suited to sliding wear situations without the additional low
friction coating over it. Many more materials need to be investigated. At the moment, the MoS:z, TiN,
and silicon CVD are fairly well developed and work very well.

H. Low Energy Ion Beam Sputtering

NASA has performed unique research on developing high emissivity thermal control coatings
using ion beam sputtering [34]. By arranging a target" near the surface to be treated that seeds the
substrate with an impurity, NASA researchers produce surfaces with a topography consisting of steep
angle cones that absorb light These surfaces have very high emissivity. Figure 19 shows the features
of one of their surfaces. These materials hold great promise for long-life thermal control, and light baffle
applications on satellites.

VII. SCALE-UP

Many of the applications described above require large areas to be coated. Ion guns of more than
60 cm in length are currently available, and at least one laboratory has a system that can handle
I-m-diameter workpieces. In' nonoptical applications, in which uniformity of the film is not a strict
requirement, very large areas could be done with present equipment by routine manipulation of the
workpieces. To date, a diameter of about 20 cm is the record for uniform optical films.

Still higher surface areas are possible by the means of continuous coating schemes like that shown
in Fig. 16. The primarily obstacle for scale-up is the requirement of line-of-sight processing, especially
for odd-shaped parts. Cylinders can easily be coated, but it is not yet clear whether or not shapes like gear ·
teeth can be reliably coated.

16-12
YIn. SUMMARY

. As a surface modification technique, IBAD retains the best features ofPVD and ion implantation
and eliminates the worst features. The choice of the appropriate beam energy is determined by a trade-off
between attaining the best film adhesion and minimizing the defects in the films produced by displacement
damage. More measurements of the energy dependence of critical-arrival ratios to achieve densification,
improved adhesion, or low stress are needed to elucidate the mechanisms that improve fIlm properties.

Simple models for the composition and thickness of silicon nitride and boron nitride films are in
good agreement with experimental data. For the reactive titanium nitride system, a preliminary model for
the amount of Nz gas incorporated into the film was presented. The good agreement with the data is
encouraging, but more development is necessary. These early results raise the expectation that a
phenomenological model can be derived that will predict the composition of mAD films in the general
case of any ionlevaporant combination.

The application of mAD films as wear- and corrosion-resistant coatings for metals and ceramics
is just beginning. Because thick (- microns) films are readily produced, IBAD will be more easily
accepted and more widely used in industrial applications than will ion implantation.

REFERENCES

1. U. 1. Gibson, Ion-Beam Processing of Optical Thin Films, in Physics of Thin Films, 11 Academic
Press, 1987, p. 109.

2. D. R. Brighton and G ..K. Hubler, Nucl. Iostrum. and Meth. in Phys. Res., B28, 527 (1987).

3. K. H. Muller, Phys. Rev. B, ~ 7906 (1987).

4. 1. 1. Cuomo, 1. M. E. Harper, C. R. Guarnieri, D. S. Yee, L. J. Attanasio, J. ADgilello, and C. T. Wu,

J. Vac. Sci. Technol., ~ 349 (1982).

5. R. P. Netterfield, SPIE, 678, 14 (1986).

6. C. Weissmantel, Thin Sol. Films, 32, 11 (1976).

7. F. A. Smidt, Int Mat. Rev., 135, 61 (1990); 1. K. Hirvonen, Mat Sci. Rep., Q, 215 (1991).

8. J. M. E. Harper, J. 1. Cuomo, R. J. Gambino, and H. E. Kaufman, in O. Auciello and R. Kelly, Eds.,

Ion Bombardment Modification of Surfaces: Fundamentals and Applications, Elsevier, Amsterdam,
The Netherlands, 1984, pp. 127-162.

9. P. J. Martin, J. Mater. Sci., n, 1 (1986); P. J. Martin and R. P. Netterfield in E. Wolf, Ed., in

Progress Optics XXIn, Elsevier, Amsterdam~ The Netherlands, 1986, pp. 11~182.

10. J. E. Greene, T. Motocka, J.-E. Sundgren, A. 'Rockett, S. Gorbatkin, D. Lubben, and S. A. Barnett,
J. Crystal Growth, 1£ 19 (1986); 1. E. GreeJ;le, T. Motcka, J.-E. Sundgren, D. Lubben, S. Gorbatkin,
and S. A. Barnett, Nuel. Instrum. and Meth. in Phys. Res., B27. 226 (1987); 1. E. Greene and
J.-E. Sundgren, in M. O. Thompson, S. T. Picraux, and J. S. Williams, Eds., Beam-Solid Interactions
and Transient Processes, Mat. Res. Soc. Symp. Proc., 1!, 1987, p. 463.

16-13
11. 1. J. Cuomo and_So Rossnagel, Nuc!. Instrum. and Meth. in Phys. Res., B27, 963 (1987);
S. M. Rossnagel and 1. J. Cuomo, MRS Bul1etin XII, No.2, 40 (Feb.-Mar. 1987).

12. G. K. Hubler, 1. Vac. Sci. Techno!., A 115, 181 (1989).

13. D. VanVechten, G. K. Hubler, E. P. Donovan, and F. D. Correll, 1. Vac. Sci. Techno!., A 8, 821
(1990); G. K. Hubler, D. VanVechten, E. P. Donovan, and C. A. Carosella, J. Vac. Sci. Technol.,
A 8, 831 (1990).

14. W. Ensinger and G. Wolf, 1. Mat. Sci. Eng., A116. 1 (1989); G. Wolf, Nuc!. Instrum. and Meth: in
Phys. Res., B46, 369 (1990).

15. M. Iwaki, J. Mat. Sci. Eng., A115. 369 (1989) and private communication.

16. C. A. Carosella, G. K. Hubler, D. VanVechten, and E. P. Donovan, Mat. Res. Soc. Symp. Proc., 128,
79 (1989).

17. G. K. Hubler, D. VanVechten, E. P. Donovan, and R. A. Kant, Mat. Res. Soc. Symp. Proc., 128.55
(1989). .

18. T. W. Barbie, Jr., D. L. Keith, L. Nagel, and W. A. Tiller, 1. Electrochem. Soc., 131. 434 (1983).

19. R. Roy, Mat Res. Soc. Sym. Proc., 128.23 (1989).

20. P. A. Thomas, M. J. Brodsky, D. Kaplan, and D. Lepine, Phys. Rev. B, ll. 3059 (1978).

21. 1. E. Yehoda, B. Yang, K. Vedam, and R. Messier, J. Vac. Sci. Techno!., A 6. 1631 (1988).

22. E. H. Hirsch and I. K. Varga, Thin Solid Films,.§2, 99 (1980); E. H. Hirsch and I. K. Varga, Thin
Solid Films, g 445 (1978).

23. D. R. Brighton and G. K. Hubler, Nuc!. Instrum. and Meth. in Phys. Res., B28, 527 (1987).

24. M. T. Robinson and I. M. Torrens, Phys. Rev. B, .2.. 5008 (1974).

25. K.-H. Muller, 1. Appl. Phys., g, 1796 (1987).

26. P. J. Martin, R. P. Netlerfield, and W. G. Sainty, 1. Appl. Phys., ~ 235 (1984 ).

27. E. P. Donovan, D. Van Vechten, A. D. F. Kahn, C. A. Carosella, and G. K. Hubler, 1. Appl. Opt,
~ 2940 (1989).

28. J. J. McNally, F. L. Williams, and J. R. McNiel; Proc. SPIE, 678. 151 (1986).

29. T. Takahashi, Surf. and Coatings Technol., Proc. of 7th SMMIB Conference, July 1991, Washington,
DC, to be published.

30. P. M. Natishan, E. McCafferty, E. P. Donovan, D. W. Brown, and G. K. Hubler, Surf. Coat. and
Technol., Proc. of 7th SMMIB Conference, July 1991, Washington, DC, to be published.

16-14
31. S. T. Ceyer, Ann. Rev. Phys. Chern., ~ 479 (1988).

32. C. A. Carosella, private communication.

33. R. A. Kant, S. A. DiIlich, B. D. Sartwell, and 1 A. Sprague, Mat. Res. Soc. Proc.• 128. 427 (1989).

34. M. Kussmaul, Surf. Coat. and Technol., Proc. of 7th SMMIB Conference, July 1991, Washington,
DC, to be published.

..

16-15
 PHYSICAL PROCESSES - IBAD

IM~!TION! ~ ~
FARADAY
CUP
,
.......... .
OUARTZ
MONITOR

"~I
/

SURFACE
'--A.,A,A-AJJ'-'Y"'"

if~
S~" -,,-,
J r;~!
~
"'-A.A..I9''-'
0 '0

GA~'~ESORPTION
I GAS REACTION

1'0 . r.
SPUnERiNG 0
t
ION JaBmCIf ®
500 eV N;' N+ 1- t @
I ® -'0.03
SO~~CE • • • ieAM
eV
I 0.15 eV
CAYO-
PUMP
H~. (2".,
I
CHARGE
EXCHANGE
VACUUM
Hi @ HElITRAUZATION
CHAMBER

Figure 1. Schematic diagram of a typical ion beam assisted deposition (mAD) system.

Figure 2 . Schematic represe~tation of the physical processes occurring during mAD.

. ,

Figure 3. Composition ratio (NISi) of mAD films vs. the current density of 500-eV nitrogen ions
(bottom) and the arrival ratio (NISi) (top). The deposition rate of Si was 10 Als. Typical
error bars are shown at three different current values. The curve is calculated from Eq. 1.

Figure 4. . Composition ratio (NIB) of IBAD films vs. the arrival ratio of NIB. The deposition rate of
B was 3 Als. The curve is calculated from Eq. 1a.

16-16
 Ra
0 0.2 0.4 0.6 0.8 1.0
1.2

(J
2xl0- 5 rORR

. ..-----
t-
Z
......... --.--- -------
0 1.0
f= 1.0
C,)
w
a: , Ii'
a: " ~--6.~
0 ,
, I
I 1 ..... ....
C,)
, I ........
en
en ... ... • FILM
IONS (CALCULATED)
w 0.8
Z .. AMBIENT
::.::
C,) • OPTICAL THICKNESS
:i:
t- o STEP MEASUREMENT

0.6
0 50 100 250 300
1.2
ION CURRENT DENSITY (I'Aicm 2)

Figure S. The thickness correction of IBAD films vs. current density of SOO-eV nitrogen ions. The
Si deposition rate was 10 Als. The open circles are from step height measurements, and
solid circles are optical thickness measurements. The solid curve is calculated.

Figure 6. The composition ratio (Nffi) of mAD films vs. the arrival ratio Nffi for SOO-eV nitrogen.
ions and a Ti deposition rate of 10 Als (solid circles); Nffi from implantation of nitrogen
ions (solid curve); Nffi from N2 gas incorporation (triangles). The pressure of N2 was
2 x 10-5 Torr.

1.2,..-----r---...----r-----:--.----,

1.0 R•• 0.00

;-
z
w
~ 0.8 ,
,,-
0(
::; t('
~ 0.6 I
I
u.. I
I
Q
;-
~

~
0.4

0.2 ,,
I
.
I
It

/
/
,'"
0.01.....::..:--::..::':.......c;:::=-------l-::---~-~:_;__-....J
10-8 10- 7 10- 6 10- 5 10-'
PRESSURE/DEPOSITION RATE (TORR/(;'/s))

Figure 7. Contribution to composition ratio (Nffi) from N2 gas incorporated in mAD TIN films vs.
=
pressure/deposition rate ratio. R. 0 (squares), R. 0.25 (circles). Curves are calculated =
from Eq. 3.

Figure 8. Microphotograph of a 2-J.UIl-thick film of Si deposited onto Ta showing delamination (left

side). The left side was shielded during bombardment; the right side was bombarded during
deposition with a l-keV nitrogen ion beam with an arrival ratio of 0.2.

16-17
 -
en
,..
0
10

8 200·C
Nb: 100 eV Ar+
-,..
en
0
15
W: 400 eV Ar+
)( )( 10
N N
E
u
6 E
u
""-
(II
""-
(II
5
G,) G,)
c:: 4 c::

W
>-
-enen
~
2 -
~

en
en
W
>- 0

-5
a:: 0
a::
t; -2
(a) ...
en -10
(b)
0.0 5.0 10.0 15.0 20.0 25.0 30.0 0.0 .02 .04 .06 .08 .10 .12

ION FLUX (mA/cm2) ION FLUX (mAlcm2)

Figure 9. Stress as a function of ion flux (a) in Nb films evaporated with concurrent 100-eV argon
ion bombardment and (b) for evaporated W films subjected to 400-e V concurrent ion
bombardment shown at a series of substrate temperatures. A tensile stress maximum shifts
toward lower ion flux as the substrate temperature is raised.

..
0.1

IS (0)
0
i=
)K

1
X

i
¢ 0.01
a:
..E :E
.. 0
....
~ 10 ¢
...,.. 0
....
iii
z
:!:
...z
z
Q
0.001 1x1
i os
u
X HIRSCH & VARGA DATA
o BINARY CASCADE MODEL
'1
1.00E·4
0 0.01 0.1 1 10
-s -4 -) -2 -I 0 I 2 ) S
RAOIAl OISTANCE FROM se ...... A.XIS , ...... , ION ENERGY [keV]

Figure lOa. A beam profile used to determine the critical current density for obtaining adhesion in Ge
films [22].

Figure lOb. Critical values of L'le ion/atom arrival ratio for obtaining adhesion for various energy ion
beams [2].

16-18
 1.0,..--"""T""--,--.,.---,-_--,,.....---,
NO IONS

.. '
.'

,, "
,,
, /aII'
1&1
, ,,
~ ,
,,

i
z
c
\ ,,
,,
,
I
I

~ 0.8
\
" , -- "
"

4.4

o
0.7
02 ION CURRENT DENSITY (~"cm-2) 400 500 600 700
lal
WAVELENGTH (nm)

1.
02 IONS

0.9
1&1
(J
Z
C
4 .0

3.5
iz
en
...Q
)(
C

! 3.0 ....a::
...>
2.5 + ........
~
\.i -/" ++"-+.
-<~ .+
...... 2.0
~
LOaI!NTZ .. LoaENZ
EQUATION
1.5
+ ..u-DIPOSITID
0.7
1.0 400 500 600 700
0 .0 0.1 0 .2 0.3 C,.4 0.5 0 .6
NITROGEN ATOM FRACTION IN NITROGEN-SILICON FILM Ibl WAVELENGTH (nm)

. Figure 11. Change in :film density with current density for Zr02 films prepared by mAD with 1200-eV
0; bombardment.

Figure 12. Transmittance of Zr02 :films prepared (a) by evaporation and (b) with bombardment by
1200 e V 0; ions. The change in transmittance when fllm is removed from the vacuum
system can be eliminated by use of mAD.

Figure 13. Comparison of the variation in the refractive index with nitrogen atom fraction in ·S iNx for
experimental results (circles) and calculations with the Lorentz-Lorentz equation.

·16-19
 ""
11\

~~ 4~----------------------------------------------------_
o
~
I-
11\
\j
Z 3
~
::(
~

11.1
I-
~ 2
Z
o
--o
I-
11\
1
Ao

-
11.1
Q
I-
Z
11.1
~

a~ o~--------~----------~--------~----------~--------~
0 1 2 3 4 5
MEASURED SILICON THICKNESS (MICROMETERS) ..
3.0----~----~~~--~----~--~--~~--~--~----~
MEASURED
- - - - CALCULATED
2.5

>-
-Z
I-
11\
2.0

11.1
Q
...< 1.5

-
U
I-
Ao 1 .0
0

0.5

O.O~----~--~----~--~----~----~---'----~----~--~
0 .6 0.8 1.0 1.2 1.4 1 .6 1.8 2.0 2 .2 2.4
WAVELENGTH (MICROMETERS)

Figure 14. (a) Deposition record of a 23-cyc1e Rugate filter prepared on a silicon substrate. (b) Optical
density vs. wavelength for the Rugate filter of (a) after a 750°C anneal.

16-20
 x
...... 20 .
.1-
Z
,/9
6,
W
U
\J.. 15
\J..
w
o 300 eV
u
Z 10
o
I-
U
Z
l-
5
X
W

10 20 30 40 50 60 70 80 90
Oz CURRENT DENSITY ().JA cm- 2 )

Figure 15. · Changes in extinction coefficient for T~Os films prepared by mAD.

PAY-OFF ION TAKE-UP

CHAMBER BOMBARDMENT CHAMBER
ION SPUTIERING DIFFERENTIAL PLASMA
PLATING PRESSURE CVD
CHAMBER
=
co I~c...tt
v

Figure 16. In-line dry coating process.

16-21
 -
C\I
<
10"

10 3
O.1M NaCI
2J.Lm
E
-<
(.)
10 2

-:::L
10 1

-
>-
en
s:::
10°

Cl> 10·

--
C

c:
Q)
10'

10·
::J
(,)
10·
D1.4 -1.1 -0.8 -0.5 -0.2 0.1 0.4
Potential (Vsce)

Figure 17. Anodic polarization curves for aluminum and aluminum with a number ofIBAD coatings
ranging from 0.01 to 2.0 J.LID.

KNOOP HARDNESS vs R
ION BEAM ASSISTED TiN (500 eV ARGON)
2750 .
-
E 2500
II)
N I Ti
-0--1
-+-2
"", ,"
",
""'
~-:",
/
" 2250 -*-3
/,' '
0 /
<
-
0
..J
en
en
w 1750
2000
",
,,'
"
/,'
/,'

z
0 ,J#
V'
a: 1500 /'
<
:I: //
Do 1250 *,.I ,/
0 ,.!
0 ,i'+
Z
~ 1000 ,~
,'/
,'/
750
0.0 0.1 0.3 0.5
R

Figure 18. Hardness of IBAD TIN films vs. arrival ratio of Ar to Ti atoms.

16-22
Figure 19. SEM photomi~rograph of a textured carbon surface on an oven-fired high conductivity
(OFHC) copper substrate. The angle with the surface is 30°, the processing time is 3 hat
5 mAlcm2 , and a 1O:-J.UIl scale line is indicated on the title block.

16-23
 17. A SUMMARY OF CRITICAL ISSUES FOR APPLICATION OF
ORGANIZED MOLECULAR ASSEMBLIES AT SURFACES

David L. Allara
Department of Materials Science and Department of Chemistry
Pennsylvania State University
University Park, PA 16802

I. INTRODUCTION

The subject of ultrathin (":'" 1-1<Y nm) organic fIlms has become of considerable interest over the
past decade because of a few existing and many potential technological and scientific applications [1].
The understanding of these materials is usually very incomplete when extrapolations are made from the
behavior of bulk phases, because interfacial phenomena, of little concern in bulk material properties, can
profoundly affect the behavior of ultrathin films. In addition, specialized procedures, designed specifically
for ultrathin fIlm synthesis, often cannot be adapted to bulk materials synthesis, and thus some materials
structures and phases can only be obtained in fIlm form. Because of these facts, it is necessary to view
ultrathin organic films as generating their own unique materials issues with regard to potential and present
applications.

One particular class of film structures for which the above points are most certainly true is highly
organized molecular films or organized molecular assemblies (OMAs). The term "highly organized" refers
to the spatial organization of the molecules. In the limit of perfect translational and orientational ordering,
the molecules form a single -crystal, which can be two- or three-dimensional, depending on whether one
or more layers of molecules are present, respectively, and also whether or not the important degrees of
freedom of the system exist exclusively in the surface plane or include the out-of-plane direction. As the
extent of translational and orientational correlations decrease, the limit of complete disorder is reached,
and the molecular assembly is no longer organized, in the sense used in this discussion. Different types
of highly organized films can exist. For example, it is common to have low translational order films in
which high orientational order exists (quasicrystals). These latter strucrures are generally considered
highly organized also. Thus the term "highly organized" is somewhat arbitrary, and indeed, to characterize
a given film as organized, one must, to be rigorous, state quantitative correlation parameters such as
correlation decay lengths and orientational order parameters.

The general properties of highly organized ultrathin films that are of the greatest interest for
applications are (1) high packing densities with low defect concentrations, (2) molecular alignment, (3) the
capability of synthesizing surfaces with tailored physical and chemical properties, especially in selected
spatial patterns, and (4) flexibility in selecting the types of molecular functionality and structural units
present Other properties such as thermal and photochemical stability are of interest, depending on the
specific application.

To actually use these types of films, a number of unresolved issues must be confronted. Is it '
possible to design a desired specific architecture and successfully synthesize the structure, or are present
capabilities limited? Given a successful synthesis, will the structure actually perform its function? Is the
given structure a stable, minimum energy structure, or will it revert in time to another more stable form?
There are a number of other similar issues that one can formulate. In the next section, a number of these ·
issues are presented.

17-1
 A number of critical issues center on film preparation. At present, there are two major preparation
methods for organized ultrathin film structures, Langmuir-Blodgett (LB) and self-assembly (SA), and films
can be conveniently classified according to which of these two methods was used to generate the' fIlm.
The LB procedure consists of a specialized dip-transfer process of a monolayer film, preorganized on a
water surface, from the water 'to a substrate. Repeated transfers result in multilayer films. The subject
of LB films has been extensively reviewed [2-4], and will not be reviewed here. The SA method has
become very popular, mostly for scientific study, in the past decade. In this method, a substrate surface
is covered by a monolayer of molecules by simply exposing the substrate to a solution (or less often
vapor) of the molecules. The process occurs spontaneously, and often, strong chemical bonding to the
surface occurs at specific sites. The bonding can occur in an arrangement that will give rise to crystalline
fIlms. Almost always, multiple layers must be prepared by chemical coupling strategies. A recent review
of SA fIlms is available [4]. The following section will assume that the reader is familiar with the details
found in the above references and other readily available current literature.

II. CRITICAL ISSUES

A. Critical Properties of OMAs for Potential Applications

In Table 1, a list of critical properties affecting various applications is presented. Other critical
properties and applications can be considered, but for purposes of simplifying the discussion, the list is
lintited to fairly common issues. The nature of the properties listed needs to be defmed in some detail.

Defects are classified into random defects, such as large patches of missing films (~0.1-1.0 f.l1ll),
small patches of missing films that are termed pinholes (:::;; 0.1-1.0 f.l1ll), and defects iIi more smoothly
varying density fluctuations arising from long-range structure correlations such as grain boundaries and
modulation between amorphous and ordered films regions, as well as other film structure subtleties such
as hollow regions in cyclic molecules.

Surface activity refers to the ambient (outer) film surface properties of chemical activity, including
acidity and basicity; wetting properties such as hydrophobicity, olephobicity, and hydrophilicity; and
combinations that can lead to biological activity.

The substrate/film interface is viewed in terms of the specific chemical bonding that may exist to
bind the adsorbate to the substrate and the nature of the charge distribution and electronic states at the
interface, which can be very important for semiconductor electronic devices.

The electrical and electronic structure of the film concerns the distribution of charge, usually in
the form of permanent dipoles, the presence of polarizable electrons. and low lying excited states. Of
particular interest in this category is the directional or orientation dependence of the above features with
respect to electrical and electromagnetic excitation. The active features, such as dipoles, must be aligned
along favorable orientations. Also the inversion symmetry of the distribution of charge or polarizability ,
elements in the film is important. For example, second harmonic generation of light can be induced by
the bulk of a fIlm only when the film symmetry is properly noncentrosymmetric (no center of inversion
symmetry for the structural repeat unit).

The stability of the film is an obvious practical consideration in applications. Thermal and
chemical stability are necessary for most exposure environments. Chemical stability can include reactions
with O2, ~O and other specific chemicals, as well as perhaps a more physical property. stability towards
desorption in the presence of solvents. In the case of optical devices, photostability may be important,

17-2
 Table 1. Critical Properties of Organized Molecular Assemblies for Potential Applications

SubstratelFilm Electrical and

Defects Surface Activity Interface Electronic Structure Stability
MuUi-
Long-Range Elec- layer
Pin Structure Chemical tronic Orien- Film Particle Capability
Potential Application Hole Correlations Activity Wetting Bonding State tation Symmetry Thermal Photo Chemical Beam
Devices
Electronic
Chemical sensors X X X X .X X X
Photovoltaics X X X X X X X
Microlithography X X X X X X
Electrochemical
Chemical sensors X X X X X X X X
Photochemical X X X X X X X X
Synthesis X X X X X X X
Optical
Photonic switches X X X X X
(nonlinear)
Electrooptical X X X X X
Displays X X X X X X
Coatings
Diffusion barrier X X X X X X
Anticorrosion X X X X X X
Antiwear X X X
Bioactive X X X
Specific wettability X X X X
Adhesion coupling X X X X X
agents
and in the case of microelectronic processing and lithography resist applications, photo or particle beam
stabilities may be desired or not, as the case may be for a given process step.

Finally, many applications require substantial film thickness, which in turn requires the film
synthesis process to have multilayer capability in order to stack many layers of molecules into a stable,
organized structure, a severe challenge in many cases.

The central points for discussion here are: what are the varieties of applications envisioned and
what critical properties must be controlled for successful engineering? After "these properties are
identified, the question of how to control them arises.

B. Preparation Variables, Critical Properties, and Potential Applications of OMAs

Table 2 relates critical film properties to the preparation variables, substrate. film materials. and
processing method. For many applications, there may be very little leeway in selecting different substrates
or film materials, and then the processing method is considered the major variable. A fairly common
situation is that the substrate is fixed. For example, to fabricate a specific molecular-based electronic
device, the only semiconductor material possible may be GaAs, but the film material and processing offer
flexibility. However, even for a fixed substrate material, there is usually additional flexibility with regard
to the substrate, particularly the degree of surface preparation, which includes cleanliness. roughness,
chemical pr~paration to generate active bonding sites. choice of particular crystal faces that determine
lattice geometry. and the degree of control in minimizing lattice defects. The choice of film material
critically depends on the nature of the film property needed, obviously, and also upon the strategy
developed to form the film structure. The organic molecular structures that can be chosen almost appear
infinite, but actually they can be conveniently divided into several simple categories derived from the
constraints of the narrow range of processing methods available. The major category, which has been used
almost exclusively for organized films, is amphiphilic molecules. These are molecules with a hydrophobic
(water insoluble) and a hydrophilic (water soluble) portion, and all surfactants are based on this structure.
A typical surfactant structure consists of a long alkyl tail (- 12-20 carbon atoms) and a water soluble head
group (ionic or hydroxylic group).

Almost all LB-processed films are based on surfactants, and the degree of amphiphilicity is a
critical parameter affecting the film qUality. LB films also can be made from highly water insoluble
molecules with no hydrophilic portion, but good quality organized films have resulted in only a few cases,
and the procedures are difficult [3]. In most cases ofLB films, the head group is attached to the substrate
by weak physisorption forces, a characteristic that can lead to poor thermal and solvent stability.

Poor thermal and solvent stability can be improved by the use of polymeric molecules produced
either by deposition of preformed polymers or by postpolymerization of monomeric films. These charac-
teristics can also be improved by the presence of strong chemical bonding of the film to the substrate.
This characteristic requires functional group reactivity with the substrate. Such a situation is obtained with
SA films, because it can be easily arranged to use substrates whose chemical propensity to react with
selected functional groups drives the assembling of the adsorbate molecules. Regardless of whether the
head group is bound at the surface by physisorption or bond-specific chemisorption, the shape of the
constituent molecule plays a critical role in determining film properties. For example, if the lattice
geometry of active bonding sites for a given substrate requires that the molecules in a SA monolayer be
bound together in an organized geometry conflicts with that allowed by the molecular size and shape, then
the film can never have as high a translational ordering as the substrate lattice. In addition, molecules
with symmetrical shapes, e.g., rod-like (common for most surfactants), can lead to very dense packing,
whereas highly asymmetric or cavity-containing molecules will pack at lower densities with a more porous

17-4
 Table 2.
Preparation Variables Which Affect Critical Properties of 0rganized Molecular Assemblies

Critical Property of Film

Substrate/Film Electrical and
Defects Surface Activit~ Interface Electronic Structure Stabilit~
Multi-
Pin Long-Range Elec- layer
Holel Structure Chemical tronic Orien- Film Chemical! Particle Capability
Preparation Variable Patch Correlations Activity Wetting Bonding State tation Symmetry Thermal Photo Solvent Beam
1. Substrate X X X X X X X X X X X
Rougtmess X X X X X X
Cleanliness X X X X X X X
Active bonding sites:
Lattice geometry X X
Lattice defects X X X
'.!
Chemical nature X X X X
2. Film Material X X X X X X X X X X X X X
Amphiphilicity X X X X
Functional group X X X X X X X
reactivity with
substrate
Shape X X X X
Multifunctional X X ,X X X X X
molecule
Polymeric molecule X X X X X X X X X
3. Processing Method X X X X X ' X X X X X X
structure. at the molecular scale .. Control of the latter porosity is a critical feature in films that regulate
charge or mass transport, such as electrochemical electrode coatings and diffusion barrier films.

For many applications, the synthesized film must contain one or more specific molecular groups
at specific locations in the film to achieve the desired function of the structure. Three generic examples
of the need for multifunctional molecules in a film structure are (1) for nonlinear optical (NLO) devices,
highly conjugated, heteroatomic pi-electronic functionality usually needs to be located in the film interior,
(2) for a surface of a specific controlled wettability, a specific type of functional group, (e.g., an OH
group), needs to located at the film surface, and (3) for an electrochemical sensor, a surface bound group
that specifically binds a target analyte is often desired to achieve high chemical specificity for the device.

The discussion above points out the general connections between processing variables and
applications properties. In Table 3, some examples of specific connections are given for selected generic
classes of applications. Without a highly specific target application object or item, it is not possible to
bring out these connections in real detail. Rather, the entries in Table 3 are designed to show the types
of connections that one should consider.

C. Major Techniques for Characterizing Critical Features of Molecular Films

Characterization is a major capability whose degree of realization can act as a gate to control
success in making structure/function correlations, but often remaiIll? a hidden factor in the advancement
of thin-mm technology. For this reason, techniques that have been successful in characterizing structural
. features ·of organized molecular films are made part of this discussion and are presented in Tabie 4. It
is this author's opinion that X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry
(SIMS), and infrared (IR) spectroscopy are the most cost-effective tools for characterizing critical aspects
of molecular film"structure. However, it is clear to workers in this field that these three techniques cannot
cover all critical features, for example, translational ordering, and that a combination of techniques is
needed in each film analysis. A further point is that different techniques may give apparently conflicting
information because of the lack of accurate interpretation of complex data or spectra, particularly in a
quantitative fashion. Having noted these problems, we return to the central issue of controlling the final
properties by control of the synthesis.

D. Important Film Characteristics for LB and SA OMAs

In Tables 5 and 6, a very abbreviated tabulation of important film characteristics is given for each
of the two major processing methods [4-9]. For detail, particularly on LB films, reference texts should
be consulted [2-4]. The major features of LB films in an encapsulated summary are: (1) excellent
multilayer capability, (2) extreme, but not complete, limitation to surfactant molecules with no capability
for multifunctional polar, hydroxylic groups, (3) low thermal and solvent stability except for the very
limited cases of pre- or postpolymerization of the film molecules, and (4) excellent, low defect crystalline
films for some rod-like surfactant molecules. Most of the early work, actually until the past half decade
or so, has been done with LB ftlms. Recently, with the discovery of new SA film/substrate systems, the
field of SA films has expanded at an accelerating pace. Table 6 presents the major SA films systems and
associated pertinent features. SA films differ markedly in two respects from LB films.

The first difference is that whereas, in general, preparation of any LB film is independent of the
particular substrate material, in contrast, the very existence of most SA films is dependent on specific
chemical interactions between a specific functional group on the film molecule and specific sites on the
substrate surface. In some cases, the interactions are very weak (e.g., weak hydrogen bonding) and as a
result, film stability toward heat or solvents will be poor. However, in the cases of many SA films

17-6
 Table 3. Selected Examples of Optimal Materials and Processing for ~pecific Target Applications

Optimum Optimum Materials

Selected Possible Major Processing
Application Requirements Method Substrate Film

Open gate, chemically Surface chemical activity; monolayer; substrate/film . SA Semiconductor, periodic Multifunctional with substrate
sensitive FET bonding and electronic states; thermal and chemical lattice of bonding sites bonding group; specific
stability; low defects; protective barrier for placement and orientation of
semiconductor surface degradation functional groups
Modified Schottky Monolayer; specific substrate/film interface SA Semiconductor, periodic Multifunctional with substrate
diode bonding; charge distribution and electronic states; lattice of bonding sites bonding group; presence of
thermal stability; pinhole defect-free; damage charge separation or
resistance toward metallization polarizable groups
Electrochemical sensor Surface chemical activity; monolayer; substrate/film SA Conducting material, periodic Multifunctional with substrate
bonding; chemicaUsolvent stability; preselected lattice of bonding sites, non- bonding group; molecular
defect channels for charge transport; redox active corrodible shape to allow transport
groups channels; redox functional
group
Photonic switch Multilayers (- 1 J.II1l); electronic structure with high LB- Optically transparent, highly Highly amphiphilic; non-
nonlinear optical response and appropriate inversion multilayer smooth, inert to water linear optical group aligned
symmetry; density fluctuation-free; photostability deposition along selected molecular axis;
liquid crystalline
Diffusion barrier Dense, defect-free packing; thermal and solvent LB- Smooth, inert to water Highly crystallizable
coating (e.g., H20, OJ stability multilayer m<;>lecule; possibly crosslink-
deposition able; amphiphilic or water
insoluble and stiff
SA Availability of dense surface Oligomeric or polymeric
bonding sites; periodic molecules with substrate
preferable bonding group; or small
molecules that densely pack
Adhesion coupling Surface chemical activity; substrate/film bonding; SA Available surface bonding Multifunctional with substrate
layer thermal stability sites bonding group and surface
chemically active group
Antiwear film Low surface wettability (low surface energy); SA Available surface bonding Substrate bonding group; low
substrate/film bonding; high thermal stability; sites surface energy groups;
uniform coverage flexible linkages; thermal
stability; possibly oligomeric
or polymeric
 Table 3. Selected Examples of Optimal Materials and Processing for Specific Target Applications (Concluded)

Optimum Optimum Materials

Selected Possible Major Processing
Application Requirements Method Substrate Film

Bioactive coating Surface bio(chemical) activity; thermal and SA Available surface bonding Multifunctional; .substrate
chemical stability; substrate/film bonding; dense sites; noncorrodible bonding group; possibly a
packing to support surface orientation and combination of functional
arrangement groups or separate molecules
. that can arrange in a cluster
to form a site with high
chemical or biospecificity
Nano-lithography resist Specific sensitivity to degradation or crosslinking SA Available surface bonding Multifunctional; surface
by photon or particle beams; specific solvent sites, preferably periodic bonding group; radiation
stability; thermal stability; low patch defects sensitive linkages; plasma
resistant groups; possibly
polymeric or oligomeric for
uniform coverage
LB- Smooth, inert to water Containing cross-linkable or
multilayer radiation degradable groups;
deposition crystallizable molecule
 Table 4. Major Techniques to Characterize Critical Aspects of Film Structure

Characterization Technique
Ellip-
sometry AFM.
(including STM XRR. He LEED.
Critical Film Feature XPS SIMS IR SE) RBS SEM (TEM) XRD Scat SFG HREELS UPS Raman ISS (TED)
1. Film Coverage
Total coverage/thickness X X X X X
Patch defects (> 0.1-1 JlID) X X X X X X
Chemistry X X
2. Elemental Comoosition
Average X X
Surface X X
Depth profile (including X X X
sputtering and nondestructive)
.
,., Image (lateral) X X
3. Molecular GroU(!S
Chemical bonding X X X X X X X
Orientation X '! X X X('!) X X X X
Conformations '! X X X X
Average composition X X X X X X X
Depth profile composition X X('!) X X X('!) X X
Composition image (lateral) X X
Electronic states X X X
4. OrderinglDefects
Pinhole defects « 0.1-1 JlID) X X X X X
Long range translational; X X X X X
density fluctuation defects
Orientational ordering X X X X X
Surface ordering X('!) X X
 Table 4. Major Techniques to Characterize Critical Aspects of Film Structure (Concluded)

Characterization Technique
Ellip-
sometry AFM.
(including STM XRR. He LEED.
Critical Film Feature XPS SIMS IR SE) RBS SEM (TEM) XRD Scat SFG HREELS UPS Raman ISS (TED)

s. SubstratelFilm Interface
Chemical bonding X X('!) X X X X X X
Pinning geometry X X X

Definition of Acronyms for Characterization Techniques

XPS X-ray photoelectron spectroscopy

SIMS secondary ion mass spectrometry
IR infrared
SE spectroscopic ellipsometry
RBS Rutherford backscattering spectroscopy
SEM scanning electron microscopy
AFM atomic force microscopy
STM scanning tunneling microscopy
TEM transmission electron microscopy
XRR X-ray reflectometry
XRD X-ray diffraction
He scat helium scattering
SFG sum frequency generation
HREELS high resolution electron energy loss spectroscopy
UPS ultraviolet photoelectron spectroscopy
ISS ion scattering spectroscopy
LEED low energy electron diffraction
TED transmission electron diffraction
 Table 5. Important Film Characteristics Possible from Processing Methods

Important Film Characteristics

Defect·Content Polar, Multi- Chemically,

functional Molecules Electronically
Long-Range for Chemical and Thermally, Controlled Unusual
Processing Wetting Stri-face Chemically Substrate/Film Multilayer Polymeric Substrate
Density
Method Patch Fluctuations Activity Stable Films Interface Capability Films Geometry
Pinhole

Langmuir- Can be made Can be made Uniform. high Chemical flexibility Lack of sub- Secondary, coin- Excellent; Uniform Poor; uni-
Blodgett very low very low by use density for very limited; mole- strate bonding cidental result in possible to polymer form cover-
under dust- of clean sub- surfactant-type cules must form gives poor a few cases; do A-B A-B films pos- age only on
free condi- strates molecules; uniform films on thermal and usually not pos- or A-B B-A sible by smooth, low
tions with large-area water (although Hg, solvent sible because of stacking of direct prep- radius of
clean sub- single crystals highly self- stability; this aqueous process- rod mole- aration using curvature
strates possible associated. can be some- ing disturbing cules to con- surfactant surfaces
(» 1 ~); hydroxylic organic what over- substrate surface trol inversion polymers or
shaped mol~ liquids and other come by poly- chemistry and symmetry for stiff aromatic
cules (cylin- similar liquids are merlc films because of lack electrical or polymers
der) can give possible); only highly of substrate/film nonlinear (e.g., poly-
controlled water insoluble chemical bonding response imide); post-
pores; e.g., molecules work, spacing consis- cross-linking
calilxaranes surfactant structures tent with LB film possible for
best; usually only packing arrange- some surfac-
one Bronsted acid- ment tant mole-
base group allowed, cules con-
but multiple non- taining vinyl
polar groups (e.g., and prop-
vinyl) are possible; argyl groups
the latter can be used
to crosslink films
after formation
 Table 5. Important Film Characteristics Possible from Processing Methods (Concluded)

Important Film Characteristics

Defect Content Polar, Multi- Chemically,

functional Molecules Electronically
for Chemical and Thermally, Controlled Unusual
LongcRange
Processing Wetting Surface Chemically Substrate/Film Multilayer Polymeric Substrate
Density
Method Activity Stable Films Interface Capability Films Geometry
Patch Pinhole Fluctuations

Self- Can be made Can be made Large-area Chemical flexibility Substrate Using 02-frt!e Poor; re- Strong sur- Any shape
assembly extremely very low using single crystals very good; require bonding can and H 2O-free quires labo- face bonds works be-
low using clean substrates possible using selective substrate lead to highly conditions, rious se- tend to kinet- cause mole-
clean sub- single-crystal chemistry based on stable films- substrates can be quence of ically trap cules are
strates; dust substrates with hard-soft donor- thermally chemically pre- chemical sur- . polymer con- carried to the
should not be low defect acceptor interactions stable to pcu:ed for organo- face modifi- formations surface by
a problem contents (e.g., to selectively bind > 200o~ pos- metallic bonding cation, fol- and chain molecular
MBE sub- one group leaving sible with reactions (e.g., lowed by configura- diffusion;
strates) others free; mole- excellent sol- bare semiconduc- coupling of tions in non- however,
cules must be vola- vent resis- tor surfaces- next layer; equilibrium high radius
tile for gas-phase tance; cross- oxide-free); special strat- frozen of curvature
assembly or soluble linking during bonding can egies needed glasses- means high
or molten for liquid- formation cause specific to avoid porous struc- index crystal
phase assembly; sol- (e.g., silox- permanent charge defects tures result planes are
vents used must not anes) gives redistribution at present and
corrode substrate. high stability the substrate overlayer
without sur- interface structures be-
face. bonds come poorly
ordered
 Table 6. Survey of Stable, Highly Organized, Self-Assembled Monolayer Systems

Characteristics of Film
General Type of SubstratelFilm Types of Multi- Potential
Substrate Absorbate Molecule Bonding functionality Allowed Physical Chemical Applications References
Si02 (amorphous X(CHJ SiCI), 1. Quasi-2D poly- X iii CH), C02CH) Highly stable; low Chemical reactions Optical devices if 4
glass or native usually n ... 18 siloxane CH .. CH2, Br, CN translational order; can be carried out high quality
oxide) network forms are typical; a variety high orientational on X; formation of multilayers with
R of soft donors and order with chain OH can lead to NLO groups are
[-O-Si-O-] acceptors possible axis oriented close condensation of formed; adhesion
I to 90° to surface second layer and coupling layer
-0 continued sequence
to multilayers

2. Occasional
Si-O-Si bonds
fonn at surface
-OH sites
AlIO) (native X(CHI). SiCI). As for SiOI CH). CH =CHI' CN Presumably Presumably similar Protective coatings; 4
oxide)-also other usually n • 18 similar to Si02 to SiOI modified electro-
hydroxylated oxides (almost no charac- chemical electrode
such as Ti02• SnOz• terization studies) surfaces
etc.
Au X(CHJ.SH. Au-SR bond; bond Highly varied. almost Thermal stability Chemical reactions Modified electro- 4-6
[X(CHJ.Sh. angle with surface any hard donor. to - 200°C; high can be carried out chemical electrode
n = 1-24 have been _ 90°-120°; acceptor. or nonpolar translational. on X; second layer surfaces; bioactive
studied; also RSH (-./3 x -./3) group: OH. NH z• orientational order can be fonned by surfaces
where R = aromatic R30° overlayer on C0 2H. CH =CH 2, with chain axis bonding of RSiCI)
rings Au(1U) CH), etc. oriented - 64° onto OH surface
from the surface
for a Au(lll)
surface
Au X(CHI).SiCI), No chemical bond- Unexplored. should Highly stable As for SiOI Modified electro- 4
usually n .. 18 ing to substrate, be same as for Si02 thermally; higher chemical electrode
only polysiloxane translational, surfaces
network orientational order
than for SiOI
 Table 6. Survey of Stable, Highly Organized, Self-Assembled Monolayer Systems (Continued)

Characteristics of Film
General Type of SubstrateIFilm Types of Multi- Potential
Substrate Absorbate Molecule Bonding functionality Allowed Physical Chemical Applications References
Au X(CH z). S (CHz)mY
~ - Au bond; Similar to RSH, Lower stability Should be similar to Probably none 4
m,n ~ 20 (RS)z than RSH, (RS)z RSH, (RS)z films because of low
presumably 0" films; chain dis- except for lower stability
donation ligand order suggests low sol vent stability
bonding translational order
Ag X(CHz). SH RS-Ag bond; bond More limited than for Similar to Au, but Unexplored; Protective coatings; 4.5,7
(Cu is similar) angle with surface Au since Bronsted chain axis is probably less varied adhesion coupling
apparently variable; Acid groups react oriented - 78 0 than for Au because layer
inconunensurate with Ag(oxide) from surface Ag is more
layer on Ag(lll) surfaces; non- corrodible
hydroxylic such as
CH], CHCH z, CH,
COzCH], etc.
Ag X(CHJ. C0 2W RC02-Ag+ ionic Unexplored except Thennal stability Generally Protective coatings; 4
bonding CH 2; presumably unexplored; chains unexplored adhesion coupling
nonpolar groups such fully extended in a layer
as CHCH 2 crystalline lattice
and oriented near
normal to the
surface
(CH Z).-C0 2H
Ag X CH (CH 2).-CO zH As above X = -O-,-S-, Thennal stability Unexplored; reac- Protective coatings; 8
unexplored; "loop" tions of X may be adhesion coupling
0
structures fonn possible layer
I with surface domi-
-C-, etc.
nated by proper-
ties of X; for
X=Hand
m + n = 30, loops
are arranged in a
crystalline lattice
 Table 6. Survey of Stable, Highly Organized, Self-Assembled Monolayer Systems (Concluded)

Characteristics of Film
General Type of SubstratelFilm Types of Multi- Potential
Substrate Absorbate Molecule Bonding functionality Allowed Physical Chemical Applications References
Al10 3 X(CH1). C01H. CH 3• CH = CH1• Thermally stable Generally Protective coatings; 4
n = 1-22 have been
RCO; AI +
=
CH CH; other non- to S; 200°C; chain unexplored adhesion coupling
studied; other acid (oxide) bonding polar or nonacidic disorder for layer
groups such as groups possible n S; 16 but more
P03H1• phenols are ordered for
possible n ~ 20; chain axis
oriented - 75-78
degrees from
surface
GaAs X(CH1).SH RS-As bonds CH3 and hard donor Thermally stable Generally Modification of 9
presumed acceptor groups such < 200°C; chain unexplored GaAs devices
as C01H. C01CH 3• ordering for
OH. etc. n,.. 18

•
(Table 6), strong ionic and covalent bonds impart considerable stability. Thus an important task associated
with building a given type of fIlm on a selected substrate is to find a suitable and specific
substrate/functional group pair with appropriate chemical affinity. One apparent exception to this rule is
the case in which the SA film is highly cross-linked, for example, in monoalkylsiloxane monolayers on
inert substrates such as gold (Table 6) for which no chemical linkages to the substrate exist, only weak
dispersion forces, and the stability is due to the insolubility and involatility of the polymerized monolayer.
However, such fIlms are still less stable than nearly identical fIlms on a substrate such as Si02, which can
form occasional bonds to the film via substrate silanol-film silanol condensation.

The second important difference between LB and SA films is that whereas LB multilayer films
can be readily formed by repeated dipping SA monolayers, in contrast, represent the completion of the
specific substrate/molecule assembling chemistry, and further layers must be formed by specific chemical
coupling steps. Innovative, complex schemes for such multilayering have been reported, and three
examples are given in Table 7. The first, the use of terminally substituted alkyltrichloro silanes, has been
the traditional method [4], but recent unique methods, using zirconyl phospho nate chemistry [10] and
amine alkylations combined with other coupling sequences [11], have recently been reported.

III. DIRECTIONS FOR FUTURE DEVELOPMENTS

There are two major directions for future work. The first is the exploration of applications for
highly organized films. In this process, problems will be encountered in designing and carrying out
syntheses ·of films that exhibit the desired functions. These problems will lead to both the refinement of
current critical is~u~s and the definition of new critical issues dealing with synthesis/structure/function
correlations. The second direction for future work is the scientific study of the most important of these
critical issues.

The mo's t important needs in the field of organized films are to develop or establish

• Quantitative methods for characterization, particularly fIlm defects

• A relationship between film structure, molecular pinning site geometry, and the adsorbate molecule
in SA films
• Theories relating wetting properties to surface molecular structure
• Synthetic protocols to make highly patterned, multifunctional surfaces
• Controlled pore size and pore distribution films
• Stable SA monolayers based on specific molecule/semiconductor surface chemistry for the major
semiconductor materials including GaAs, Si, Ge, and InP
• Multilayer film synthesis strategies to provide low defect, highly oriented superlattice structures.

17-16
 Table 7. Strategies for Constructing Multilayer Film Structures Using Self-Assembly and Chemical Coupling Starting with an Si0 2 Surface

First Layer Second Layer Third and Additional Layers

Reagent Film Structure Reagent Film Structure Reagent Film Structure
I. Convert

I
X
}X 2. X
X~OH

I
}-F>-X Repeat second
layer steps
n-I times J+ooor-+. x

Sia,
SiCl,

Si~
OH
OH
OH
fOlH2
I
Si(CH h
OH
3 ~~ PO,H2
1. ~
2. P03H2

I
J=~ ~-PQ,H2
PO,
/
,/'lz ,
o,P--~H2
Repeal second
layer stepS
0-1 times
Jt~~:~P=t~H2
PO, o,P P03H2
PQ,H 2
OH n

Q (CH2h
.Ot 01CH21
OH
I
(CHV3
"- N
/
OH
I
(CHV3

01CH2 N
1:0-0 00 2/
'OH
1. (a3SiOhSi~

2.
OH
I
No
PYA
}IG~: 's;~'pv+o,§
I .02
SiI, v 3. (a3SiOhSia 2 - Repeat IhiRllayer stepS for thicker
0, SiOPV A layers
- Repeat first and second layer steps for
another 0a0:t layer
- Repeat all steps for complete repeating
multilayer structures
REFERENCES

1. 1. D. Swalen, D. L. Allara, J. D. Andrade, E. A. Chandross, S. Garoff, J. Israelachivili,

T. 1. McCarthy, R. Murray, R. F. Pease, 1. F. Rabolt, K. 1. Wynne, and H. Yu, Langmuir,.1 932
(1987); this article is based on a panel report for the Division of Materials Sciences, Basic Energy
Sciences, Office of Energy Research, Department of Energy, 1987.

2. G. L. Gaines, "Insoluble Monolayers at Liquid-Gas Interfaces," Interscience, New York, NY, 1966.

3. G. C. Roberts, Adv. Phys., .2!. 475 (1985).

4. A. Ulman, "An Introduction to Ultrathin Organic Films, from Langmuir-Blodgett to Self-Assembly,"

Academic Press, New York, NY, 1991.

5. P. E. Laibinis, G. M. Whitesides, D. L. Allara, Y. T. Tao, A. N. Parikh, and R. G. Nuzzo, J. Am.

Chern. Soc., 113. 7152 (1991).

6. C. A. Widrig, C. A. Alves, and M. D. Porter, J. Am. Chern. Soc., 113. 2805 (1991).

7. M. M. Walczak, C. Chung, S. Stole, C. A. Widrig, and M. D. Porter, J. Am. Chern. Soc., 113,2370
(1991); M. A. Bryant and J. E. Pemberton, J. Am. Chern. Soc., 113, 3629 (1991).

8. D. L. Allara, S. V. Atre, C. A. Elliger, and R. G. Snyder, 1. Am. Ch~l!l. Soc., 113, 1852 (1991).

9. C. W. Sheen, J. Shi, J. Martensson, A. N. Parikh, and D. L. Allara, J. Am. Chern. Soc., 114, 1514
(1992).

to. For example, see T. M. Putvinski, M. L. Shilling, H. E. Katz, C. E. D. Chidsey, A. M. Mujsce, and
A. B. Emerson, Langmuir, Q, 1567 (1990); the original discovery of this method was made by
H. Lee, L. 1. Kepley, H. G. Gong, and T. E. Mallouk, J. Am. Chern, Soc., 110, 618 (1988).

11. D. Li, M. A. Ratner, and T. J. Marks, J. Am. Chern. Soc., 112, 7389 (1990).

17-18
 18. STATUS OF SURFACE MODIFICATION FOR MINIMIZING DIRT RETENTION:
ORGANIZED MONOMOLECULAR ASSEMBLIES

Lois M. Speaker
Manufacturing Research and Engineering Organization
Eastman Kodak Company
Rochester, NY 14650-2104

ABSTRACT

Soiling significantly hinders the cost- and energy-effective deployment of many surfaces used in
solar technologies. Because soiling expresses the universal, irresistible drive toward lowest surface free
energies, preventive technology will logically be directed toward reducing surface energy and physical
roughness while maintaining desired bulk and optical properties. Surface modification with fluorinated
ultrathin oriented fllms (Langmuir-Blodgett films or self-assembled monolayers) has been demonstrated
to hold promise for this application.

I. INTRODUCTION: SOILING AND SOILING RESISTANCE

A. Soiling as a Generic Problem

MittaI has pointed out that "people dealing with surfaces are afflicted with molysmophobial , and
rightfully so" [1]. Dirt retention on surfaces, known also as soiling, fouling, contamination, and a host
of more colorful, less scientific, and occasionally unprintable terms, is an energy-consumptive, cost-
enhancing problem that exerts continuing negative impact on every technology. Recent years have brought
increased attention to its cost, giving rise to extensive applied and fundamental research, to current-
awareness journals like the Fouling Prevention Research Digest and to conferences such as the 1990 '
Conference on Biofouling at SUNY-Buffalo and the quadrennial International Conferences on Fouling
and Cleaning in Food Processing.

B. Soiling as a Problem for Solar Energy Technologies

Soiling is of particular concern when operations rely on stable, optimized performance of a

solid/fluid interface, like the interface between a heliostat and ambient air. Heliostats, whether silvered
glass or the newer silvered-polymer membranes, incorporate many interfaces, each with its special
susceptibility to soiling and degradation. The compromise of each interface exerts a unique influence on
the efficiency of the total unit The first surface is the most susceptible, because it must confront the
synergistic actions of ultraviolet light, atmospheric gases like oxygen and water vapor, varying
temperatures, and bombardment by a wide variety of soilants that can cause both physical and chemical
degradation.

Figure 1 is a highly magnified schematic of a "worst-case" reflector surface, with no particular

attention given to relative scale or to material of composition. Because the glass or polymer portions of
many reflectors are insulators, they tend to build up electrons at the interface. Because some potential
soilants bear positive charges, they are electrostatically attracted to reflector surfaces. Other soilants may

1 Molysmophobia: fear of dirt or contamination, from Mrs. Byrne's Dictionary of Unusual, Obscure, and
Preposterous Words, University Books, Secaucus, NJ, 1974, as cited in Reference 1.

18-1
be attracted by long-range forces and attach by combinations of physical adsorption and chemisorption,
as discussed below.

From a macroscopic point of view, this reflector surface is undoubtedly very smooth; it may even
be microscopically and optically smooth. However, no mechanical polishing, chemical treatment, etching
technology, sputtering, or polymer-casting technique can produce a surface that is smooth on a molecular
scale. Even a very large molecule, the smallest entity that could be defined as "dust" or "soil," will
perceive this surface as rough, with cracks and crevices of widely varying shapes, sizes, and depths. Such
irregularities offer sites for soil particles; given fortuitous matching of irregularities, "lock and key"
adhesion may render even small particles virtually impossible to remove, despite the lack of an "energetic"
reason for their permanent attachment.

The Solar Energy Research Institute has stated that "short-term specular reflectance losses of
Aglglass mirrors are from O.S% to 1.0% per day at the Sandia site, with losses approaching asymptotic
values of 19% in 1.8 years. Short-term power losses of photovoltaic modules, attributed to soiling, are
4% to 7% per month, approaching asymptotes of 2S% to 60% for periods of greater than 1 year,
depending on site and season. The loss of power produced in central receiver concepts is roughly twice
that of the loss in reflectance of the heliostats; therefore, eliminating soil from reflecting elements is a
necessary condition for optimum performance of such a system . . . present first and second mirror
materials do not last for the time periods required for cost-effective concentration of solar energy" when
"exposed to the real environment [2]. Czanderna has said that "our ability to prepare interfaces with the
desired performance properties that will also retain stable performance will be critical (present author's
underlining) in the reliable deployment of [solar energy conversion] technologies" [3].

Roth and Pettit [4] and Clark et al. [S] supported Czanderna's evaluation [3] with their results
from studies of silvered-glass mirrors at Albuquerque, NM [4], and various cover plate materials at New
River, AZ, Miami, FL, and Gaithersburg, MD [S]. Figure 2 reproduces Roth and Pettit's diagram of
projected reflectance changes for the cases of "ideal" mirror cleaning, washing in which cleaning agents
cause degradation, and long- and short-term soiling in the absence of any cleaning. Figure 3, from the
same study, shows actual specular reflectances of glass mirrors undergoing soiling-cleaning cycles of
various lengths. "The average daily reflectance loss for, respectively, the 2-,6-, and 12-day cycle mirrors
was 0.008S, 0.0061, and O.OOSI reflectance units. Thus, the rate of dust accumulation decreases as the
amount of accumulated dust increases" [4]. Moreover, "net scattering by the accumulated particles
increases with decreasing wavelength and with increasing level of soiling" [4].

C. Cost, Energy, and Environmental Benefits of Modification

SERI has said that reflector cleaning constitutes a large fraction of the lifetime cost of operating
a [future] solar thermal power plant. The logical solution is to render mirror interfaces permanently
adhesive so that they repel soilants throughout their lifetimes. There are associated indirect benefits:
heliostat cleaning with strong reagents like aqueous solutions of hydrofluoric acid and surfactants is a
serious source of environmental concern. Minimizing the use of cleaning agents would benefit the
environment as well as the dollar-and-energy-cost package.

An optimized antisoiling technology would fmd alternative applications in optical devices and
instrumentation manufactured from transparent or reflective polymers and glass. Soiling and fouling also
compromise operations in many diverse fields, including the critical industrial operations of separations
and heat transfer. These consume vast amounts of energy that could be substantially reduced by strategic
minimization of soiling and fouling.

18-2
II. SOILING-PREVENTION DESIGN PARAMETERS

A rational approach to soiling prevention by surface alteration must take into account at least the
following practical considerations: '

• Performance-related cleanliness criteria

• Maintenance of applications-related bulk and surface properties
• The driving forces behind soiling .
• Cost, energy, and environmental analysis of modification.

A. How Oean is Clean Enough?

Although we speak freely about "maintaining" cleanliness, a clean or adsorbate-free surface is in

fact a rarity in the real world. According to Morrison, "There are three types of contamination that. must
be removed in order that the results can be described as representing a clean surface. One is a separate
phase, such as an oxide on a metal. The second is adsorbed gases and impurities. The third is crystal
damage, including implanted ions near the surface. The problem of crystal damage arises particularly
when sputtering'is used to clean the surface" [6]. By these criteria, we may postulate that clean surfaces
were never available until it became possible to prepare and maintain, for at least a limited time, single-
crystal surfaces by cleavage in a vacuum of < 10-9 Torr, or by ion bombardment and annealing cycles.

. Fortunately for solar energy technologies, the definition of "clean" is not nearly this stringent:
a clean solar technology interface is simply one that retains the performance properties for optical surfaCes,
such as refractive index, specular reflectance, absorption, reflectivity, and transmittance for optical
surfaces, that characterized it prior to exposure under use conditions. Nevertheless, implementation of
even this limited objective has proved challenging.

B. Origin and Experimental Assessment of Adhesive (Soiling) Capability

1. A Schematic of a Soiled Surface

Eirich commented in 1967 that "there are no free, or pure, surfaces in nature. Every so-called
surface, in actuality, is an interface between two physically recognizable phases and is covered
spontaneously with a hierarchy of adsorbed layers such that the free surface energy becomes minimized"
[7]. Patrick labeled Eirich's scheme the "Hierarchy of Spontaneously Adsorbed Layers" and named the
first monolayer the "A" film, characterized by such strong adsorption to the virgin or atomically clean
surface that it can be removed only through literal destruction of the interface (Fig. 4) [8]. An A film
potentiates strong attachment of B-Iayer soilant, removable by energy-intensive chemical and mechanical
procedures such as scrubbing with a surfactant solution. B-Iayer soilant, in turn, invites relatively loose
attachment by C soil, which is quite chaotically arranged and can be removed with minimal energy input,
for example. by shaking or evacuation to facilitate desorption.

This schematic points up important issues: the apparently irresistible drive of most surfaces to
form new interfaces by sorbing A layers; the impossibility of removing an A layer, once established; and
the fact that A layers usually, if not always, potentiate the buildup of B and C layers.

2 .. Energies and Rates of Substrate-Adherend Interactions

Roth and Pettit observed that "The initial forces of adhesion are probably dominated by
electrostatic forces and surface energetics, while after sufficiently long periods of time, stronger chemical

18-3
and physical bonds can develop. The few experiments that have been perfonned show that the forces of
adhesion in general increas~ with decreasing particle size and with increasing time of surface contact" [4].

Having been drawn toward an interface by gravitation or swept toward it by convective currents,
wind action, or other "mechanical" means, potential soilants may be more closely attracted by "long-range"
forces, then attached by physisorption and chemisorption. Detailed discussions may be found in many
books, including the classic treatise of Adamson [9] and a briefer, but excellent, text by Myers [10].

Long-range forces comprise electrostatic interactions, which are as powerful as covalent bonds and
decay with the inverse square of the distance between charges, and van der Waals forces. Vander Waals
forces can be further subdivided into pennanent dipole-pennanent dipole interactions (two orders of
magnitude less powerful than covalent or electrostatic bonds and responsive to the inverse cube of the
interdipole distance); penn anent dipole-induced dipole interactions, with energies proportional to the
inverse sixth power of the interpolar distances; and London dispersion forces, also proportional to the
inverse sixth power of the distance. Dispersion forces, the most important to adhesion, arise from
quantum mechanical effects, are exerted by all chemical species, and can act over ranges as long as
10 om [9,10].

Once long-range forces bring a sorbent and substrate together, the stage is set for physisorption
and chemisorption. Figure 5 reproduces a diagram of the overlapping regions of these phenomena,
demonstrating that they must be cooperative. "Curve 1 represents the energy diagram for physical
adsorption... As the [sorbent] approaches the surface, there develop van der Waals interactions leading
to an energy minimum representing the heat of adsorption, MIads• At some distance, there begins to
develop ... a repulsive interaction. Curve 2 represents ... chemisorption, which ... involves specific
interactions between the adsorbent and the adsorbate... If the two adsorption processes were mutually
exclusive, the activation energy of chemisorption [~] would be so high that it would occur only under
rather vigorous conditions . . .. it becomes clear that physical adsorption is an important component of the
overall chemisorption" [11].

Chemisorption is "by nature limited to the fonnation of a monomolecular adsorbed layer, ...
whereas physical adsorption has no activation energy, . . . is diffusion controlled, [and can] form
multi molecular thicknesses in a pseudo-liquid assembly (as in the B layer of Fig. 4) [12]. Chemisorption
is relatively slow because of an activation energy barrier, operates only within the range of chemical bond·
distances, and can be regarded as playing no role in the initial attachment of soilants" (present author's
underlining).

3. The Unique Aspects of Aerosol Impingement and Adhesion

Aerosol impingement is of great concern for solar energy applications, particularly in seashore
regions where atmospheres laden with salt and pollutant aerosols are common. Liquid or solid aerosols
impinging on and adhering to surfaces constitute very special cases of liquid/solid and solid/solid
interactions. Particles descending to one J.1IIl or below are of the same order of magnitude as surface
roughness, making it possible for actual embedment to enhance the more usual forces leading to adhesion.
Small aerosol diameters, their potentials for labile electrostatic charging, and their extensive dispersion
greatly enhance adhesion in a complicated manner.

To quote Rumpf and Schubert: "This is the world of fine particles; their behavior depends much
more on surface phenomena than on volume forces" (present author's underlining) [13]. Adhesion to a
substrate of particles larger than one cm in diameter is very sensitive to gravitational effects. As particle
size diminishes, gravitational influences decrease rapidly, but adhesional influences such as material

18-4
bridging, sintering, van der Waals attractions, and electrostatic effects (see Fig. 6) remain powerful. As
Myers observed, "It is recognized that the main driving force for sintering is surface tension rather than
external pressure. Atoms or molecules located at sharp asperities on the surface experience a greater
surface tension force and have a greater surface mobility than those on planar surfaces. Furthermore, the
actual area of contact between particles undergoing sintering will be small so that even at relatively low
total pressures, the pressure applied at the points of contact will be multiplied so as to exceed the yield
value of the material" [15].

Davies, in a classic 1973 review of experimental literature on particle adhesion, filter clogging,
and filter penetration [16], concluded that:

• Th~ probability ofliquid or solid particle adhesion depends directly on aerodynamic drag and therefore
on both velocity and particle size.

• Adhesion begins to fail at a flow rate of 4 mls for particles greater in diameter than 0.5 JlIIl. At flow
rates below 1 mls. adhesion is nearly comolete for all particles up to 1 urn in diameter. Initial
deposition efficiency and adhesion decrease With increasing co11isi~n velocity.

• Deposited particles are rarely distributed evenly over surfaces and often build up chain aggregates [at
asperities] to form pseudo-fibrils (Fig. 7).

• Particles with diameters of 2 to 6 JlIIl are very unlikely to be redispersed after adhesion to reasonably
clean surfaces.

Consistent with this, Roth and Pettit's particle-size distribution measurements showed that small
particles are preferentially retained at mirror surfaces. Moreover, particles within the aerosol range
produced the most catastrophic effects on mirror reflectivities [4].

4. Relationship of Soiling Propensity and Surface Energy

A-layer soiling is a powerful expression of the universal drive toward the lowest free-energy states.
An array of molecules in the asymmetric surface environment is virtually defined by its high energy,
relative to that of an array of the same type and number of molecules in the bulk. "Excess" (surface) free
energy arises from the unique interfacial environment, in which atoms experience the effects of anisotropic
force fields. The manner of surface preparation and postpreparation history greatly influence surface
energy; a rough surface, for example, will have tightly focused high-energy regions surrounding asperities.
Frictional wear and corrosion, as well as adsorption, can radically modify surface energy.

Metals have intrinsically high surface energies, and" 'clean' surfaces of ... cryStalline, metallic,
and inorganic glassy materials, (with) surface energies of l(f-l~ mJ m-2, ••• will literally "do anything"
in order to lower their surface energies, including especially the adsorption of almost any available
molecule ... nitrogen, oxygen, water, or any other material present in the environment" [17]. The
kinetics of such adsorption are extremely rapid at high-energy interfaces and much slower at the surfaces
of polymers, which are generally characterized by lower surface energies, polydispersity, noncrystallinity,
and randomness. Polymers, however, experience virtually constant chain relaxations in their continuous
attempts to approach equilibrium, with slow but real effects on surface energies and sorptive propensity.
Adsorption at the surface of glass is intermediate in rate between metals and polymers.

Water, present to some extent in even desert atmospheres, exerts a particularly important influence:
"Even very hydrophobic, rigid polymers such as polymethylmethacrylate which contains somewhat

18-5
hydrophilic ester side chains will, in contact with water, undergo surface molecular reorientation due to
the interaction of water with the ester groups. The interfacial region becomes plasticized (roughly put,
softened) because the water-ester interaction liberates to some extent the side chains and increases their
mobility ... these surface interactions can dramatically change the interfacial characteristics of a polymer.
... Glass (as well) ... has been shown to undergo interactions with liquids such as water which lead to
specific alterations in its surface properties" [18].

5. Experimentally Relating Surface Energy and Wettability to Adhesion

Direct determinations of surface energy are impossible for solids because, by definition, they
cannot be reversibly deformed; expansion or contraction introduces bulk strains that energetically dwarf
surface free energy. Adhesiveness and its antithesis, abhesiveness, thus can be related to surface energy
through wettability, an experimentally accessible measure of the density and uniformity of interfacial
contacts [19].

During wetting, an interface between the substrate surface and one fluid (air or test-liquid-saturated
air) is replaced by an interface between the same substrate and a second fluid (the test liquid). Both the
thermodynamics and the kinetics of this process are multifaceted, and the kinetics have not been amenable
to treatment by hydrodynamic theory. Thus, the reality is emphasized that wetting and sorption are
functions not only of the properties of the substrate, the incumbent fluid, and the displacing fluid, but also
of the two substrate-fluid interfaces and the single fluid-fluid interface.

Predicting adhesiveness from wettability starts with Young's equation describing the shape (contact
angle) of a liquid drop on a solid. Zisman defined an empirical "critical surface tension" or CST (a) for
solids, based on the extents to which they could be wetted by liquids of different surface tensions [20].
Ogarev [21] combined the defining equation for work of adhesion (WsJ and the Girifa1co-Good equation
[22] as condensed by Huntsberger [19] with the mathematical expression of the Zisman CST, then
differentiated to obtain

WSL, maximum =0.04 [1 + 0.04(CST)]2)/2

Thus, the CST of a solid is a justifiable indicator of its work of adhesion. In general, it is understood that
a necessary, but not sufficient, condition for liquid adhesion is that the surface tension of a spreading
liquid must be lower than the CST of the substrate [23]. One characteristic of an adhesive surface will
be a low CST.

We often describe a surface in terms of its hydrophilicity (oleophobicity) or oleophilicity

(hydrophobicity), implying a wettability -spectrum like that shown in Fig. 9, which shows the influences
of both chemistry and morphology on CST (labeled in this chart as 'Yc). This wettability spectrum covers
the range of possible dispersion-force interactions, which are markedly reduced when either a surface or
an adherend is perfluorinated. Most materials are fluorophobic, and perfluorinated materials are both
hydrophobic and oleophobic, indicating that fluorination is an excellent approach to imparting
adhesiveness. Moreover, configuration of a surface in either an oriented-monolayer or a crystalline
morphology is likely to enhance adhesiveness.

Ill. SURFACE-MODIFICATION TECHNOLOGIES

As long ago as 1967, a Symposium on Interface Conversion for Polymer Coatings emphasized
rendering metallic or nonmetallic substrates more amenable to the attachment of polymer coatings [24].
Recognition of the critical importance to many technologies of interfaces and, therefore, of interface

18-6
 modification, has blossomed over the last decade. There are now regular meetings of the International
Conference on Surface Modification Technology, which focuses chiefly on alterations of metallic and
ceramic interfaces, and Gorham Advanced Materials Institute very recently organized "Thin Films '91,"
its third "international business and technical conference focusing on the growth of the $10 billion thin
films market in the 1990's" [25]. Several journals, notably the Journal of Adhesion Technology and Thin
Solid Films, regularly publish related artiCles.

Techniques for characterizing interfaces have burgeoned in recent years, spurring both increased
appreciation of the meaning of cleanliness and the development of new methods for approaching it. These
analytical approaches (including Auger electron spectroscopy [AES], X-ray photoelectron spectroscopy
[XPS], electron spectroscopy for chemical analysis [ESCA], ion scattering spectroscopy [ISS], secondary
ion . mass spectrometry [SIMS], ellipsometry, plasma chromatography, ion chromatography,
microfluorescence, evaporative rate analysis, indium adhesion, surface potential difference, wettability,
scanning tunneling microscopy [STM), atomic force microscopy [AFM], and many others) reach a
precision and resolution undreamed of only a few years ago.

Surface cleaning and modification technologies are legion and include, but certainly are not limited
to, treatments with solvents, plasma, ultraviolet (UV)/ozone, mechanical ablation; ion milling, ion
implantation, laser ablation, chemical vapor deposition (CVD), plasma-assisted CVD,ion beam deposition
and etching, sol-gel or polymer coating, photo-induced reaction, cathodic sputtering, surface chemical
attack, and various hybrid technologies. Many, if not most, of these are more suitable for modification
of ceramics or metals than for modification
.
of polymers [25].,

Any acceptable soiling-prevention technology must exert either beneficial or minimal negative
effects on such original material characteristics as rigidity, density, and coefficient of thermal expansion.
If a modification does not enhance stability toward physical; chemical, and thermal degradation, it must,
at the very least, not destabilize. Solar energy applications place one very special demand on interfaces:
any coating as thick or thicker than one-quarter of the wavelength of visible light is likely to disturb the
optical' characteristics that are of primary importance. Thus, a modified interface either must have
precisely the same set of optical properties, including refractive index, as the original surface, or it must
be thinner than 120 Dffi. It stands to reason that a coating with optical properties identical to those of the
bulk is likely to be compositionally identical and, thus, similarly adhesive. The preferred modification,
therefore, will produce an extraordinarily thin adhesive coating that is molecularly smooth and permanent.

Among surface treatments directed specifically at improving the performances of solar energy and
optical devices have been antireflection coatings through sol-gel processing of optical thin films [27],
fabrication of polycrystalline thin films for photovoltaic devices [28], coating of photovoltaic devices with
a fluorinated silane that bonds covalently with the surface [29], and plasma polymerization of fluorinated
monomers at the interface [30]. Implantation of fluorine at the surface might appear to have great promise
for increasing adhesive and barrier characteristics of polymers; there are indications, however, that the
damage incurred by polymer exposure to an ion beam actually overwhelms any barrier properties that
might result from fluorine addition [31].

IV. ULTRATIIIN ORIENTED MOLECULAR FILMS FOR SOIL RESISTANCE: ANTI-FOULING

1ECHNOLOGY (AFT)

It is clear that intervention before long-range substrate and adherend forces can swing into
operation will prevent the physisorption and chemisorption necessary to soiling. The most direct and
practical approach will minimize asperities and cancel or reduce the London dispersion forces exerted by
the substrate in the direction of potential adherents.

18-7
A. Oriented Molecular Films for Soiling Resistance

Compositionally, oriented films are formed from amphophilic compounds; their unique behavior
results from the high precision.with which they can be packed and oriented on a surface, as well as their
thinness (- 25 A) and the tenacity with which the first monolayers often cling. For many years after their
discovery by Langmuir [32] and initial explorations of their properties by Blodgett [33], oriented films
were regarded exclusively as laboratory toys. As two recent books on the subject [34,35], many reports
in the scientific journals,. and Chapter 17 in this volume attest, however, fundamental and applied research
in the area has been vigorous over the last decade; it is probable that industrial applications are just around
the comer.

Monolayer films can be applied to a variety of substrates, including polymers, glass, and ceramics,
either by the classical Langmuir-Blodgett (LB) dipping technique (LB films) or by the formation of self-
assembled monolayers (SAM). Both technologies, as well as properties of the ftlms and many potential
applications (but not antifouling) are described in detail in the books referenced. Substrates covered with
intact oriented films often display a combination of properties directly opposite to those known to
potentiate soiling or fouling: they are physically smooth on a molecular scale, usually hydrophobic, and
chemically homogeneous. · .

Figure 10 schematically represents the heliostat surface of Fig. 1, now "ideally" coated with an
oriented monomolecular film of a long-chain pyridinium bromide (RrPyrBr), and where Rr represents a
hydrocarbon chain fluorinated at one end. It is apparent that the heliostat surface has been radically
altered with regard to those properties that potentiate soiling: molecular smoothness has been conferred
by the LB film, the static charge has been at least partially neutralized, and impinging soil particles may
now be repelled by the perfectly oriented low-energy perfluorinated methyl layer. TIlis approach to
converting a surface from attractiveness to repulsiveness toward soil ants has been given the acronym AFr,
for Anti-Fouling Technology [36].

B. AFr for Membrane Separations

The utility of AFT was first explored for anion-exchange membranes in electrodialysis (ED)
stacks. These membrane systems are most seriously affected by fouling; because of their negative charges,
most foulants are electrostatically attracted to the permanent positive charges on the membranes. The
resulting fouling leads to sharp increases in the power requirements for the stacks and severely limits the
application of ED.

In a 1981 research effort supported by the Department of the Interior, my coworker and I
deposited LB ftlms on two types of commercial polymer anion-exchange membranes, challenging the
resulting "composites" in a laboratory ED stack for up to 184 h by concentrations of (sodium humate)
foulant four orders of magnitude greater than those occurring in natural waters [37,38,39]. The electrical
resistance of a stack containing untreated membranes is profiled in the central curve of Fig. 11. Only one
oriented molecular layer of a fluorinated amphophilic material on the membrane effectively prevented
increases in resistance (the lowest curve of Fig. 11), indicating enhanced adhesiveness at the membrane
surface.

Conversely, a single molecular layer of arachidic acid significantly increased the initially observed
electrical resistance, as well as potentiating rapid rise to a steady-state resistance almost twice that of the
untreated membranes (top curve of Fig. 11). The initial high resistance presumably was due to formation
of a high-resistance "sandwich" membrane by the LB film of neutral or negatively charged foul ant
(arachidic acid) at the surface of the positively charged membrane. This nonfluorinated oriented layer (a

18-8
perfect "A" layer) may then have served as a base for denser attachment of B and C layers than ordinarily
could have occurred. The influences of AFr on wettabilities of these membranes correlated well with
their soiling resistances. The rate at which untreated membranes sorbed (with swelling) a standard water
droplet was noticeably retarded .by treatment with fluorinated films and enhanced by layering with
arachidic acid.

Later work showed AFr to be effective as well for pressure-driven membrane separations, in
which the usual figure of merit is flux at constant pressure. Figure 12 shows the effect of fluorinated LB
fIlms on the fluxes of polysulfone ultrafiltration membranes during the first 7 hours of operation under
dead-end fouling conditions [40,41]. At first, the flux of both treated membranes is lower than that of the
control being stirred at the same s~d, indicating that the LB film has reduced the pore sizes; within only
3 to 4 h, however, there is crossover because of the rapid flux decay of the untreated control.

Figure 13 summarizes the results, between 10 and 23 h after initiation, of humate fouling
experiments with regenerated cellulose ultrafiltration membranes under a different set of ultrafiltration
conditions [42]. Total permeate volume is the consequence of cumulative flux; concentration of foul ant
at the membrane surface reflects both membrane selectivity and the challenge against which the membrane
must work. Treatments with FHxUA (perfluorohexyl undecanoic acid) and FHpPB (perfluoroheptyl
undecanyl pyridinium bromide) produced highly efficient composites that were more selective while
simultaneously maintaining higher fluxes, even against both precipitated gels of humate and the highest
possible solution concentrations of humate.

C. AFr for Heliostats

In 1985, my research group at Georgia Institute of Technology undertook two successive SERI-
sponsored programs to determine whether AFr might provide effective soiling protection to heliostats
while maintaining the original optical properties. Although there were significant problems with
reproducible deposition of LB films due to the hand:-aperated equipment and poor vibration isolation, the
results indicate that AFr may be an important step toward adhesion enhancement, especially in devices
for which thinness and precise arrangement of the modifying layer are critical [43].

The substrate of choice was ECP-300A, a four-layer film (polyester release liner, acrylic adhesive,
silver reflecting layer, polymethylmethacrylate coating) fabricated by the 3M Company, Energy Control
Products Division, for glass- or aluminum-supported or stretched-membrane heliostats. As received,
ECP-300A did not readily accept LB layers, possibly because of contaminants or because manufacturing
additives like UV retardants had become segregated at the surfaces; brief oxygen plasma treatments prior
to layering resolved this problem.

We developed a "mud-pack test" for initial screening, coating heliostat samples with a thick slurry
of common Georgia red clay in tap water. After drying horizontally for 24 h, the samples were rinsed
for about 1.5 min under running tap water and allowed to dry again before their reflectivities were
measured by FTIR (Fourier transform infrared) spectroscopy. This challenge "exaggerate[d] the [adhesive]
difference[s] between different coatings" [43]; treatments that survived it were used to prepare samples
for SERI.

In tests more readily extrapolatable to real-life exposure, Pitts of SERI dusted the samples with
standard dust from an air-driven gun and exposed them in an accelerated weathering tester for two light '
cycles followed by condensing humidity [44]. This exposure cycle is said to be equivalent to 1 year of
outdoor exposure. After samples had air dried for 1 to 2 h and been rinsed with deionized water from

18-9
a paint sprayer, their relectances at 650 nm were measured at four different full-cone angles of 4, 8, 12,
and 31 mrad at SERI.

As cost matching for an earlier government contract [39], 3M had provided to us a variety of
proprietary fluorinated surfactants, which were re-examined for this application. Two of these, 3M
'compound L-l0089 (a fluorinated carboxylic acid) and 7FlOH itaconate (7FlOilltc, perfluoroheptyl
undecanyl itaconate, a polymerizable fluorinated amphiphile), showed promise.

Figwes 14 through 16 compare representative reflectance spectra of the best (most reflecting)
samples of untreated heliostat controls with the best treated samples of each type after one mud-pack
challenge followed by rinsing. Post-mud-pack reflectivities are summarized in Fig. 17. Reflectivities of
ECP-300A coated with one monolayer of 7FlOillt, L-l0089, L-11238, and L-11239 were significantly
higher than that of the control after one challenge cycle, while three layers of 7FlOillt appeared to confer
approximately the same protection as one layer of the same compound. One particular treatment with
carboxylic acid L-l0089 provided protection far superior to that of any other, including coating with three
layers of the same compound. In view of the mechanical problems with fIlm deposition, we believe that
this sample (Fig. 16, 33f) provides an example of the performance that may be expected when the LB
coating has been applied with the greatest .possible control of order, orientation, deposition speed, and
other process parameters.

Figure 18 shows that, in several but not all cases, average contact angles of pure water on
ECP-300A were increased by monolayers of fluorinated materials. Compound L-I028 was a fluorinated
quaternary ammonium salt, and L-11238 and L-11239 were both fluorinated acrylates that were
polymerized after deposition. The three films that produced reflectivity increases as monolayers had the
same effect when deposited in trilayers. Reflectivity results cannot be strictly correlated with the
wettabilities: the effect ofL-l0089 on water contact angle was by no means dramatic, although one
sample was strikingly nonwettable. Moreover, wettability was apparently decreased by a polymerized
monolayer of fluorinated acrylate L-11239, even though this compound afforded some protection against
soiling (Fig. 17).

Figures 19 and 20 proftle representative SERI reflectivity evaluations at 4 mrad as samples were
subjected to 20 soiling-cleaning cycles. Results of the SERI tests at all cone angles are summarized in
Figure 21, where it is evident that a 4-mrad cone angle exposes reflectivity differences most effectively.
Samples 29 and 31 had been treated with one and three layers, respectively, of 7FlOHITc, and samples
33 and 35 were treated with one and three layers, respectively, of L-l0089. All treated samples showed
higher reflectivities than untreated controls at virtually every stage of the test, with highest honors reserved
for a sample coated with one layer of L-l0089 (Figure iO). As Shutt noted, "the effect of the AFT
coating did not diminish in time, indicating that the film is sufficiently robust to endure extreme
environmental exposures. . .. since the sample showed no apparent decreasing trend in time, it is believed
that the protection which is afforded by the AFT coating would last substantially longer than this in actual
use" [43]. .

Finally, Fig. 22 compares post-mud pack photographs of an L-l0089-treated sample of

ECP-300A(a) and an untreated control sample (b). Photograph a, on the left. is mostly dark because it
images the camera pointed toward the sample, i.e., its surface reflectivity has survived the challenge of
the dried soil. In contrast, the control was encrusted with soil except where it had been mechanically
wiped, and it demonstrates virtually zero reflectivity.

18-10
V. CONCLUSIONS AND RECOMMENDATIONS

, On the bases of both theoretical considerations and the exploratory stUdies reported above, AFf
may well be a viable solution to the soiling-related problems of solar technologies. The influence of the
fluorinated LB film on wettability and permeability may positively benefit delamination tendencies and
corrosion of the silver layer. AFf also could impart abrasion and wear resistance, as has been well
demonstrated by a recent flurry of research on the tribology of oriented films [34,35].

Much work remains. There has not yet been adequate exploration, under optimized conditions,
of the relativ~ influences of the substrate-oriented fIlm interaction, amphiphile chain lengths, the natqre
of permanent charges, degrees of ionization, extents of fluorination, the density of amphophilic chain
packing, and other relevant parameters. We have observed, for example, that improved ordering of a
substrate surface produces higher quality and presumably more permanent LB films. There are now a
number of polymerizable fluorinated amphiphiles, one of which may lead to significant improvements in
durability. Lifetime testing on a statistically valid number of samples is an essential task. Finally, once
optimal systems have, been decided on, it will be necessary to establish the methods and best processing
windows for production of antisoiling coatings.

VI. ACKNOWLEDGMENTS

Mr. Walter Forrister and Dr. Daniel P. Campbell were vital members of the AFf-heliostat research
team during the 2 years that I directed it, making many valuable contributions. Dr. Joel D. Shutt
succeeded me as project director and prepared the Final Report; his scientific integrity and communication
skills are greatly appreciated. I wish to thank the Research Library staff of the Eastman Kodak Company,
particularly Ms. Diane Ely, for their timely assembling of the literature reviewed for, this paper.

REFERENCES

1. K. L. Mittal, "Surface Contamination: an OVerview," in K. L. Mittal, Ed., Surface Contamination:

Genesis, Detection, and Control, Plenum Press, New York, NY, and London, United Kingdom, 1980,
pp.3-45.

2. "Soiling and Cleaning of Solar Col1ectors," SERI Draft Document, 1988, Solar Energy Research
Institute, Golden, CO, 80401.

3. A. W. Czanderna, "Surface and Interface Studies and the Stability of Solid Solar Energy Materials,"
in L. E. Morr, Ed., Solar Materials Science, Academic Press, New York, NY, 1980, pp. 93-143.

4. E. P. Roth and R. B. Pettit, in L. E. Morr, Ed, Solar Materials Science, Academic Press, New York,
NY, 1980, pp. 199-227.

5. E. 1. Clark, W. E. Roberts, 1. W. Grimes, and E. J. Embree, "Solar Energy Systems-Standards for

Cover Plates for Flate Plate Solar Collectors," Report NBS TN 1132 to the U.S. Department of
Commerce, December 1980.

6. S. R. Morrison, The Chemical Physics of Surfaces, Plenum Press, New York, NY, 1990, p. 121.

7. F. R. Eirich, in P. Weiss and G. D. Cheever, Eds., Interface Conversion for Polymer Coatings,
Elsevier, New York, NY, 1968, pp. 350-374 .

18-11
8. R. L. Patrick, "The Effect of Water on the Adhesive Bond," lecrure presented at the Symposium on
Adhesion: Principles and Practice, Kent State University, June 16-20, 1980. Information and
reference courtesy of Dr. E F. Cuddihy, Jet Propulsion Laboratory, Pasadena, CA. .

9. A. W. Adamson, Physical Chemistry of Surfaces, Fifth Edition, Wiley-Interscience, New York, NY,
1990.

10. Do Myers, Surfaces, Interfaces, and Colloids, VCH Publishers, New York, NY, 1990.

11. D. Myers, oi:>. cit., p. 126.

12. D. Myers; op. cit., p. 125.

13. H. Rumpf and H. Schubert, "Adhesion Forces in Agglomeration Processes," in G. Onada, Jr., and
A. L. Hench, Eds., Ceramic Processing Before FIring, John Wiley and Sons, New York. NY, 1978.

14. H. Schubert, "Particle Adhesion to Solid Surfaces," in G. Hallstrom, D. B. Lund, and C. W. Tragadh,
Eds., FuncfumentaIs and Applications of Surface Phenomena Associated with Fouling and Cleaning
in Food Processing, University of Wisconsin, Madison, WI, 1982.

15. D. Myers, op. cit., Ref. 10, p. 114.

16. C. N. Davies, Air FIltration, Academic Press, New York, NY, 1973.

17. D. Myers, op. cit., Ref. 10, p. 117.

18. D. Myers, op. cit., Ref. 10, p. 122.

19. J. R. Huntsberger, "Mechanisms of Adhesion," J. Paint Technol. 39, 199 (1967); also in R. L. Patrick,
Ed., Treatise on Adhesion and Adhesives, Dekker, New York, NY, .1966, p. 119.

20. R. C. Bowers and W. A. Zisman, in E. Baer, Ed., Engineering Design for Plastics, Reinhold,
New York, NY, 1964, p. 689.

21. V. A. Ogarev, "'Dynamic' Critical Surface Tension of Wetting of Powders," Colloid 1. USSR, 45(6),
997 (1983).

22. R. A. Good and L. A. Girifalco, J. Phys. Chern., M:. 561 (1960).

23. M. Rosen, Surfactants and Interfacial Phenomena, Wiley-Interscience, New York, NY, 1978.

24. GM Symposium on Interface Conversion, in P. Weiss and G. D. Cheever, Eds., Interface Conversion
for Polymer Coatings, Elsevier, New York, NY, 1968.

25. Gorham Advanced Materials Institute, announcement of symposium, Thin FIlms '91, Gorham, Maine,
1991.

26. T.S. Sudarshan, Ed., Surface Modification Technologies: an Engineer's Guide, Marcel Dekker, Inc.,
New York, NY, 1989, pp. 493-566.

18-12
27. C. S. Ashley, in announcement of Symposium on Thin Films '91, op. cit, Ref. 25.

28. R. Noufi, in announcement of Symposium on Thin Films '91, op. cit., Ref. 25.

29. E. F. Cuddihy and P. Willis, "Antisoiling Coatings for Solar-Energy Devices," NASA Tech Briefs,
10(2), 90 (1986).

30. H. Beiderman, "Deposition of Polymer Films in Low Pressure Reactive Plasmas," Thin Solid Films
.M.. 125 (1981).
31. K. O. Legg, N. Tillman, and L. M. Speaker, "Plasma and Ion Fluorination for Chemical Hardening
of Synthetic Rubbers, Final Report to the U.S. Army Materials Technology Laboratory,
Watertown, MA, November 1989.

32. I. Langmuir, J. Am. Chern. Soc., 39, 1848 (1917).

33. K. B. Blodgett, J. Am. Chern. Soc., R 1007 (1935).

34. A. Ulman, An Introduction to Ultrathin Organic Films From Langmuir-Blodgett to Self-Assembly,

Academic Press, New York, NY, 1991.

35. G. Roberts, Ed., Langmuir-Blodgett Films, Plenum Press, New York, NY, and London, United
Kingdom, 1990, pp. 1-16.

36. L. M. Speaker, "AFT (Anti-Fouling Technology) for Membranes and Nonpermeable Surfaces," in
D. B. Lund, E. Plett, and C. Sandu, Eds., Fouling Clean. Food Process., Pap . Invited Contrib. Int
Conf., 2nd Edit, 1985, pp. 454-65.

37. Southern Research Institute, "Oriented Monolayer Assemblies to Modify Fouling Propensities of
Membranes," Final Report to the U.S. Department of the Interior, May 1981. Available from NTIS
as PB82-254913.

38. L. M. Speaker and K. R. Bynum, "Oriented Monolayers to Mitigate Membrane Fouling" in

K. L. Mittal, Ed., Physicochemical Aspects of Polymer Surfaces, Plenum Press, New York, NY,
1983, pp. 817-841.

39. "Materials Having Improved Nonfouling Characteristics and Method of Making Same," U.S. Patent
4,554,076, November 19, 1985; reissued as Re. 33,273, July 24, 1990.

40. L. M. Speaker, W. B. Forrister, H. Goo, E.S.K. Chian, D. P. Campbell, K. D. Goebel, and

R. M. Stem, "Anti-Fouling Surface Modification for Longer-Lived Membranes with Constant Fluxes
and Selectivities," Final Report to the U.S. Department of the Interior, Reston, VA, April 1988.

41. L. M. Speaker, "Fouling Prevention in Separations and Purifications," in H. G. Kessler and

D. B. Lund, Eds., Fouling Oean. Food Process., Pap. Invited Contrib. Int Conf., 3rd, 1989, Prien,
Bavaria, Germany, pp. 305-312.

42. L. M. Speaker, "Treatment of Membrane Surfaces with Oriented Monolayers for Improved
Renovation of Impaired Water," Final Report to the U.S. Department of the Interior, April 1991.
Available from NTIS as PB91-206649/AS.

18-13
43. 1. D. Shutt, D. 1. O'Neil, P. M. Hawley, D. K. Dawson, and J. A. Kearns, "Anti-Soiling Reflector
Research," Final Report to the Solar Energy Research Institute, Golden, CO, 1989.

44. R. Pitts, personal commu.nication, May 1989.

18-14
 Figure 1. Heliostat soiling from a molecular point of view

i _

I
_
-- --
~::::-_ _ _ _ _-::-::::

- - _ _
.....
:: ..,. Iff'tt

...........,. Iffect

---
It

"'--

Figure 2. Expected long-term reflectance behavior of an exposed mirror, with and without periodic
cleaning (from Reference 4)

·18-15
 ~.'~----~----------~

Figure 3. Specular reflectance of mirrors undergoing (a) 2-day, (b) 6-day, and (c) 12-day cleaning cycles.
The solid lines trace losses as the mirrors soil, and the dashed lines trace reflectance restored
on cleaning (from Reference 4).

Figure 4. Eirich's and Patrick's "Hierarchy of Spontaneously Adsorbed Layers"

18-16
 Activation energy for
+ chemisorption
2_

Figure 5. Schematic of energetic paths of physical adsorption and chemisorption, showing the crossover
point at which they become cooperative phenomena (from Reference 10)

with material bridges without material brid2es

p chern. bonding
sinter bridge JO v.d.W aals

to
Zl·
bonding material ~
~:jO
c:ryst.diss.malerial ~
-- el ec trostatic
(insulator)

p liquid bridge
viscous bonding t~O
:-
electrostatic
(conductor)

Figure 6. Various mechanisms by which aerosol particles irreversibly adhere to surfaces, including
material bridges (from Reference 14) .

18-17
Figure 7. Buildup of localized chains in preference to homogenous distribution of sodium chloride
aerosol (Watson, as cited in Reference 16)

CST

Ci)
q,
w
w w
Z a:
Cl
III w
o
(J
C

A POLYTETRAFLUOROETHYLENE(TEFLON)
B F. E. P. TEFLON
C POLYHEXAFLUOROPROPYLENE E
o PERFLUOROBUTYRIC ACID MONOLAYER
E PERFLUOROCAPRYLIC ACID MONOLAYER F
F PERFLUOROLAURIC ACID MONOLAYER

0~ ____ ~ ______ ~ ______ ~ ____ ~~ ____ ~ ______ ~ ______ ~ ____ ~90

o 4 8 12 16 20 24 28 32
SURFACE TENSION (200C) DYNES/CM

Figure 8. Contact angles for a series of liquid n-alkanes on fluorinated solid surfaces. The intercepts.
(CSTs or 'Yes) represent the "critical surface tensions" of the solids (from Reference 20).

18-18
 CST
o 10 20 30 40 50

C,
~ F, t
-CF-2 H ,,-F 2 - -CF 2 -CFH- -CFH-CH 2 -
<t H -CF 3 -CF 2- -CF 2 CH2-
IL
a: ... FLUORINATION
::l

~ ~I
U B
-CH 2-
U
t ~CH~
- CH2 -,~ CH ~

-..- - - - - HYDROGENATION
o C ~--------------------------------------~U~U--rl----~
~~ ~i'l CCIH-CH 2 - t - C(;1 2
~
CHLORINATION ---__t__-CCI 2 -CH-
~ C'Ir----------------~b:r-------v-g---.,--;
z 0, -CHOH-CH2- -C02 -CH2- ~CH~
o H
u

~u C, ~---------------------------------------~~r_,_Ir~--__,
f110 l - r
~ N, -CfN0213 t
<t 0, -CH20N02 -CH NHH0
2 2
H Lfl0t)-. ~-.;;;.J

UCRYSTAL I MONOLAYER bPOLYMER

Figure 9. The wettability spectra of selected low-energy surfaces, showing effects of chemical and
morphological modifications (from Reference 20)

Figure 10. Schematic of heliostat surface protected from soiling by an ultrathin oriented monomolecular
mm

18-19
 80 ( _ - _ - _ - _ . _

70 _ 1 LAVER ARACHIDIC ACID

• UNTREATED CONTROL
.. 1 LAYER RfpyrBr
60
E
.=
o

~ 50~
riz ~.----------.----.-----..

i 4°T
30r

80 90 100 110120130140 150160 170180 190 200

TIME. h

Figure 11. Electrical resistance proftIes of electrodialysis cells containing aqueous sodium humate
challenges of untreated anion-exchange membranes (central curve), membranes treated with
one LB layer of arachidic acid (top curve), and membranes treated with one LB layer of a
fluorinated amphiphile (from Reference 37)

Ii. Untreated control, aUr rate 80 rpm

C) o Untreated control, aUr rate 375 rpm
C) 5.0 • 1 LB layer 3M compound L·l0089, stir rate 375 rpm
C)

• 1 LB layer 3M compound L·l0089, stir rate 375 rpm

4.0

CI)
~
3.0
as
:::J
cr
en
"0 ~

~ 2.0

1.0 -t-....,...--r--.-~...,....-r--.--r--..,....-r- .......-,--...--"T""-.-.....,

o 50 100150200250300350400

Time, min

Figure 12. Flux profiles of polysulfone membranes challenged at 40 psig in a stirred dead-end ultra-
filtration cell by 25 ppm (initial concentration) sodium humate solution (from Reference 40)

18-20
 r-----------------------------~~
A T-8142
• T-8143
FHzUA: T-8142, 1-8143; FHPPB: 1·1245 + 1-8171
300
=
y 121.6 + 2Uz "!t X t& EtiIW

E
a.
./ •
•
1-8273
1-8274

a. fJ:IRfa
a 1.1152

....
c • 1·1162
o 200 • 1·lf64
x T.I245
C
II>
EHpPBICd
U
C • T·I231
o
u
B2fI
6.6.
6. T·I293
100 o T.I2N
• T·1301
• T·13tt
• T·1314
kIm1mJa
o 1·BRCt
o -t----.--.,..-----r-......-.-,.--.--...---~ 6. 1·BRCS
o 2 4 6 8 10

Cumulative permeate volume, liters

Figure 13. Nominal concentrations of sodium humate in retentate as functions of total permeate volumes
for two control membranes (BRC-l and BRC-5) and membranes modified by LB monolayers
to various fluorinated amphiphiles; Tests were run at 25 psig in stirred dead-end ultra-
ftltration cells against initial concentrations of 25 ppm humate (from Reference 42).

1.2 -.
SampleC2

1.0 -

0.8 "-
~
c::
~
CD
li
II:
0.6
I
~
___
-
0.41-

0.2 -

O.O~ ______I~ ________~I__________~I____________~I_________~

700 800 900 1000 1100
Wavelength (nm)

Figure 14. "Residual" FTIR reflectance spectrum of untreated control ECP-300A, after mud-pack .
challenge and rinsing (from Reference 43).

18-21
 1.2 ~
$ample 31e

1.0 I-

0.8~----------J

0.41-

0.2~

0.0~ __ ~~1 ________~1________~1________-41________~

700 800 900 1000 1100
Wavelength (nm)

Figure 15. "Residual" FUR reflectance spectrum ofECP-300A treated with one oriented layer of7F-lOH
itaconate, after mud-pack challenge and rinsing (from Reference 43)

1.2 ~

Sample33f -
1.0 I-

0.8 I-
Q)
u
c:
-
u
C1S

a)
;;::
a)
0.6 I-
a:
0.4 ~

0.2~

O.O~ ____ ~I __________L-I________~I__________I~______~

700 800 900 1000 1100

Wavelength (nm)

Figure 16. "Residual" FfIR reflectance spectrum of ECP-300A treated with one oriented layer of 3M
compound L-10089, after mud-pack challenge and rinsing (from Reference 43)

18-22
 100~--------------------------------~
~
1 layer
80 1-- -.--- -.- - - - -
3 layers
E
c 60'··- - - - - - ~
oL.!) Control
ill
@ . 40 I------IC~

20 "' -"'-....---...-..-~-

None 7F1OHIt 10089 1028 11238 11239

Surfactant

Figure 17. Summary chart of "residual" FTIR reflectivities at 650 run, after mud-pack challenge 'and
rinsing, for ECP-300A treated with LB films of fluorinated amphiphiles (from Reference 43)

100
~
Before

--( f)
<l>
<l>
'"-
0">
80 ~
After

--<l>
'D

.s!.
0">
C
60

<t:
~

u 40
B,...
(j
u
20

7F1OHltc L10089 L1028 Ll1238 L11239

Sample #

Figure 18. Effect on ECP-300A-water contact angles of coating with single oriented layers of various
fluorinated amphiphiles. The compounds are briefly described in the text (from Reference 43)

18-23
 100
•
Control
80 ...
7F1OH-lt
--->-
:~ 60
---u
Q)
=Q)
0:::
40
~

20

00 5 10 15 20
Cycle #

Figure 19. Effect of soiling and cleaning by 20 cycles of the SERI protocol (described in the text) on the
reflectivity of ECP-300A treated with one LB layer of 7FlOH-itaconate (from Reference 43)

100
•
Control
80 ...
L-10089
>-
:~ 60
u
~
Q)
0:::
~
40

20

OL---------------------------------------~
o 5 10 15 20

Cycle #

Figure 20. Effect of 20 cycles of soiling and cleaning by the SERI protocol (described in the text) on the
reflectivity of ECP-300A treated with one LB layer of 3M compound L-10089 (from
Reference 43)

18-24
 1DO r - - - - - - - -

80

60 cs:

31 flllCld

20

o 29C&0 31C&0 33C&0 35C&0 C\r1s

Figure 21. Summary of reflectivities at various' cone angles for ECP-3OOA films treated with one and
three layers, respectively, of 7FlOHITc (Samples 29 and 31), and one and three layers,
respectively, of L-l0089 (Samples 33 and 35) (from Ref. 43). Samples had been subjected
to 20 cycles of the SERI soiling-cleaning protocol.

Figure 22. Photographs of (a) ECP-300 silverized poly methyl methacrylate LB-treated with fluorinated
compound L-loo89 and (b) an untreated control sample. Both have undergone the smearing,
drying, and rinsing steps of the "mud-pack test;" the resistance to soiling of the treated sample
is demonstrated by its reflection of the camera (from Reference 43).

18-25
 19. APPLICATIONS OF SOLAR ENERGY TO SURFACE MODIFICATION PROCESSES

1. R. Pitts, E. Tracy, and Y. Shinton

National Renewable Energy Laboratory
1617 Cole Boulevard
Golden, CO 80401

C. L. Fields
Department of Chemistry
University of Northern Colorado
Greeley, CO 80639

ABSTRACT

. Recent work at the National Renewable Energy Laboratory (NREL) has demonstrated the utility
of using highly concentrated solar radiation to carry out surface modification processes. lhis highly
concentrated radiant energy provides a controllable means ·of delivering flux densities of up to 1<t ViIcm2
to solid surfaces. The resulting thermal energy can cause phase changes, atomic migrations. and chemical
reactions on a surface without greatly perturbing the bulk properties. It is also possible for the photons
to directly interact with species on the surface to carry out photolytic reactions. These changes result in
improved material properties either by making the surface harder. more corrosion- or wear-resistant, and
thermally resistant, or by giving it lower coefficients of friction than the base material. depending on the
change produced. In a solar furnace. this flux can be delivered in large quantities over large areas or can
be tailored to match the demands of a particular process. Furthermore. this occurs without. the
environmental liability associated with providing power to more conventional light sources. At NREL.
fluxes in the range of 100-250 W/cm2 have been used to induce beneficial surface transformations.
Significant results have been obtained in the area of.phase-transformation hardening of steels and melting .
powders and preapplied coatings to form fully dense, well-bonded coatings. Composition. hardness. and
microscopy data are discussed, and advances in coating technology using highly concentrated solar beams
to induce chemical vapor deposition and other processes are described.

I. INlRODUCTION

It is economically and ecologically attractive to modify the surfaces of materials using directed
energy beams. Compared to bulk processing. this technique conserves materials and energy. For example.
ion beams are used either to erode surfaces in prescribed ways or to implant species into a solid lattice
[1-4]. Electron and photoIi beams are used to facilitate surface reactions and to supply thermal energy
to surfaces to melt thin-film regions for annealing or welding applications [5-~]. The rapid growth in
these areas of surface modification results from dramatic improvements in the quality and reliability of
beam sources and from our increased knowledge and understanding of the fundamental nature of the
systems. As a result. many products have been significantly improved.

Materials processing using directed energy beams is an energy-intensive endeavor. Conventional

surface heating processes require converting primary energy (fossil fuels) to heat, heat to electricity. and
electricity back to heat. A number of .surface processing techniques require an additional step of
converting electricity to radiant forms to be applied to the surface of a material. Generation and
transmission losses account for a substantial amount of the original energy resource and can contribute
significantly to operating costs for some applications. Further compounding this situation are the
environmental liabilities associated with producing this energy with fossil ·fuels. These liabilities can

19-1
largely be avoided for applications that are suited for surface processing in a solar furnace, in which no
fossil fuels are needed and radiant energy can be used to heat surfaces directly. Solar energy has been
explored as a bulk processing energy source for years. However, only recently has it been realized that
the main contribution of solar energy to materials processing may be in the realm of surface modification.
Some of the applications of directed energy beams now being used or considered have solar counterparts.
In this article, we review areas of recent work in solar induced surface transformation of materials
(SISTM) and point out where solar energy may have other interesting applications.

The National Research Council recently summarized its evaluation of the status of materials
science and engineering in the United States [9] .. The council found that materials science rep~esents an
"enabling" technology that is on the verge of unprecedented progress in a number of exciting areas, but
the U.S. position in "synthesis and processing" and "processing performance" is relatively weak. The need
to develop new synthesis and processing routes, coupled with increasing energy costs and increased
environmental pressures, suggests that it is time to explore some nonelectric applications for highly
concentrated (> 100 W/cm2) solar radiation in the area of materials processing.

Modem solar furnaces range greatly in size and total power deliverable to a surface. Table lUsts
some solar facilities and their capabilities. The basic features of solar furnaces are exemplified in the
recently constructed solar furnace at NREL, illustrated in Fig. 1. All solar furnaces direct the sun's
radiation to a focus. There is, however, considerable flexibility in designing the optics to accommodate
and optimize a variety of process parameters. Beams may be designed to accommodate irregular shapes,
focal lengths can be adjus~ to mitigate damage to the optical elements by sputtering or outgassing of

Table 1. Some High-Flux Solar Facilities

Location Total Power (kW) Peak Flux (W/cm2)

AJbuquerque, ~
CRlF1 5000 240
Furnace 22 300
Atlanta, GA
Furnace 1.3 950
Golden, CO 10 21002
White Sands, ~ 30 360
Odeillo, France
Horiz. Furnace 1000 1600
Vert. Furnace 6.5 1500
Rehovot, Israel
CRRF3 290
Furnace 16 1100
Uzbek, USSR 1000 1700
1 Central Receiver Test Facility
2 Average flux measured at the exit aperture of a nonimaging
secondary concentrator
3 Central Receiver Research Facility

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the target materials, and a variety of secondary concentrator configurations are possible to adjust the flux
levels to the most useful range for carrying out a processing step. It is possible to concentrate the solar
radiatfon to about 2000 W/cm 2 with a single imaging concentrator, and up to 10,000 W/cm 2 with
nonimaging concepts in a medium with an index of refraction greater than 1 [10]. An additional benefit
is that scaling to very large power levels is possible. The Central Receiver Test Facility at Sandia
National Laboratories in Albuquerque is capable of delivering 5' MW of optical power on target. With
such large power levels available, it is conceivable to process very large areas. The radiation is delivered
directly on target, resulting in processes that are inherently clean and efficient There is no need for
auxiliary cooling at the optical source. Reaction chambers can be operated in cold wall processes, because
the beam is'delivered directly on target. These features suggest some interesting applications that will be
discussed in more detail in subsequent sections.

SISTM operates with terrestrial solar radiation, which is essentially a 6000 K blackbody band of
radiation extending from the near-ultraviolet portion of the spectrum (30S nm), through the visible portion
(maximum at 700 nm), into the infrared (2S00 nm). As Fig. 2 illustrates, many materials are better
absorbers of visible radiation than they are of infrared radiation. Most materials absorb solar radiation
efficiently, even without the use of special coatings or tec1iniques. Thus, concentrated sunlight impingiI1g
on surfaces causes extremely rapid heating. Dvernykov has calculated the time required for a number of
substances to reach their melting points when absorbing a flux of 2 x I~ W/cm2 [11]. The values in
Table 2 have been adapted from Dvernykov and reveal that a surface with low thermal diffusivity reaches
its melting point quickly, allowing the bulk of the sample to remain below its melting point. Furthermore,
upper layers of atoms in a solid can undergo rapid migration at temperatures that are approximately' 60% -
of the solid's melting point in what has been termed two-dimensional melting [12]. Therefore, even much
shorter times·than those in Table 2 can be used to modify surfaces exposed to concentrated solar radiation,
and a number of in~resting surface modification processes are possible at the flux levels achievable with
a solar furnace.

A. Solar Furnace

The solar furnace at NREL was completed in January, 1990, and it incorporates a number of
interesting design concepts that allow it to be used in a variety of experiments, such as the detoxification
of hazardous wastes and advanced materials processing (Fig. 1). The heliostat (A) has a 31.8 m2 area,
with a front surface ultraviolet (UV)-enhanced aluminum coating (O.S-mrad slope error, O.I-mrad
specularity, 92% solar weighted reflectivity). The primary concentrator (B) is composed of 23 hexagonal
facets that are spherical mirrors ground to a 14.6-m radius of curvature. The facets comprise an area of
I1.S m2 and are arranged so that the focal point is 30° off axis as illustrated in the drawing. The mirrors
are ground to 0.2-mrad slope error and OJ-mrad specularity and are front surface, UV-enhanced
aluminum. At the target, 94% of the energy falls inside a 1O-cm circle. The beam shape is Gaussian with -
a peak flux of 2S0 WIcm2 • A nonimaging secondary concentrator can be used to increase the peak flux
to 2S00 W/cm2 , and there are plans to demonstrate a refractive, nonimaging secondary that will raise the
peak flux to over SOOO W/cm2• The attenuator (C) is a vertically opposing two-plate design that trims the
light arriving from the top and bottom concentrator facets as it closes. It is located 1.78 m from the focal
plane, in the region of 2.5 WIcm2 peak flux. The plates move with speeds adjustable in the range of S to
70 mmls and are computer-controlled. Flux or temperature profiles can be programmed, and compensation
for minor fluctuations in the solar insolation is possible. The shutter (not shown) is an air-actuated
guillotine that can be operated in a manual or computer-controUed mode. It is located 3S cm from the
focal plane, is actively cooled, and opens or closes in 0.5 s. In addition to these features, the long-focal-
length primary mirrors allow flexibility in experiment size and orientation. There are remote video
monitors with color cameras for real-time viewing of the target zone and flux mapping. and there are over
100 data acquisition channels for thermocouple. pyrometer. weather. and insolation data.

19-3
 Table 2. Calculated Heating Rates

Melting point, Time to reach

Material Tm (0C) Tm (S)1
Metals
Al 660 0.42
Cu 1083 3.10
Ni 1453 1.03
Steel 1535 0.79
Ti 1670 0.23
Cr 1857 1.46
Mo 2617 4.70
W 3407 9.80
. Oxides
Sial 1720 0.014
TiOl 1870 0.044
Al10 3 2050 1.00
Vl O3 2410 0.107
CaO 2580 1.66
HfOl 2780 0.188
MgO 2800 2.59
Zr°l 2900 0.089
Carbides
TiC 3200 9.14
NbC 3500 0.86
ZrC 3540 0.112
SiC 3830 0.56
Nitrides
Si3N4 1900 0.059
AlN 2200 1.32
BN 3000 0.545
TIN 3200 0.611
1 Time required to reach Tm while absorbing a flux of 2000 W/cml

B. Target Assemblies

One result of the material processing work at NREL has been the fabrication of sample chambers
and related equipment designed specifically for material processing using a concentrated solar beam.
Among the equipment necessary for an experimental materials'processing facility, NREL has installed an
xyz platform for translating specimens, a rotatable mirror that redirects the solar beam onto horizontal
surfaces, an optical laser pyrometer to accurately measure and control sample surface temperature, low-
power alignment lasers, and secondary concentrators to increase the available flux densities. Sample
chambers include designs for maximizing temperature gradients by cooling the backside of the sample
with forced air or water, and chambers that allow control of the sample atmosphere. The most
sophisticated sample chamber to date includes a four-gas mass flow control system connected to a sample
chamber whose pressure can be controlled dynamically with a butterfly valve backed by a two-stage rotary
pump. The chamber can also be pumped to a pressure of < 1.0 x 10-7 Torr by a turbo-molecular pump,

19-4
and the chemical species in the sample chamber can be monitored by residual gas analysis. A wide
variety of experiments can be accommodated with the current hardware, and many more are possible with
relatively minor flXturing.

II. SOLAR ADVANTAGES

There are a number of advantages to using solar radiation for the surface processing of materials.
Some of these were mentioned in the Introduction. Primarily, radiant sources of energy are well suited
to surface modification because the energy is converted to heat at or near the surface, where it is used
directly. The resource is matched to the process. This conserves energy and affords the possibility of
minimizing cost Furthermore, solar radiation need only be dirj!cted and focussed, not converted to other
forms. There are no generating and transmission losses. The processes are inherently efficient and carry
little environmental liability. Otherwise, using solar radiation is very similar to using other light sources
(lasers, high-intensity arc lamps, or infrared heaters) for transient thermal processes.· The primary
advantages are as follows:

• TIle radiation is supplied in a broad spectral range, where most materials absorb efficiently without
special coatings. High heating rates are possible.

• Because the beam is delivered on target without prior conversion processes, there is little waste,
efficiency is high, and there is usually no requirement for auxiliary cooling.

• Scaling to very large powers and large areas is straightforward.

• The optics for a particular process are ordinary and can be designed with long focal lengths. This
makes sample areas flexible and manipulation convenient, and it reduces fouling of the optical train.
It is also easy to shape the beam and control the pulse to the target zone.

• There is minimal environmental impact in using this technology.

• The spectral range of the radiation is 0.305 to 2.5 J.1ffi. It is possible to stimulate a number of .
interesting photolytic processes on material surfaces.

• Systems analysis indicates that, depending on the location, the cost of energy delivery is less than that
of more conventional techniques.

The primary disadvantage is that a solar furnace requires good, direct normal insolation. This
means that it doesn't work at night or on ali overcast day. Consequently, one must either be very smart
about the use of labor during these periods, or have a hybrid operation.

III. DEMONSTRATED AREAS OF APPLICATION

A. Transformation Hardening of Steels

The process of transforming steel to martensite is called "transformation hardening." For some
applications, it is desirable to have a hard wear-resistant surface with a softer, ductile subsurface. To
achieve this end, it is necessary to preferentially heat the surface. Typical methods of applying heat to
the surface include flame, induction, or laser heating. One of the most recent techniques for surface
hardening of steel-laser transformation hardening-is now being used by the automotive industry .for
engine and drive-train components. This acceptance of laser transformation hardening was an

19-5
encouragement to develop the data base for the solar hardening of steel. Experimental confirmation of
surface hardening of steel using concentrated solar radiation and a favorable economic comparison between
a laser facility and a solar furnace [13] encouraged an examination of this application for solar furnace
technology.

Over the last 8 years, considerable research has been conducted on surface hardening by solar
energy [14-21]. The literature reveals that workers in China accomplished most of this work, but one
report was published in the Soviet Union [22]. The solar furnace used in China is a 1.56-m parabolic
concentrator with a focal length of 663 mm and a 6.2-mm image at the focal point. A flux of
3000 W/cm2 is claimed (calculated, not measured), with a maximum temperature around 3000°C (ZrB 2
melted). A hardened spot almost 5 mm in diameter was obtained with a I-s exposure. Longer exposures
enlarged and deepened the hardened region. The wear resistance of solar-hardened steel was compared
with that of steel hardened by an undisclosed method Superior wear characteristics of the solar-hardened
specimen were attributed to the high intensity of heat at the surface, which gave a fully martensitic
structure. Carbon was applied to the surface of some samples to increase the rate of heat absorption.
Some relatively complex surfaces were hardened by a scanning process across the cutting edges of reamers
and bits.

We have also experimented using solar furnaces in the United States to harden steels [23,24]. The
solar fluxes available for our experiments were of somewhat lower intensities than those reported by the
Chinese researchers. Consequently, the hardened zones in our work penetrated deeper into the surface and
resulted in relatively thick transition regions between the fully hardened zone and the unaffected, soft
s\lQstrate material. Transformation hardening experiments on tool steels were carried out in air at the solar
furnace in Albuquerque. Samples 2' x 6" x 0.5" were mounted onto a frame and clamped to the
positioning table. After the solar beam was directed onto the sample, it was translated in the z direction
to obtain a strip of hardened material. To obtain more information from a single pass, the translation rate
. was maintained at a single value while the incident flux was varied as a linear function of position.
Thermocouples were spot-welded at 2-in. intervals on both the front and back portions of the sample so
the temperature of the piece could be monitored. Selective hardening of the 4340 tool steel occurred in
the range of 200 W/cm2 at scan speeds in the range of 0.5 mmls. The fully hardened region was 1-2 mm
in depth and approximately 2 cm in diameter, with a heat-affected zone penetrating another 4-5 mm into
the plate (Fig. 3a). The hardness decreased from the fully hardened zone to the unaffected bulk region
smoothly as shown by the graph of microhardness (Fig. 3b). The unaffected zone was completely
unhardened, just like the material as supplied from the manufacturer. For massive targets such as these,
further work at 200 W/cm2 would be fairly uninteresting. Based on mathematical modeling, we have
postulated that the scan rate can be increased and the depth of hardening reduced by increasing the solar
beam intensity by a factor of 5. Figure 3a shows the overall shape of the hardened region, which follows
the gaussian distribution of the incident flux. A flat beam shape would result in a more uniform hardened
region. Modeling work at NREL has demonstrated that solar furnaces can be constructed to create flat
beam shapes, as well as more exotic figures.

In other experiments, nitride-grade steel samples, 89 mm in diameter and· 6.4-mm thick, were
exposed to the solar beam under a controlled atmosphere of either nitrogen or argon, using the previously
described vacuum sample chamber, and were water cooled from the backside to increase temperature
gradients and to decrease quench times of the heated sample. They were exposed to fluxes up to
185 W/cm2• Hardening was observed at the higher fluxes but was not uniform at the surface. Instead,
there were hardened dendritic-like needles beginning on the surface and extending 2 mm into the bulk.
The transition zones in this case were sharp. Regions on the surface between the fully hardened needles
were only partially hardened, indicating a nucleation phenomenon for the hardened zones. This nucleation
and growth phenomenon is expected for the austenitic transformation and is a function of both the

19-6
temperature and the composition of the steel. Because the nitride-grade steel contains less carbon than
the tool steel, itis expected to show more resistance to nucleation. Using a more intense solar beam and
elevating the surface to a higher temperature would produce a fully hardened localized region at the
surface.

B. Cladding of Preapplied Powders

It is sometimes desirable for the surface properties of a material to exhibit particular properties,
which may either be incompatible with desired bulk properties or cost-prohibitive to achieve throughout
the part. To overcome these problems, techniques such as plasma spray coating, laser melting of powders,
and shock cladding have been developed to apply desired coatings to a material surface. Although these
techniques can apply a powder or other fonils of material to a surface, it may be necessary to postprocess
these films to improve the adherence of films to the substrate, close or mitigate porosity, or cause solid-
state chemical reactions to take place in the film to form the desired phases. A solar furnace can be used
to melt powders onto substrates as well as postprocess films applied by other means.

Soviet scientists have already demonstrated that slip coatings can be melted onto substrates in a
solar furnace [25]. These coatings of fme powders have the advantage of strongly absorbing the solar
radiation, thus making the process more efficient The coatings were melted onto steel and titanium alloys
to produce coatings 50-150-m thick. The coatings had two general compositions, TiC-Ni-B and WC-Ni-B,
and were wear- -and corrosion-resistant A 2-m diameter SGU-5 solar furnace was used to expose the
samples at 600-1200 W/cml. _The coatings interacted with the substrate by diffusion, with most of the
volume of the substrate remaining unchanged. The coatings had satisfactory surface qualities, good
density, a framework structure, and good bond ·strength between the coating and substrate. The report
summarizing these fmdings was considered a proof-of-concept demonstration, and work at NREL was
conducted to corroborate and expand these concepts. We have experimented with a number of preplaced
powders using the solar furnaces at Sandia National Laboratories and NREL [26]. In the existing furnace
designs, the sample surface is perpendicular to the ground and therefore parallel to the forces of gravity.
This resulted in some difficulty in obtaining consistent melts, because the powders tend to falloff with
increasing temperature. We have recently installed a turning mirror at the NREL solar furnace, allowing
easier manipulation of the sample surface and improved control over the process.

Even given the difficulties associated with the older sample mounting system, we were able to
achieve excellent results. Using a technique in which powder Is impregnated with polymethylmethacrylate
(PMMA) by diffusing a solution of PMMA in methyl ethyl ketone (MEK) into the powder layer, we clad
a number of different alloy powder types onto 4340 and 1040 steel. Figure 4 is a set of micrographs
illustrating effective clads with a wide variety of alloy powders. These claddings were formed with a
range of exposure conditions, but we found that fluxes in the range of 100 W/cm1 produce very effective
coatings. These micrographs support the observation that the melted powders form excellent metallurgical
bonds with the substrate layer and that the clad material exhibits a high degree of densification. X-ray
diffraction studies have confirmed that the desired metallic and intermetallic compounds were either
preserved or formed in all cases.

The results from our studies and the Soviet experimentS suggest other applications. For example,
consider coatings for dissipating heat in high-temperature systems. Some example emissivity agents used
in thermal protection systems (IPS) are SiC, SiB4 and MoSi1• These materials efficiently radiate heat,
thus reducing the flow of heat into the substrate. Coatings of these materials have been applied in the '
metal and refractories industries and are now being used in the aerospace industry. Energy use has been
reduced by an average of 24%-38% for the refractories industry. Difficulties have been experienced in
applying the emissivity agents in TPS coatings to carbon-carbon materials, according to Fisher [27].

19-7
 Composites .are another class of materials in which good applications for solar processing exist.
Carbon-carbon materials are currently used as the heat shield for the space shuttle nose cap and wing
leading edges. Carbon-carbon materials are also contenders for various high-temperature parts of aircraft
turbine engines, such as exhaust nozzles in which high ·strength-to-weight ratios are important. Reducing
both the heat and the rate of oxidation of the carbon-carbon materials is extremely important. Silicon-
. based coatings are being explored because they produce SiC with good emissivity, as well as other silicon
compounds, like SiOz, that have good oxidative stability. For example, Smialek [28] reports that slurry
mixtures of aluminum and silicon powders in a nitrocellulose lacquer vehicle can be fused onto carbon
with some success. Fusion times of up to 2 h at temperatures in the range of 1300°C were used to
produce the fused coatings. Problems included aluminum vaporization, porous external surfaces on some
samples, and thin coatings on other samples because the coating infiltrated the pores (leaving a much
thinner than anticipated outer layer of < 25 JlIIl in thickness). Using SISlM to process coatings similar
to these might reduce process time, minimize vaporization, and increase the smoothness of the coating.
Similar coatings are being explored for use on an aero-assisted orbital transfer vehicle [29]. Concentrated
solar energy has been used to react layered Si3N4-C and BN-C systems to form SiC and B4C between the
layers [30], demonstrating that such SISlM techniques are possible.

C. Self-Propagating High-Temperature Synthesis (SHS)

An interesting observation related to powders might be added at this · point. It has been
demonstrated that some mixtures of powders will react with the release of energy. Once initiated, the
exothermic reaction becomes self-sustaining and will propagate through the reaction mixture. lhis is
called self-propagating high-temperature synthesis (SH~ .£31,32]. We have found that SHS can be
initiated in a solar furnace. Powders of AI and Ni have been mixed and bonded to substrates, and multiple
layers of vacuum-deposited thin fIlms have been placed on targets. Both types have been exposed to
thermal pulses in the solar furnace. When reacting, such powders and fIlms add their heats of reaction
to the solar beam, allowing temperatures to reach the melting point of refractory metals and ceramics.
High.;quality thin fIlms with very narrow heat-affected zones can be produced in this manner (Fig. 5).

Modem high-performance ceramics offer unique combinations of properties that make them
attractive materials [33-35]. Processing techniques are of utmost importance when high temperatures and
stresses are encountered Indeed, developing novel techniques for coating and joining ceramic composites
is listed as one of the future needs in the ceramic industry [36]. Fisher [27] recently reviewed applications
of ceramic coatings requiring retention of mechanical properties at high-temperature, tribological
properties, and corrosion resistance to high-temperature fluids. The use of SISlM to initiate and sustain
the SHS processes to produce these coatings is an intere~ng possibility.

D. Plasma and Flame Sprayed Coatings

Plasma- and flame-sprayed coatings are widely used throughout industry, and the techniques have
recently been reviewed [37]. A significant problem encountered by researchers using these techniques is
the porosity of the coating. 1bis porosity results in less than optimum corrosion resistance on many metal
components. Also, cracks are initiated and propagated along these voids, resulting in delamination and
failure. Laser-beam treatment of these coatings has been somewhat successful [38] but is known to
produce cracking [1]. A logical extension of the solar melting of powders previously described is to use
solar beams to remelt and density preapplied plasma- or flame-sprayed coatings. Preliminary work to
explore this possibility is under way.

19-8
E. Films Produced by Physical Vapor Deposition (PVD) Methods

. Various physical deposition methods can be used to produce layers of selected films on substrates.
Subsequent heating of these layers can result in the production of the desired coating either by solid-state
diffusion and reaction or by melting aI\d liquid diffusion and reaction. The process has been .used to
produce compound semiconductor films by direct synthesis from layers of the constituent elements
deposited on insulator substrates [39]. The stoichiometry of the initial layers cru:t be adjusted by the
composition, relative thickness of each layer, and number of layers of each composition deposited in the
original sample. Some example compounds prepared this ·way are AlSb, AlS, CdTe, CdSe. ZnTe, and
ZnSe. A tyPical energy source for this type of process is laser irradiation. The small size of the laser
beam results in the melting of small portions of the sample at a time. Although useful in producing
electronic devices, laser irradiation is more difficult to justify for large structural applications. For this
reason, a solar beam with large deliverable energy and a relatively wide spot diameter may prove to be
an effective alternative to a laser or other similar processing source. We have carried out preliminary
studies into intermetallic compound formation using various combinations of aluminum and nickel layers,
which form nickel aluminides with excellent high-temperature and corrosion-re~istant properties. The
initial set of diffusion bonding SHS reaction experiments were carried out in air, and samples were water
cooled on the back side of the sample surface. The various combinations of Ni and AI layers were
sputtered onto 4340 steel and pure iron targets using a magnetron sputtering unit The outer coatings were
aluminum, to increase oxidation resistance during the test. However, the high reflectance of aluminum
made energy transfer inefficient Applying carbon to the surface of some coatings reduced exposure times.
The reactions were followed by optical pyrometry and by visually monitoring the sample surface with a
remote video system. X-ray diffraction studies conducted after samples were exposed to the solar
radiation demonstrated conclusively that it was ·possible to form the desired intermetallic phases.

IV. CURRENT RESEARCH AND DEVELOPMENT

The electronics industry has qeveloped extremely sophisticated surface modification techniques,
and some of these are candidates for large-area applications. Techniques that are being examined for
SISTM applications include chemical vapor deposition (CVD) and its variations, rilpid thermal annealing
(RTA), and zone-melting recrystallization (ZMR). These surface modification techniques are not exclusive ·
to the electronic materials industry. For example, CVD is an exceedingly important method of creating
advanced materials and coatings. Applications of CVD are found in the fabrication of electronic
components, fiber-reinforced composites, corrosion-resistant coatings, and coatings in the tool industry.
A recent review examines the use of CVD in these and other applications [40].

A. Chemical Vapor Deposition

Broadly defined, CVD is the formation of solid products from the chemical reaction of gaseous
reactants on or near surfaces (see Chapters 12 and 13, this volume). It is important to note that all of
these reactions are initiated by heat and/or radiation. CVD reactor units can be classified as either hot-wall
or cold-wall systems. Hot-wall reactors are modifications of a typical furnace through which the reacting
gases pass. These reactors are commonly used but suffer from inefficiency because chemical reactions
take place on other heated surfaces in the reactor system (in addition to the sample). Cold-wall reactors
concentrate the reaction activation energy on or Close to the surface to be coated by using induction
heating or radiant energy from such sources as lasers and arc lamps. Solar furnaces fitted with CVD
reaction chambers are very good cold-wall reactor systems. The sun's radiant energy can be nicely
controlled to deliver prescribed amounts of heat for predetermined time periods. The systems are very
clean and energy efficient In addition to thermal activation from the solar beam, there is the possibility
of photolytic activation if the chemical systems contain an absorption band in the high energy portion of

19-9
the solar spectrum. The production of TIN, TIB 2, SiC, and hard carbon films using a solar furnace is
being explored at NREL. Based on a limited amount of work accomplished to date, relatively small solar
fluxes are required to produce CVD fllms. Films could be applied to large areas using this technique.

The solar furnace may also be used for rapid thermal chemical vapor deposition (RTCVD), a
process that normally uses radiant heating lamps in combination with a CVD chamber. These reactor
systems are capable of rapidly heating surfaces for short periods of time to deposit thin fllms. Such
RTCVD reactor systems are being developed in the electronics industry to produce high-quality films of
Si, SiC, and Si3N4 [41,42].

B. Rapid Thermal Annealing

Ion implantation techniques are desirable in the semiconductor industry because the quantity and
depth of carrier moieties can be precisely controlled (see Chapter 15, this volume). Traditionally, defects
produced by ion implantation have been annealed out in furnaces. Temperatures of 900°-1200°C are used
for silicon samples, and temperatures of 8000 -1000°C are used for GaAs samples. The annealing
temperature is uniform throughout the whole wafer because the sample is held at these temperatures for
15-30 min. Unfortunately, under these conditions, dopants can undergo extensive redistribution. This
makes it difficult to fabricate shallow junctions and small devices for very large scale integration (VLSI)
circuits. To reduce the annealing time, three different transient-annealing techniques have been introduced.
These techniques are pulsed laser or electron beam, scanned laser or electron beam, and . RTA with
incoherent light. For reasons outlined in an article by Fan [43], the RTA process is the most desirable
of the three. The RTA process uses radiative heat sources such as tungsten-halogen lamps and annealing <0.,

times of I-tO s. These conditions are remarkably similar to those found in the high-flux region of a solar
furnace. The application of SISTM to annealing ion-implanted surfaces may have advantages that are
unanticipated at this time. SISTM should even be applicable in the production of solar cells [44,45].

RTA work in progress at NREL is directed toward using the solar furnace to produce high-
temperature superconductor films on substrates such as SrTI03, Zr02, and MgO. The fllms are produced
by metalorganic deposition and are subsequently treated by an RTA process in a solar furnace to produce
the superconducting phase [46,47].

C. Metalorganic Deposition

Metalorganic deposition (MOD) technology is a rapidly growing alternative to CVD techniques

for forming certain types of thin films on solid substrates. Research at NREL has concentrated on high-
quality, high-critical-temperature (TJ superconducting films and metal films that can be grown on various
substrate materials using this technique. Optical coatings are another area of interest, but these have not
yet been studied in this laboratory. A key step in producing the highest-quality fIlms is RTA in a
controlled atmosphere. The ability to control the thermal pulse simultaneously with the atmosphere, and
thereby control the properties of the resulting fllms, offers the possibility of tailoring the films for specific
applications.

For the superconductors, MOD followed by an RTA in a SOlar furnace has two distinct advantages
over the more conventional approaches. The MOD technique produces fllms of great uniformity and high
critical current densities, because the precursors are mixed at the molecular level and are easily adjusted
to produce exact stoichiometry. Reacting the precursor material in an RTA process can orient the grains
with respect to the substrate and provides access to phases not available with nonnal thennal treatment
With a solar furnace, it is possible to scale up the area of rapid thennal processing to any practical size
by designing the optics of the furnace for that application. Furthermore, it will be possible to explore the

19-10
 effects of using optical fluxes that are up to two orders of magnitude larger than those obtainable with
commercial RTA equipment

. D. Joining

Certain geometries are difficult to join, because there is a mismatch in the coefficient of thermal
expansion of materials, because the particular structure of the pieces cause warpage upon heating and
cooling, or because there are heat-sensitive parts in the assembly. In some cases, these problems can be
overcome by using radiative heating to make the desired joint. The joint is made by applying heat just
in the region of interest by sweeping the beam along an appropriate seam. We are engaged in work that
addresses making joints in castable alloy figures of peculiar shapes and in ceramic pieces in which parts
of the assembly contain heat-sensitive components. Preliminary investigation indicates that the radiative
joining technique with the solar beam will work well for these applications.

V. FUTURE DIRECTIONS

Solar furnaces may have applications in a number of interesting areas of materials science and
surface processing. Relatively new and exciting topics include the production of nanophase materials, the
rapid thermal treatment of ceramics and composites, and cheiirlcal vapor infusion. Some other areas of
interest are described in the following sections.

A. Electronic Materials Growth and Processing

A vacuum system with a window and flow control for gases, combined with an intense solar beam
provides excellent control over process conditions. The beam allows fast thermal ramping of the target
in a cold-wall reactor, and the mass flow system provides the ability to rapidly change the process gases
over the target. Thus, RTCVD can be combined with diffusional steps or used by itself to grow
multilayered electronic materials. Where the desire is to grow large-area semiconductor materials, as in
photovoltaic panels, and where the energy costs are a substantial fraction of the overall processing costs,
there may be good reason to investigate the possibility of using solar technology to accomplish the film
growth. For certain applications, such as the growth of extremely low-defect single crystals in a .
microgravity environment, concentrated solar radiation may be the only energy resource that can be
used [48].

B. Zone-Melting Recrystallization

Graphite heaters [49] or lamps [50] have been used to scan across multilayered samples deposited
on substrates such as silicon, germanium, or sapphire. Heating an intervening layer, typically a fine-
grained silicon film, causes it to convert slowly to a recrystallized silicon fIlm at a scan rate of I mm/s.
1bis ZMR technique creates large-area films and may provide excellent substrates for the epitaxial growth
of GaAs [51]. The ZMR processes described may possibly be carried out using SISTM. These processes
represent interesting areas for further development.

C. Weather/Space

Effectively operating a solar furnace facility requires a good resource of direct normal radiation.
In the continental United States, a location within a five-state area (including Arizona, Colorado, Nevada,
New Mexico, and Utah) or in a portion of one of the bordering states is essential. The facility cannot
operate during the night or during periods of dense cloud cover. Consequently, a facility must be sized
to provide the required throughput during the available hours of operation, and the prudent use of labor

19-11
is mandatory. With these considerations as ground rules, it is possible to compare the cost of processing
with a solar furnace to the cost of processing with more conventional tools.

Systems studies were .performed to compare the performance of appropriately designed solar
furnaces for a generic materials processing task to that of the more conventional techniques using lasers
and arc lamps. These analyses indicate that for sites with good insolation and batch processing, the solar
furnace is extremely competitive [13]. In fact, moving to larger fluxes and larger total powers, the solar
furnace economics become progressively more favorable as larger fluxes and total powers are employed.
This is because capital equipment costs and power consumption become more important and labor costs
become less important as the size of the facility increases. Light is reflected once or twice during
concentration, giving losses of 5% to 10% at each reflection, but there are no energy conversion losses.
Other optical power supplies typically convert the heat obtained from the combustion of fossil fuels to
electricity and then must convert the electrical energy into light. The overall efficiency of using electricity
derived from fossil fuels is approximately 9% for high-pressure arc lamps and 4% for CO2 lasers.

As interesting as these arguments are for terrestrial applications of solar furnace technology, they
become even more compelling for space applications. FIrst, there is 70% more power density from radia-
tion in space than there is terrestrially because of the lack of atmospheric attenuation [52]. This figure
assumes 1367 W/cm2 mean direct normal radiation at earth orbit and air mass 0, versus 800 W/cm2 direct
normal availability at air mass 1.5 for the southwestern United States. Second, there are more UV
radiation and shorter wavelengths for any mission that requires photolysis. Additionally, direct
concentration of the solar resource is the most efficient way to apply large optical fluxes to a target. For
example, a I_m2 dish could deliver about 1 kW of optical power to a target. It would take at least an
additional 10 m2 of collector area to supply the electricity to operate an arc lamp, or an additional 25 m2
of collector area to supply the electricity to operate a CO2 laser. .In addition, there is the problem of waste
heat rejection. Certainly, some processes can be carried out without the need for radiant energy. In these
cases, it is probable that other energy sources would look attractive. In low earth orbit, where a satellite
is regularly in the shadow cone of the earth, or for a deep space probe, where there is a diminishing
amount of solar radiation to use, other energy sources are required Nevertheless, there are many missions
for which a solar concentrator would be worth serious consideration.

A number of significant applications exist for solar concentrator technology in space. These
include cleaning of the wake shield and fixtures in the materials science experimental and processing
areas, supplying energy for a number of materials processing tasks (requiring heat and light), fabricating
and repairing structures, mining and manufacturing on the moon, treating and recycling human and
operational waste materials, and generating electrical power. All of the direct applications are particularly
interesting because they use the energy delivered in the solar beam without intermediate conversion to
electricity. This implies improved efficiency, reliability, and economy. More detail about these ideas is
given elsewhere [53].

VI. CONCLUSIONS

Directed energy beam processing is an innovative and rapidly growing method for surface
modification. Ion beams, electron beams, and laser ' radiation each have their advantages and
disadvantages. Highly concentrated solar radiation is an additional option that has some features not easily
produced in the other energy beam sources; consequently, it is also being explored as a surface processing
too1. Because solar energy can rapidly deliver large amounts of heat to a surface, this heat can be used
to induce transformation hardening, surface alloying. and CVD. The suggested applications presented here
constitute examples of whole areas of SISTM that could be explored. Given the scope of the surface
processing field, we can expect that other applications will emerge. This article deals only with surface

19-12
processing technologies that seem to be a good fit to the solar resource. No mention is made of the areas
of basic research into the chemistry, physics, and metallurgy of materials in the high-temperature, high-
solar-flux environment Work in the surface chemistry of materials exposed to highly concentrated solar
energy reveals interesting processes that modify the surface composition of alloys [54-56] and implies
photolytic enhancement of surface reactions. These possibilities for SISTM are Just beginning to be
explored. We hope that the potential applications presented in this paper will stimulate additional ideas
and interest in the field.

ACKNOWLEDGMENT

We wish to acknowledge support from the U.S. Department of Energy under Contract No.
DE-AC02-83CHl0093. C. L. Fields wishes to acknowledge Associated Western Universities, Inc. (AWU)
for sabbatical leave support during which some of this review was accomplished.

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19-13
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19-14
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and T. E. Seidel, Eds., Rapid Thermal Annealing/Chemical Vapor Deposition and Integrated
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Interaction and Transient Thermal Processing/1984, Publishers Choice Book Mfg. Co., Mars, PA,
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K R. Padmanabhan, Appl. Phys.Lett, 51(5), 2152 (1987).

48. T. Overfelt, Director of the Center for the Space Processing of Engineering Materials, Vanderbilt
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49. 1. C. C. Fan, 1. Cryst. Growth, Q1 453 (1983).

50. A. Kamgar, G.A. Rozgonyi, and R. Koell, in 1. C. C. Fan and N. M. Johnson, Eds., Energy
Beam-Solid Interactions and Transient Processing, Elsevier North Holland, New York, NY, 1984,
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51. J. C. C. Fan, in Extended Abstracts of the 16th (1984 International) Conference on Solid State
Devices and Materials, Kobe, Japan, August 1984, p. 115.

19-15
52. C. J. Riordan, D. R. Myers, and R. L. Hulstrom, Spectral Solar Radiation Data Base Documentation,
Volume II, NREUTR-215-3513B, July 1989.

53. J. R. Pitts and T. Wendelin, in P. A. Nelson, W. W. Schertz, and R. H. TIn, Eds., Proceedings of
the 25th Intersociety Energy Conversion Engineering Conference, Reno, Nevada, August 12-17, 1990,
.1 American Institute of Chemical Engineers, New York, NY, 1990, p. 553 :
54. G. B. Smith, G. Zajac, and A. Ignatiev, Solar Energy, 29(4), 279 (1982).

55. A. Mesarwi and A. Ignatiev, Solar Energy Materials,.!1 353 (1984).

56. A. Mesarwi and A. Ignatlev, Surface Science, 166. 75 (1986).

19-16
 IIl411Ir.ii~iiiiiill1 (b) Primary concentrator

-_ (d)
Vacuum, ....... "
pump 6 '-'-,
\ \
\
\
\
\
Cooling \
pons I
I
I
I
I
I
I

)' ,/
; ;/'
Gasinle~ ....""
(a) XYZ Translation
table
... _-------_ ...."

.. Figure 1. High-flux solar furnace located on South Table MOUIitain, Golden, CO. (a) Heliostat,
(b) Primary concentrator, (c) Attenuator, (d) Shutter, and (e) Vacuum target assembly.

Laser energy systems

fd-Nd-Yag Nd-Yag
"\ \ Ruby
Q)
(.)
~
.0
0.6
-\
\
,, --AM1 solar spectrum
---Iron
······Copper
~

£ 0.5 . \
.0
.;..;. ·1
," 1200 _
-'§.
al

-g.
~
( .)
Q)
{).4

0.3
I
1000
C)I
800 E
al
E 600 ~
0 0 .2 Q)
z 400 g
.~
0.1
200 -g...
L-~~____~~~~__~__~-L-L__~O
...
0.6 1.0 2.0 4.0 8.0 10.0
Wavelength (pm)

Figure 2. Power density in the solar spectrum. Superimposed are the absorption spectra of Fe and Cu
and miscellaneous laser lines for comparison.

19-17
 600~------------------------------------------'

Hardness Transverse of Test 3 4340 Steel

500
Surface

I
Cl.
o
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If)
Q)
c
"E
en
I

300

200 0 200 300 400 500

Bottom Distance (.001 ") Top
of specimen of specimen

Figure 3. (a) Macrophotograph of solar hardened tool steel. Photograph of the steel plate after exposure
to the solar beam. (b) Microhardness data compiled on a hardened tool steel plate.

19-18
Figure 4a and 4b. Micrographs of various alloy powders melted onto steel substrates. Note the high
density of the melted powder and the good metallurgical bonding between the coating
and the substrates. (a) 761 (NilCrlB) powder onto 4340 steel. (b) 316 SS powder
onto 1040 steel.

19-19
Figure 4c and 4d. . Micrographs of various alloy powders melted onto steel substrates. Note the high
density of the melted powder and the good metallurgical bonding between the coating
and the substrates. (c) WC (6%) in Co onto 1040 steel. (d) Ni (95%) AI (5%)
onto 1040 steel.

19-20
Figure 5. NiAl thin film on Fe substrate. The film thickness is 1 Jll1l, and the zone affected by heat is
about 7 J.UI1.

19-21
 20. PANEL ON CORROSION PROTECTION

" W. Smyrl, University of Minnesota, Chairman

1. W. Halley, University of Minnesota
G. Hubler, Naval Research Laboratory
A. Hurd, Sandia National Laboratories
D. MacDonald, Pennsylvania State University
D. Snyder, General Motors Research Labo"ratories
J. Williams, Oak Ridge National Laboratory

1. INTRODUCTION

Corrosion and materials degradation in transportation systems are major costs to society. In a
1987 National Materials Advisory Board report (Agenda for Advancing Electrochemical Corrosion [1]),
it was estimated that the cost of corrosion of automobiles was $15 billion per year. The cost to all
transportation systems, including trains, aircraft, and ships, is consIderably higher, possibly as much as
$30-$60 billion per year. While exact numbers are difficult to pinpoint, it is reasonable to assume that
at least a third of this cost is avoidable through better design and engineering, appropriate education, and
the use of currently available corrosion control technology. Accordingly, the avoidable cost of corrosion
in the transportation sector of our economy alone might be as high as $10-$20 billion, which is more than
the gross national products of many countries in the world community..

While the cost of corrosion is spread more or less uniformly throughout our society, the cost to
transportation and, in particular, to road transportation systems, is of particular importance because of the
manner in which these systems pervade our society at all levels. For example, one in seven jobs in our
society is directly or indirectly related to motor vehicles; motor vehicles cost an average household $5,187
per year. An estimated 739,000 of these jobs are in the motor vehicle manufacturing sector alone, and
many times this number is in ancillary sectors.

While other sectors of the transportation industry are not as large, they are, nevertheless, important
to the health of our economy and to our fmancial and social well-being. Thus corrosion and materials
degradation in the air, rail, and ship transportation industries together represent a capital investment that
is a significant fraction of society's investmentin road transportation vehicles; in some cases (e.g., air
transportation), the corrosion-related failures can be catastrophic.

The goal of the "Corrosion Protection" working group was to review the current state of the art
of corrosion science and engineering and corrosion protection technology in the transportation and utility
industries, excluding nuclear, fossil, and hydroelectric power generation. Because the three excluded
technologies represent by far the major components in electricity generation, we have chosen to emphasize
the road transportation industry. As noted above, this industry represents a major activity in our society
and is often regarded as a barometer of the health of our economy. Furthermore, the road transportation
industry has a significant impact on everyone's daily life, and the damage caused by corrosion is evident
to all. What is not evident, however, is the enormous cost of corrosion or the manner in which corrosion '
affects the safety of our road transportation systems. The purpose of the material that follows is to review
the impact of corrosion on transportation and solar energy technologies with emphasis on road
transportation. The impact of corrosion on other sectors of our economy and on other technologies is dealt
with on a case-by-case basis elsewhere in this report.

20-1
 The remainder of this report addresses the needs and opportunities for improved corrosion
protection in transportation and solar utilities systems. The emphasis will be given to surface modification
and sUrface characterization because recent advances have provided a basis to propose that marked
advances will be realized in the near future by focused efforts in both. Many of the modification
techniques, such as overcoating with a metal or an organic layer or film, are highly developed and mature,
while other high energy deposition techniques are still being developed. The characterization efforts
support surface modification in two general ways: first, failure of films or coatings may be caused by
interfacial processes, either mechanical or chemical. Analysis of defects, both the scale and the type, and
analysis of surfaces help to identify the degradation processes; second, characterization of surfaces and
interfaces provides a foundation on which to base new or improved modification techniques. Because the
interface of a reactive metal or semiconductor oxide film is usually buried beneath tJ'te protective
overlayer, study of that interface presents special problems.

The survey of surface modification and characterization will be preceded by illustrative systems
that are near success and by a system in which long-range efforts are required. And finally, a list of
_specific recommendations will be given for future work in corrosion protection.

II. IMPACT OF CORROSION CONTROL BY SURFACE MODIFICATION AND

CHARACIERIZATION

The prevention of corrosion by surface processing enjoys significant economic leverage, and as
evidence, one may cite the widespread use of coatings, films, and inhibitors for metals and semiconductors
in many service environments. Corrosion control contributes to the vitality of existing and developing
technologies in automobiles and in solar energy systems. The successful implementation of existing
surface modification methods has greatly reduced the effects of corrosion in automobiles over the past
decade, in response to consumer demand. The application of available corrosion control methods has also
been effective in solar thermal and solar photovoltaic systems. Nevertheless, significant problems remain
because of the limitations of existing control techniques, or because increased lifetimes are desired.
Because incremental improvements in these and similar engineering systems will ensure their economic
viability, they are considered to be over the threshold establishing feasibility. Discussion of those areas
in which progress has been made calls attention to both the strength of present technologies and the need
for long-term corrosion research based on a systematic and comprehensive approach.

As expected, these successful corrosion control methodologies have focused on three main issues
of surface modification:

• Improved quality control to minimize defects

• Improved materials selection to reduce susceptibility
• Development of more advanced, tougher, and more durable coatings and films.

In addition, improved design can contribute to improved corrosion resistance.

In the following examples, the surface modification techniques discussed are metal overcoats,
which provide galvanic protection for automobile body panels, and polymeric encapsulants for solar
mirrors and photovoltaic systems. In both cases, the essential protection processes are known, i.e., "active"
galvanic protection of the iron substrate by a sacrificial zinc overcoat for automobiles and by a polymer
barrier layer to reduce the penetration rate of aggressive species from the environment into solar collection
devices. Even though the modifications are understood, and indeed they have been used effectively,
JIlodest improvements would have large economic benefits. Thus, improved materials, improved' surface
processing, and improved understanding of the corrosion systems are needed.

20-2
A. Corrosion in Road Transportation Systems

Automobiles are complex systems composed of structural components, a power plant, a drive train,
electronic controls, and features for passenger comfort. Failure mechanisms in automobiles include
corrosion, wear, fatigue, and combinations of all these processes. When new mater!als are introduced, the
failure mechanisms change as well. At present, for example, lighter, stronger materials are entering
vehicle design to reduce weight and thus to improve fuel economy. As U.S. automobile manufacturers
use more of these lightweight materials, the basis for understanding those factors that determine durability
and those that lead to failure must be improved.

Today's vehicle is based on steel, with significant fractions of aluminum alloys, magnesium alloys,
and polymers. Structural and body panel materials must resist road damage and corrosion from salt and
acid rain. These components are now protected with sacrificial coatings, with conversion coatings, and
by paint. Material for the fluid control and power train components must withstand wear and corrosion
when in contact with coolant, refrigerant, fuel, oil, and transmission fluid. Couplings of different materials
must be managed carefully to avoid galvanic couples, which induce corrosion.

American automotive manufacturers have introduced zinc-coated steel throughout the vehicle as
the major protection system against salt-induced corrosion. The material is roll-coated by the steel.
manufacturer, using either hot-dip or electrodeposition processes. At present, American manufacturers use
pure zinc coatings for the outer body panels, but advanced hot-dip coatings are now being accepted. Zinc-
based coatings are sacrificial ·to the body steel and prevent iron corrosion when the paint layers are
damaged. Japanese and European manufacturers also use zinc or zinc alloy coatings. The Japanese have
established a leadership position by developing a large number of binary alloys at the production scale.
Two factors are presently driving a search for replacement sacrificial coatings:

(1) Zinc is highly active electrochemically and corrodes without coupling. Alloying is considered a route
to longer-lived coatings by reducing the self-corrosion of zinc, thus extending the life of zinc. A
second goal may be to reduce the zinc-iron galvanic current to the minimum required for acceptable
protection of the iron. It is desirable to estimate the size of an iron surface (exposed, for example,
through a hole in the protective overplate) that may be cathodically protected by the nearby zinc or
zinc alloy.

(2) Pure zinc coatings weld poorly, cause paint adhesion problems, and powder or gall in stamping dies.
Selected alloy coatings have fewer manufacturing problems and are ~heaper t<l process, but it has yet
to be established that the alloys have adequate corrosion resistance.

A recent paper has noted the need for scientific understanding of the interaction of such alloys with saline
corrosive environments to improve the selection of materials and the design of superior coatings [2].

A new set of needs is also emerging as automotive manufacturers move to reduce weight by
substituting polymers and light metals for steel and by moving to lower-mass designs. Both aluminum
and magnesium alloys are completely recyclable, and there are processes under development that could
reduce the production cost of magnesium, in particular. Aluminum alloys are already used
extensively-for wheels, trim, air conditioners, and drive train components-and magnesium alloys are
growing in acceptance. For the present applications, corrosion is manageable by anodizing or conversion-
coating the metals and striving to remove galvanic couples in the vehicle. However, as the light metals
become used more in functional parts of the vehicle-notably in the drive train-and as the thickness of
the alloy drops for weight reduction, the need for robust corrosion prevention grows. Technical issues
include (1) understanding and tailoring the aluminum (and magnesium) passive layer for alloys,

20-3
(2) identifying factors, that control the corrosion of light metal alloys, and (3) using accelerated tests to
assess the corrosion rate of light metals in automotive applications.

Vehicles are manufactured by a series of forming, joining, and coating operations. After assembly,
vehicle bodie~ are frrst coated with a chemical phosphate conversion layer that improves final corrosion
resistance and anchors the paint. Industrial phosphate conversion coatings are based on the reaction of
the metal substrate with phosphate anions to facilitate the precipitation of phosphate crystals [3]. The
reaction is heterogeneous with distributed anodic and cathodic areas. As soon as 95%-99% of the surface
is covered with phosphate, the active deposition of phosphate stops, and portions of the metal surface
remain uncoated. Those parts of the surface that are not coated will be unprotected and also may not bond
well with the overcoats. Chromates and inhibitors have been used to provide temporary protection to the
uncoated areas. It is desirable to have a process that will provide complete coverage. After phosphate
treatment, bodies are electrophoretically painted in an immersion tank. After the primer step, the coating
is completed with spray-on color and protective layers. Aluminum components, such as air conditioners
and wheels, are either anodized and painted or conversion-coated to resist corrosion.

A quantitative assessment of the quality of manUfacturing processes and the evolution of corrosion
damage requires the use of monitors that are sensitive and accurate and provide an output that can be
related to a component dimension and the geometry of the damage (e.g., general attack versus pitting).
Monitors are also required to assess the quality of painting, formation of phosphate conversion coatings,
and electrophoretic deposition of primers. The monitors should operate in "real time," so that the output
is available as the manufacturing process proceeds. The development of effective monitors for quality
assurance is a critical issue in any highly competitive manufacturing activity (such as the automobile
industry), in which economy of scale depends on uninterrupted throughput.

An area of particular concern in the automobile industry is the development of quality assurance
monitors for the phosphate conversion and electrophoretic coatings. Because researchers desire to monitor
in "real time" and to have minimal impact on the manufacturing activity, the desired monitors should be
remote and hence should use optical or electrical techniques where possible. The optical monitors may
use absorption, scattering, or fluorescence phenomena at Closely specified excitation frequencies employing
tunable lasers and narrow band sensors. Neural networks and expert systems might be employed to
provide a diagnostic capability, so that the manufacturing and processing parameters may be closely
controlled for optimal performance.

Because of the extremes in pressure (force) and temperature experienced by components in modem
high-performance engines and drive trains, a need exists to develop reliable sensors for corrosion and
wear. Examples of such sensors include monitors for coolant corrosion and corrosivity, engine wear, oil
lubricity, transmission fluid viability, etc. The outputs of such sensors would provide data to a central,
on-board computer that in turn would provide continuous diagnostics of the mechanical and tribometric
state of the engine and drive train, so that the vehicle may be operated in the most efficient manner
possible.

An on-line sensor for engine wear and corrosion is a short-term possibility, because crude sensors
of this type already exist in the aircraft industry. This sensor would provide "real-time" measurements
of wear and corrosion of critical engine and drive train components and might become the basis for
scheduling the maintenance and replacement of these components. Because of the high sensitivity of
radioactive isotope detection, radionuc1ear techniques would seem to be promising.

20-4
 Sensors are also required to monitor corrosion inhibitor levels and oil breakdown products in high-
performance engines and drive trains. Again, "real-time" monitoring and diagnosis are desired, with both
an output and memory that are available for system servicing. .
Sensors for coolant viability appear to be a relatively near-term possibility. These sensors might
monitor pH and the buildup of degradation products, with particular emphasis on adjusting coolant flow
for optimum engine performance. Because the generation of acidic breakdown products is of major
concern, the pH might be a parameter of great importance.

Finally, with regards to the emerging needs for improved corrosion protection, it should be noted
that there is renewed worldwide interest in the electric vehicle (EV). This interest has kindled active
development of batteries and fuel cells that are capable of high energy" and power densities and that exhibit
long cycle lives. In these power plants, the energy is stored and delivered by electrochemical reactions.
Corrosion is a principal cause for EV power plant degradation, and the mechanism of corrosion in these
systems is often electrochemical. The first EVs most likely will be powered by advanced lead-acid
batteries, which have high power densities, moderate energy densities, and long cycle life. The positive
grid is a nonequilibrium system, and progressive grid oxidation decreases capacity. Conductive diluents,
such as carbon, for the active lead dioxide improve life, but they commonly oxidize too rapidly to be
practical. Corrosion of the metal negative grid is an undesirable corrosion reaction that also reduces
battery life. Metal hydride batteries-typically including the nickeVnickel oxide positive-are a strong
contender for the second-generation EV battery. Corrosion of the hydride-forming e1ectrode material is
a problem, because the formation of any oxide passivates the system and reduces performance. The nickel
positive electrode requires a nonpassivating grid surface, crucial when the lower-cost nonsiiltered
construction is used. Cost-effective surface modification routes to a nonpassivating nickel electrode could
increase the nickel-IJletal hydride battery performance to a level matching EV requirements. In the
elevated temperature sodium-sulfur battery, a major problem has been to maintain a seal between the beta-
alumina separator and the reactants, sodium and sulfur. Corrosion in the lithium solid polymer electrolyte
battery and in polymer electrolyte fuel cells has a ' significant impact on performance, because the
electrolyte is immobilized, and corrosion products formed at an electrode-polymer interface are not easily
removed or circumvented. Lithium solid polymer electrolyte batteries are among the most promising EV
power sources over the long term.

Mechanisms by which electrochemical energy conversion systems degrade are complex and take
place on a small scale, typically occurring at interfaces. The combination of powerful, sophisticated
vacuum spectroscopies with microscopy techniques used in corrosion science can identify these
mechanisms from the reaction products and, thereby, lead to appropriate alternative material combinations.
Electrochemical impedance analysis has the ability to pr()be a battery or fuel cell during operation to
follow degradation processes as they occur. Finally, the current/potential models of corrosion science are
directly applicable for identifying system instabilities and for guiding battery/fuel cell designers in
minimizing harmful reactions.

B. Solar Energy Systems

A capacity of over 50 MW of a photovoltaic (PV) electric power has been installed in the United
States. The lifetime of the PV modules appears to be on the order of 10-15 years. For solar PV power
to be economically viable, the power packages must have a useful life of 30 years. Likewise for solar PV
concentrator power packages, and for solar thermal heat and power generation, the lifetime of the parabolic
mirrors is a critical limiting factor in the longevity and reliability of the power system. Second-surface
mirrors are used so that the surface can be periodically cleaned. 'The most common mirror consists of

20-5
glass!AgiCu/paint and polymethyJmethacrylate (PMMA)/Agladhesive/AI. The latter is more desirable,
because it is flexible all:d much lighter in weight and hence requires a less massive support structure.

A requirement of both mirrors and solar cells is that they be fabricated from inexpensive materials,
because future markets indicate that many square miles of solar cell arrays will be manufactured, and the
cost/kWh must be kept as low as possible to compete with fossil fuels and nuclear power. For this reason,
the lightweight mirror mentioned above has an inexpensive PMMA protective coating over the Ag. Over
a period of time, the PMMA either reacts with the Ag, or impurities and H20 penetrate the PMMA and
cause the Ag to turn black and to roughen. The exact degradation mechanism is not known. The
corrosion problem limits the lifetime of these inexpensive mirrors.

Flat-plate photovoltaic modules are distinguished by the photon absorber, such as single-crystal
silicon (c-Si), polycrystalline silicon (p-Si), amorphous Si (a-Si) , copper-indium-diselenide (CIS), or
cadmium-telluride (CdTe). The solar conversion efficiencies are approximately 14% for c-Si, 12% for p-
Si, and less than 10% for a-Si, CIS, and CdTe. Most flat-plate modules have Ag or AI contact grids or
fIlms that need corrosion protection from moisture. The lifetime needs to be 20-30 years. For
photovoltaics to be cost-effective for terrestrial applications, low-cost pottants are needed over areas up
to 2 m2 • The terrestrial and space-qualified c,:,Si modules are similar in design. However, in order to
reduce the cost, lower cost materials have been substituted in the terrestrial modules. The module
structure is glass (substituted for fused quartz)/ethylene-vinyl-acetate pottant (substituted for silicones)/Ag
or AI contacts (substituted for PdfAg)/Si cell. The problem with this cell is ultraviolet (UV) degradation
of the pottant and subsequent reaction with the contact materials by the degradation products; this limits
the useful lifetime of the photo voltaic modules. · . .

Electrochromic materials have optical absorption properties that may be changed on demand by
an externally applied potential. Many of the materials respond to insertion or intercalation of ions from
a contiguous electrolyte, and on release of the inserted species, the optical properties are switched back
to those of the starting material. The basic phenomena can be used for a variety of technologically
important solar applications, such as light modulation or reflectance. The reversibility of the switching
process is essential, and the stability of the electrochromic character has emerged as a key factor that limits
the use of the present systems. Many of the promising materials are transition metal oxides that are hosts
for cation (e.g., H+, Li+) guest species. "Smart windows" for homes or offices and "smart mirrors" for
automobiles have been demonstrated and installed in consumer products on a limited basis. The general
outlines of the process are reasonably well understood, and further work to enhance the cycle life of the
materials will support a more widespread use. A recent symposium has described the progress in research
on the materials and their use in a variety of electrochromic devices [4].

III. SURFACE MODIFICATION 1ECHNIQUES

The improvement of corrosion resistance of metals by modification of the surface has been
practiced since the invention of metal tools. AIl engineering metals used in today's technological societies
are unstable with respect to corrosion, which causes the loss of properties. Natural oxide films provide
protection against continued attack for some metals, and alloying extends the life of other metals by
developing highly stable passive films. Metals may not always be protected by oxide films, and other
modification methods have been developed. Some of the earliest techniques to prevent corrosion involved
coating with greases or natural oils. More modem methods developed in the 19th and 20th centuries
include multiple coatings (the most common of which are paints and polymer films), Zn galvanizing
(sacrificial coatings), electro- and electroless plating of other pure metals, and vacuum physical vapor
deposition of mostly pure metal coatings by electron beam, and radio frequency (RF) and direct current
(DC) magnetron sputtering. The metal coatings are better barriers than the organic films because of the

20-6
lower permeability of the former to moisture and oxygen. Inhibitors or conversion coatings as primers
for paints are also used by paint manufacturers, and they remain, even today, highly proprietary in nature.

The use of organic coatings to protect metal surfaces is widely practiced. Much of the use is for
atmospheric exposure of vehicles as well as for structural units such as bridges and buildings. The
technology of such coatings has advanced significantly in the past few decades. Automobile coating
systems have been developed that, under favorable conditions, last the lifetime of the vehicle. However,
coating technologists and coating scientists acknowledge that much is unknown and that new processes
and understanding are the keys for further progress [3], Defects in the metal substrate and in the
overlayers are among the primary concerns, because they are the source of localized corrosion phenomena.
Defects may occur on length scales from atomic level lattice vacancies to arrays of defects at grain
boundaries (for crystalline materials), or to random pores or cracks (for example in noncrystalline films).
Avoiding such defects by proper quality control is a major concern in coatings science and technology.

In the past 15-20 years, an explosion of interest in surface modification techniques has mostly
involved depositing thin films, applying coatings, and forming surface alloys. The development of many
of the techniques has been driven by" the need for the semiconductor electronics industry to create
improved processing procedures. As a spin-off of the advancing technology, other fields, such as
corrosion protection, can benefit from the new processes.

. It is not the purpose here to explain each of the new processes in detail, but some familiarity with
them will be assumed. As an aid to further discussion in this section, however, Tables I and 2 are
provided as a compilation of surface" modification techniques. The list is not all-inClusive, but is intended
chiefly to highlight advanced methods that may have application to corrosion protection. The techniques
of surface modification are divided into three broad categories:

• Low energy inorganic coating techniques~ For the most part, these are mature technologies that have
been used for many years. Table 1 summarizes factors pertaining to the use of these techniques.

• Techniques involving the use of energetic ions. These techniques have largely appeared within the
last to-IS years; several have neither reached maturity nor found use for corrosion protection. Higher
densities and better adhesion of the coatings are among the commonly accepted advantages of these
techniques. Table 2 summarizes the relative features of the energetic techniques.

• Polymer coatings include traditional paints, thermoplastics, polyvinylchlorides, epoxies, urethanes, and
polymethylmethacrylate.

Because many of the techniques for corrosion protection in the automobile industry must be low
cost and scaled up to large areas and high volume, only those techniques in the tables that are designated
as low cost and highly scalable are viable, although future advances in the other techniques could place
them in a viable category. In addition, most techniques that involve vacuum processing are too costly for
automotive applications. For solar energy problems, vacuum deposition is already used in processing steps
so that many of the vacuum deposition techniques may be applied without cost penalties.

A. High Energy Surface Modifications

High energy surface modification processes currently find their widest use in the electronics
industry. Ion implantation, for example, is used in all economically advanced countries for controlled
doping of components of integrated circuits. In part because of this success, research is now directed
toward surface modification for other purposes, including corrosion protection to preserve the useful

20-7
 Table 1. Low Energy Inorganic Coating Techniques

Thickness Throwing Areal Environmental

# Technique Ref Cost (microns) Power Scalability ' Wet/Dry Impact
1 Oxide passivation Low 1 Yes Yes Wet High
2 Electroplating (i) Low 1 to 10 No Yes Wet High
3 Electroless metallizing (i) Low 1 to 5 Yes Yes Wet High
. 4 Galvanizing Low 1 to 10 Yes Yes Wet Low
5 Conversion coatings (silicates, phosphates) Low 1 Yes Yes Wet Low
6 Physical vapor deposition (PVD) (ii) Low 1 to 20 No Yes Dry Low
7 Chemical vapor deposition (CVD) (ii) Med 1 to 10 Yes Yes Dry Low
8 Laser assisted CVD (LACVD) Med 1 to 10 Yes Yes Dry Low
9 Sol-gel (iii) Low Yes Yes Wet Med
10 Plasma spraying Med +400 No Yes Dry High
(i) See Chapter 10, this volume
(ii) See Chapters 12 and 13, this volume
(iii) See Chapter 14, this volume.
 Table 2. Coatings Techniques Involving Energetic Ions
(All are performed in vacuum and provide for low substrate temperature.)

Approx. lllickness Thowing Dry/ Areal Comments, Special

# Technique Ref Energy/Atom Cost (Microns) Power Vacuum Scalability Suitabilities
1 Sputtering (magnetron) A 10 eV Med 1 to 20 Yes Yes High In wide use
Ion beam sputtering 10 eV No Med Excellent control
Biased sputtering 100 eV Yes Med Highest energy
2 Pulsed laser deposition B 10 eV Med 1 to 10 No Yes Low Epitaxy .. complex
(PLD) materials
3 Plasma assisted CVD G lOeV Med 1 to 25 Yes Yes High Wear/corrosion
(PACVD) coatings
4 Ion plating A 10 eV-lOO eV Med 1 to 10 Yes Yes Med Wear/corrosion
coatings
5 Ion cluster beam (ICB) C 10 eV-lOO eV Med 0.1 to 6 Yes Yes Med Mirrors, epitaxy,
controllability of
energy, no co-ions
6 Ion beam deposition D 10 eV-lOO eV High 0.1 to 1 No Yes Low Epitaxy, DLe
(IBD) compound
semiconductors
7 Ion beam CVD (IBCVD) G 100 eV-l keY Med 1 to 100 No Yes . High DLC, new
technology
8 Ion beam assisted E 100 eV-20 keY Med 1 to 20 No Yes Med ControVgraded
deposition (IBAD) composition!
microstructure
9 Ion implantation F 100 keV-400 keY Medl 0.1 to 1.0 No Yes Med High flexibility
high for all types of
substrates
 Table 2. Coatings Techniques Involving Energetic Ions (Concluded)

References

A. D. M. Mattox, J. Vac. Sci. Technol., A7(3), 1105 (1989); D. M. Mattox, Electrochem. Tech., b 295 (1964).

B. J. T. Cheung and H. Sankur, CRC Critical Reviews in Solid State and Materials Science,ll. 63 (1988); MRS Bull., 17(2), 1992.

C. I. Yamada, Appl. Surf. Sci., ~ 23 (1989).

D. T. E. Haynes, R. A. Zuhr, and S. J. Pennycook, Mat. Res. Soc. Symp., 144,311 (1989); L. Wu, Mat. Res. Soc. Symp. Proc., 152.13 (1989);
M. Mirtich and D. Swec, Thin Sol. Films, 131, 245 (1985).

E. G. K. Hubler, Mat. Sci. Eng., A115. 181 (1989); this volume, Chapter 16.

F. G. Dearnaley, 1. H. Freeman, R. S. Nelson, and J. Stephen, Ion Implantation, North-Holland, London, United Kingdom, 1973.

G. R. E. Clausing, L. L. Horton, in J. Angus, and P. Koidal, Eds., Diamond and Diamond-Like Films and Coatings, NATO-AST Series B, Physics,
266. Plenum, London, United Kingdom, 1988.
properties of substrate materials. Research and applications in the area of wear resistant and corrosion
resistant coatings for metals by means of several of the energetic deposition techniques listed in Table 2
are just beginning. Others are quite mature.

Because films deposited using energetic deposition techniques are dense, ~gh1y adherent, have
few pin-holes, and can be laid down at extremely low temperatures, they are attractive for corrosion
protection applications. It could be said that with the results of research already conducted, that corrosion
problems involving planar and cylindrical geometries can already be solved using dry energetic deposition
techniques. The problem then reduces to which technique to use, and how one can reduce the cost by
scale-up of processing. Ion beam assisted deposition and ion implantation have the best adhesion
properties, while RF sputtering has the best throwing power, so which one to use will probably be decided
by the specific application.

From the historical standpoint, many of the techniques identified in Table 2 have some connection
either to the ion plating technique invented by Mattox [5] or to the high energy ion beam irilplantation
technique [6]. The latter technique came into wide use in the 1970s for the carefully controlled
introduction of dopants into elements of integrated circuits. The ready availability of processing
equipment anp the general scope of the enterprise helped stimulate research into the use of high energy
ion beams for surface engineering of all types, including corrosion, wear, optical, and conducting
properties. The advantages of high energy processing soon became apparent. Direct implantation has the
disadvantage of rather low throwing power, however. Therefore hybridization of beam techniques with
other deposition processes to achieve high energy depo~ition together with more mass deposition has
occurred. Meanwhile, for the plasma techniques,·microwave plasma generation and RF plasma generation
have come into wider use.

As has been pointed out [7], three important factors affecting the performance of films and
coatings are porosity, adhesion, and stress. Direct high energy ion implantation may have some
advantages in all three categories for pure corrosion protection. This assumes that the surface alloy
formed by ion implantation itself has suitable corrosion resistance and that externally applied mechanical
stresses associated with the application are not severe enough to damage the thin treated surface.
Although there are compressive stresses in ion implanted surfaces due to added atoms, delamination by
buckling is practically unknown. It might seem that effective porosity (weakness in the treated layer)
could exist due to shadowing of the surface from the beam by contaminating particles. Thus far this
problem does not appear to have been identified, but the exact reason is not known. Porosity remains
something of an issue for pure corrosion protection by the other techniques as well [7]. A possible
attractive application for direct ion implantation is in the area of fretting corrosion, in which even
energetically deposited coatings might fracture and spall due to the repeated vibratory impacts.

With the exception of ion implantation, only a few studies on corrosion have been done on films
deposited using energetic deposition methods. The early results look promising. Wolf [8] has studied ion
beam assisted deposition (IBAD) Pt, TiC, TiN, B, DLC, CrN, BN, CrZ0 3• and Si on metals with good
success, and others have studied AI, Ta, and W on carbon steel. Carbon steel is cheap and workable, and
IBAD films have good adhesion and high corrosion resistance. Thus, even though the process may be
expensive, use of inexpensive substrate materials can obviate some of the processing cost.

Ceramic compound films such as AlZ0 3 and. Si3N4 and TiN also offer excellent corrosion
resistance. Takahashi in Japan has set up a processing line which coats steel sheet continuously with AI,
TiN or Alz03 [9]. His system provides for sputter cleaning, evaporative coating or CVD coating in series
in one vacuum process line. Part of the success of IBAD films is that they are adherent and more ductile

20-11
than bulk materials due to the microcrystalline or amorphous structures. Therefore, they can yield along
with the metal sheet so that some working of the metal is possible after application of the coating.

Many of the applications described above require large areas to be coated. Ion guns more than
60-cm long are ~urrent1y available, and at least one laboratory has a system that can handle I-m-diameter
workplaces. In nonopticaI applications, in which uniformity of the film is not a strict requirement, very
large areas could be coated with present equipment by routine manipulation of the workplaces.

Still higher surface areas are possible by the means of continuous coating of rolls inside vacuum
as mentioned above. The primary obstacle for scale-up is the requirement of line-of-sight processing,
especially for odd-shaped parts. Cylinders can easily be coated, but it is not yet clear whether shapes like
gear teeth can be reliably coated.

Electrodeposition is very inexpensive but may be phased out where there is a severe environmental
impact of waste products associated with the process. Dry processing with techniques such as physical
vapor deposition (PVD) are inexpensive but suffer from poor adhesion and low-density films. Chemical
vapor deposition (CVD) films are very attractive when the pieces to be coated can be heated to high
temperature, and this process will probably always win against energetic processes. However, adhesion
is often a problem with the CVD technique. When the substrate requires a low deposition temperature,
when perfect adhesion and no pin-holes are required (as it is when a material of low thermodynamic
stability is to be coated), then energetic depositio!l methods are a viable choice.

Costs are difficult to determine because only the work by Takahashi [9] has attempted to scale-up
these processes to large area sheets. A useful comparison is the cost of magnetic tape or coatings for Lo E
windows, which are both made by PVD or sputtering techniques. Energetic deposition processes will be
somewhat more expensive than the other processes for coatings of magnetic tape or windows. The cost
should be in the area of $1-$15/ff.

B. Protective Layers of Zinc

Zinc coating is a surface modification technique that has a substantial history, several aspects of
which have created renewed interest In the last 5 or 6 years, essentially all steel components of vehicles
sold in the United States have been zinc coated. The improvements in corrosion protection have been
dramatic, but the costs have also been substantial (- $1 billion/year). The principle of galvanic protection
with sacrificial zinc coatings is well established, because it has been discussed in textbooks [10-13] and
in the specialist literature. Galvanic interactions have also received attention from mathematical modeling
[14-18] including situations that simulate atmospheric exposure [19,20]. A more complete understanding
of the role of alloying, microstructure and microcomposition, phosphate plating, and electrophoretic
primers and paints in corrosion protection would permit improved design of the zinc layer with significant
cost savings.

C. Surface Modification by Sol-Gel Films

A general discussion of sol-gel fIlm technology is given in Chapter 14 of this volume. Broadly
speaking, a sol-gel film is a coating or free-standing film that is formed from a sol through continuous
stages of increasing concentration of a solid precursor. Typically, the sol is a solution of polymeric
species or a suspension of "oligomers" including. possibly, particles in the colloidal size range. During
deposition through states of increasing solids concentration, this sol might gel. as in bulk sol-gel
processing; however, the gel state is often a fleeting transient that quickly empties of liquid. Nevertheless.

20-12
the structures formed during this stage, with varying amounts of porosity, influence the structure of the-
final film. .

Sol-gel processing offers high compositional and homogeneity control at low temperatures. In
comparison with vacuum and CvD techniques, sol-gel coating is not equipment-intensive or directional.
Complex shapes of arbitrary size can be coated with reasonably good uniformity. Single-coat thicknesses
depend strongly on sol concentration and fabrication technique; for dip and spin coating, 200 nm is a
typicai (but not unsurpassable) upper limit, and 5 nm is a typical lower limit. Multiple coats are feasible,
generally requiring thermal treatment between coats in the absence of well-matched thermal expansion
coefficients. The cost of high-purity liquid prec\lfSors can be high, but in thin-film applications, the
materials cost would normally be negligible.

Commercial sols are available for protective coatings that offer both corrosion and abrasion
resistance. "c Resin" from Dow Corning Corporation is a sol-gel that contains fumed silica particles for
strength and wear resistance. A similar siloxane-based product, "H Resin," is available for corrosion
protection of microcircuitry [21]; it has the distinct sol-gel advantage oflow-temperature.(down to 175°C)
application. Tests have demonstrated its effectiveness in preventing salt-water attack.

D. Nonchromate Alternatives to Alodine Conversion Coatings

Most schemes for the corrosion· protection of aluminum are based on highly toxic hexavalent
chromium; "alodine" is a proprietary chromate-based conversion co~ting used widely in the aircraft
industry. Applied by dipping or spraying, alodine imparts superior corrosion resistance to aluminum with .
an added bonus: scratches heal themselves. Apparently the migration of chromium into scratches inhibits
corrosion. In addition, for some applications, the relatively high conductivity of alodine can be exploited
(e.g., the RF shielding effectiveness of aluminum casings).

Unfortunately, chromate is toxic, and it may be eliminated by future mandate. Therefore,

alternatives to chromate conversion coatings are in high demand, as are protective coatings for all light
metals in general. Although polymeric coatings are under study, the ideal replacement must resist UV
degradation to satisfy aircraft requirements.

IV. SURFACE CHARAClERIZATION lECHNIQUES

Surface characterization techniques have been used for corrosion studies over wide length scales
from the detection of damaging surface species (like chloride or sulfur) to the location of defects in
protective films. The use of such methods has become more sophisticated as their·capabilities have been
enhanced, especially their sensitivity to surface and near-surface regions of reactive metals and
semiconductors. For the purposes of the discussion here, these methods may be categorized as either ~
situ, meaning characterization of the surface in vacuum or out of the working environment, or in situ when
referring to analysis in the environment. In the latter category, we include techniques that can be used
to interrogate "buried" interfaces below protective fIlms that remain in place. The shift in emphasis to in
situ techniques has been based on recent advances, and we anticipate that this will accelerate in the future.

Monitors or sensors that operate on devices in use, in factories, on operating solar devices, or on
working vehicles form a third category of engineering characterization technology relevant to corrosion
science. Many of these monitors are based on in situ surface characterization techniques.

Practically all of the vacuum ex situ techniques have been reviewed in Chapter 1 of this volume.
They include Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), secondary ion

20-13
scattering spectroscopy (SIMS) secondary neutral mass spectrometry (SNMS), ion scattering spectroscopy
(ISS) and Rutherford back scattering spectroscopy (RBS). Many of these are useful for characterization
of passivation layers and other interfaces subject to corrosion.

Particularly for systems subject to aqueous corrosion (of primary interest here), the ex situ
techniques have the disadvantages that removal of the sample into vacuum may have uncontrolled effects
on the surface and that the corrosion processes cannot be monitored in real time. In situ techniques avoid
these problems. Recent developments include environmental scanning electron microscopy in which
electron microscopic images are obtained in ambient pressures up to 10 Torr of arbitrary gases, including
highly reactive species such as HCI, H20, and S02' We will discuss the in situ techniques in some detail
because they are especially promising for new corrosion studies.

A. Tunneling and Atomic Force Microscopy

A tremendous advantage of these methods is that they permit angstrom-scale images in aqueous
environments. A disadvantage is that, until recently, it has been impossible to distinguish one atomic
species from another in the images; this distinction may soon become possible through the use of a
scanning tunneling spectroscopy (STS), in which the conductance of the interface is studied as a function
of tip position.

. If a relation can be established between the local density of states and the species over which the
tip is suspended, then the needed identificatio~ can be made. Theoretical calculation of the local density
of states as well as a better theoretical characterization of the tunneling process itself have a role to play
in putting this advance on firm ground. Recent papers by Chidsey [22] and by Snyder and White [23]
have discussed recent progress on studies of reactive surfaces.

B. Grazing Incidence X-ray Diffraction

X-ray probes are the primary direct tool for structural analysis of materials, including oxides.
Until recently, only indirect structural probes were used to study anodic oxide films whereby the structure
was inferred on the basis of some physical property such as capacitance, photo electrochemistry, or
spectroscopy. Very few direct structural measurements were reported, and these were dominated by
electron scattering. This limitation has been overcome through the use of grazing-incidence X-ray
scattering using synchrotron light sources. A recent review of surface X-ray studies summarizes the recent
progress at electrochemical interfaces [24]. By variation of the angle of incidence, one can probe, in turn,
the upper interface, the bulk, and the buried lower interface of a thin film. The technique is sensitive to
monolayers. The first application of this technique to an anodic film of Ti02 was reported recently
[25,26]. Studies have begun to appear for other systems as well [25].

C. Extended X-ray Fine Structure Spectroscopy (EXAFS)

Although not an inherently surface-sensitive technique, EXAFS can be useful for surface studies
if the interface is labeled with a species not present in the solution or the substrate metal. Surface studies
with EXAFS and surface extended X-ray fine structure spectroscopy (SEXAFS) have been reviewed in
Chapter 7 of this volume. This labeling can be done by underpotential deposition as in the work of
Melroy et al. (see [24] and references therein). The characterization of passivation layers has been carried
out by 1. Kruger, G. Long, and coworkers [28], by Froment et al. [29], and by O'Grady and coworkers
at NRL [30]. EXAFS spectra are sometimes difficult to interpret as a consequence of ambiguities in
attempts to fit existing theoretical models for the absorption spectra, and this aspect requires theoretical

20-14
attention. EXAFS provides information on local coordination number and neighbor distances. It can be
used for surfaces and for buried interfaces.

D. Neutron Reflectometry

Although X-ray reflectometry has been a standard, if not widespread, surface characterization tool
for some time, its counterpart using neutrons is relatively unknown. (The recent dearth of neutron sources
in the United States has stunted growth in this area.) Nevertheless, certain advantages for neutron
reflectometry for studying "buried interfaces" should be brought to the attention of the corrosion
community.

Neutrons will reflect specularly from a smooth interface with high efficiency when near the critical
angle (glancing a few degrees from the surface). Two interfaces create a characteristic interference p'attern
that can be used to measure layer thickness; density variations within the layer (normal to the substrate)
can be determined from the interference signature. Most important to corrosion problems, perhaps, is the
diffuse scattering parallel to the surface around the specular reflection, because it contains information
about in-plane variations on the interface.

The key advantage for neutroii experiments vis-a-vis X-rays is penetrability. Metal overlayers that
stop X-rays present no special impediment to neutrons. Because the scattering length density is, roughly
speaking, a random function of atomic number z, isotopic labeling is often useful. Spatial resolution for
neutron reflectometry is typical of small-angle scattering: 1 to 100 nm. Jlfational user facilities have been
established for neutron reflectometry at LANSE (Los Alamos) and the National Institute of Standards and
Technology (NIST).

E. Electrochemical Impedance Analysis

Variable frequency techniques to characterize reactive interfaces are mature and continue to
expand. Reaction rates at interfaces, the deposition and growth of corrosion product films, and the
evaluation of coatings (e.g., permeability, defects and pores, film delamination, and heterogeneous
pathways for ionic species) are addressed by impedance measurements (MacDonald [31] has a recent
review of such applications, as does Mansfeld and Bertocci [32]). Localized scanning methods have
appeared recently (see Lillard, et al., [33]), but their use is not widespread. There are also international
symposia in which impedance analysis is discussed, including results for corrosion systems (The Second
International Symposium on Electrochemical Impedance Spectroscopy will be held in 1992 in the United
States). For simple·systems, the use of impedance is straightforward, but more complex, heterogeneous
surfaces have multiple processes that occur simultaneously. In the latter case, the measurements must be
used in conjunction with theoretical models based on the fundamental processes taking place at the
interfaces. Fortunately, such modeling for the interpretation of experiments has begun to appear (e.g., the
work of Newman [34] and references therein).

F. Spectroscopic Ellipsometry

Although this is not a new method, it has been insufficiently used for characterizing the electronic
structure of the passivation layer in corrosion studies. A major reason has been the difficulty in
interpreting the rather complex spectra. Recent advances in the calculation of optical conductivities of
microscopic models of highly disordered oxides have begun to make these interpretations feasible [35,36].
The extension to the study of the interface between the substrate metal and the protective ovedayer is one
of its most promising features.

20-15
G. Imaging Ellipsometry

Problems in microcircuit fabrication, wetting, and coating have driven the recent development of
. ellipsometers capable of imaging (e.g., Streinz, et aI. [37]). Based on standard photometric ellipsometers,
imaging systems have been incorporated covering a range of transverse spatial resolutions from 1 to 5 IJIll
at the low end to fields as large as 2 cm, depending on the problem of interest In general, spatial maps
of film thickness and index can be obtained at a given wavelength, although, in principle, multiple
wavelengths could be used. The main difference between imaging ellipsometers and conventional
ellipsometers that scan the sample point by point is the ability to capture time-dependent phenomena over
a wide field of view.

H. Phase Detection Interferometric Microscopy (pDIM)

PDIM is rapid, versatile, and more accurate than traditional interferometric microscopy.
Instruments are available that have a vertical resolution of 0.2 run and a larger lateral resolution of
- 0.5 1JIll. PDIM has been used for topographical imaging of reactive surfaces (White et aI. [38]) and for ·
thickness and refractive index measurements of solvent swollen films (Smith et aI. [39]). The instrument
has a demonstrated capability of monitoring changes of morphology of a buried interface beneath an
aqueous solution or polymer film; it may also be used to measure film detachment or deadhesion.

I. Infrared and Raman Methods

Infrared methods that are partly surface-specific have begun to be used, although they require very
good surfaces. Surface enhanced Raman scattering (SERS) remains difficult to interpret due to problems .
in quantitatively characterizing the various enhancement mechanisms. Spectroscopic techniques for surface
studies have been reviewed in Chapter 3 of this volume .

.J. Second Harmonic Generation (SHG)

SHG is a useful in situ optical method and has been discussed in Chapters 4 and 5 of this volume.
A general difficulty is that theory seriously lags behind experiment in its ability to quantitatively predict
spectra, given a microscopic model. This means that only qualitative interpretations are possible at
present. Theoretical efforts to account for the effects of the aqueous (or other solvent) environment are
in a preliminary stage.

K. Optical Fiber Probes and Near Field Microscopy

Optical fibers have proved to be a versatile and valuable tool for investigations that range from
spectroscopic probes to physical optics. Further, they are the basis for developments of several sensor
systems. In the latter field, Butler and colleagues [40-41] have used optical fibers to study chemical
interactions of metals with gaseous environments, and the extension to liquid systems is straightforward.
Moreover, Betzig et al. [42] have fabricated microfibers to obtain optical spatial resolutions of the order
ofl/SO, far below the diffraction limit The use of such techniques to perform super resolution microscopy
on reacting surfaces in situ could give useful information.

L. Quartz Crystal Microbalance (QCM) Gravimetry

The QCM has been used extensively in gas and vacuum systems for monitoring film thickness
changes [43]. Single layers of inhibitors, self-assembled monolayers, Langmuir-Blodgett f1lms~ or
corrosion product films could, in principle, be detected because the QCM is sensitive to fractions of an

20-16
atomic layer. Corrosion of several metals has been investigated in gaseous or humid ambient
environments, as well as in liquid solutions. When associated with electrochemical and spectroscopic
measurements, surface degradation processes of some complexity can be characterized. Recent reviews
are available for corrosion applications of the QCM, including atmospheric exposure [44,45].

M. Modeling

Successful surface characterization depends in many cases on successful modeling of the interface
being characterized in order that the experimental output of the measuring instrument can be'meaningfully
interpreted. As examples, we have mentioned the model dependent interpretation of SEXAFS, SERS,
STS, and ellipsometry above. ·Generally, modeling capability has increased significantly in the recent past
as a consequence of dramatically improved computing capability as well as the introduction of various
simulation techniques (molecular dynamics, Monte Carlo, equation of motion, Car-Parinello methods and
others) to electrochemical and corrosion problems.

Corrosion systems consist of complex interconnected and interrelated components and phenomena.
Time-dependent multiple reactions and processes, distributed laterally across surfaces as well as throughout
interfacial films, lead to system behavior that is difficult to analyze. The influence of geometry,
thermodynamics, kinetics, transport processes, and the nature of the surface and environment'may all be
important In addition, the mechanical state of a degrading interface may affect phenomena such as stress
corrosion cracking or film cracking and delamination. One justification for modeling and analysis is that
-judicious modeling, combined with experiment, is generally less expensive than experimentation alone.
Mathematical models (once established) have quantitative predictive capabilities for accelerated testing,
and for scale-up and scale-down. The models have the additional benefit that they provide general insight
that may translate into understanding other corrosion phenomena as well.

Accelerated life testing cannot be meaningfully interpreted without reliable understanding of the
degradation mechanisms occurring in the corrosion processes (see Chapter 25 of this volume). This need
requires more extensive and basic modeling efforts than have been characteristic of corrosion studies in
the past. To be useful to an accelerated testing program, modeling must take place both at the microscopic
and macroscopic time and length scales, and it must take place in close coordination with carefully
controlled experimental programs to verify the concepts and parameters in the models. Relevant modeling
technologies include, at the electronic level, band structure methods and their extensions to disordered
systems; at the atomic level, molecular dynamics methods and electronic structure methods; and at the
macroscopic level, Monte-Carlo and engineering methods of simulation. Taken together, the goal of the
modeling efforts discussed in the report is to provide predictions and simulations of systems (e.g.,
automobiles, buses, and trucks) so that they are relatively trouble-free for extended periods of service.

v. RECOMMENDATIONS

A. Systems Near Success

Surface modification has advanced the state of the art in corrosion protection in several of the
transportation and solar energy technologies. Improvements in protection systems would provide the
increment~ advances needed to achieve desired lifetimes. The economic savings would be large.

First, enormous resources are currently devoted to corrosion prevention by Zn galvanizing of steel
parts in U.S. vehicles. Opportunities to reduce these costs arise from the existence of new galvanizing
alloys and from the possibility of greatly improved understanding of the structures and processes

20-17
associated with galvanic protection afforded by these alloys using modern surface science characterization
and modification techniques.

• Recommendation: We recommend significant new programs to characterize and improve galvanizing

alloys on steel.

Second, primary parabolic mirrors fabricated for solar energy collectors consist of PMMAIAgi
adhesive/AI or stainless steel multilayer assemblies. Corrosion of the Ag occurs beneath the PMMA.

• Recommendation: Research to understand the interface degradation reactions and mitigate.the cause
of the reaction andlor to develop a UV degradation-resistant, inexpensive coating to replace PMMA
should be conducted.

1bird, single-crystal Si solar cells can compete with amorphous and polycrystalline Si solar cells
for terrestrial applications when less expensive materials and fabrication procedures are substituted in
production. In these, solar cells are encapsulated under a glass cover (substituted for fused quartz) using
ethylene vinyl acetate for environmental protection. The pottant is subject to UV photothermal
degradation and may chemically react with Ag or AI metallization (substituted for PdIAg) on the solar cell
surface, thereby degrading performance because of optical losses, reactions with degradation products, and
unbalancing the cell circuitry.

• Recommendation: Research should be conducted to develop a UV stable, organic, or inorganic pottant

to encapsulate the solar' cell and bond to the cover glass.

B. Surface Characterization

Surface characterization of corroded surfaces and of protective coatings and fIlms is on the
threshold of significant advances, particularly as a consequence of the ·recent development of improved
in situ techniques. .

• Recommendation: Programs are recommended that will exploit and further develop new in situ
surface characterization methods for applications to corrosion problems (see Chapter 26 in this
volume).

C. Surface Modification and Surface Characterization of Emerging Systems

First, the increasing use of light metal alloys-notably aluminum and magnesium-in vehicles will
increase fuel efficiency dramatically. Corrosion and wear limit alloy life, and surface modification
becomes an essential part of the application.

• Recommendation: We recommend programs to design these surfaces for light-metal alloys and alloy
composites, guided by modem surface/interface characterization techniques.

Second, commercialized, electrochromic windows will provide a dramatic energy savings in the
nation's buildings. Electrochromic systems have not yet demonstrated the long-term durability required
in this application. Because this is an emerging technology, fundamental understanding of the materials,
interfaces, and degradation mechanisms should be carried out to underpin its widespread use.

20-18
• Recommendation: We recommend characterizing technologically feasible electrochromic systems
using surface and interface characterization techniques and then solving any life-limiting problems
with advanced surface modification.

lbird, electric vehicles will require better power sources than the lead-acid battery currently
available. These advanced batteries and fuel cells must withstand extended cycling under a broad range
of driving conditions. Typically corrosion limits the life of an electrochemical power source.

• Recommendation: We recommend specific efforts be devoted to identifying corrosion phenomena in

batteries and fuel cells for electric vehicles and then finding the solutions with surface modification.

D. Basic Research in Corrosion

The way to future progress in corrosion protection must be paved by ongoing basic research.
Knowledge of the' mechanisms of corrosion, its prevention, inhibition, and repair are the stepping stones
for advances in new materials and processing.

• Recommendation: We recommend that the basic studies of surface modification and characterization
be expanded by long-term commitments, to reveal the processes by which coatings and films fail, and
to advance general methods of corrosion protection.

REFERENCES

1.
...
W. Smyrl (Chairman of Panel), Agenda for Advancing Electrochemical Corrosion Science and
Technology, NMABINRC 438-2, National Academy Press, Washington, DC, 1987.

2. D. Snyder, Zinc-Based Steel Coating Systems: Metallurgy and Performance, in G. Krauss and
D. K. Matlock, Eds., The Minerals, Metals and Materials Society, Warrendale, PA, 1990.

3. W. Funke, H. Leidheiser, Jr., R. A. Dickie, H. Dinger, W. Fischer, H. Haagen, K. Herrmann,

H. G. MosIe, W. P. Oechsner, J. Ruf, J. S. Scantlebury, M. Svoboda, and J. M. Sykes, 1. Coatings
Techno!., ~ 79 (1986).

4. M. K. Carpenter and D. A. Corrigan, Eds., Electrochromic Materials, The Electrochemical Society,

Pennington, NJ, 1990.

5. D. M. Mattox, J. Vac. Sci. Techno!., A 7(3), 1105 (1989); D. M. Mattox, Electrochem. Tech., b 295
(1964).

6. G. Dearnaley, J. H. Freeman, R. S. Nelson, and J. Stephen, Ion Implantation, North-Holland, London,

United Kingdom, 1973. .

7. G. K. Wolf and W. Ensinger, Nuc!. Instrum. and Meth. in Phys. Res., B59/60, 173 (1991).

8. W. Ensinger and G. Wolf, J. Mat. Sci. Eng., AIlS, 1 (1989); G. Wolf, Nucl. Instrum. Meth. in Phys.
Res., B46, 369 (1990).

9. T. Takahashi, Surfaces and Coatings Technology, Proceedings of 7th SMMIB Conference, July 1991,
Washington, DC, to be published.

20-19
10. H. Kaesche and R. A. Rapp, Metallic Corrosion, National Association of Corrosion Engineers,
Houston, TX, 1985. -

11. D. A. Jones, Principles and Prevention of Corrosion, Macmillan, New York, NY, 1992.

12. M. G. Fontana, Corrosion Engineering, 3rd Edit., McGraw-Hill, New York, NY, 1986.

13. L. L. Shreir, Corrosion, Newnes-Butterworths, London, United Kingdom, 1979.

14. E. McCafferty, J. Electrochem. Soc., 124. 1869 (1977).

15. 1. T. Waber, J. Morrissey, and J. Ruth, J. Electrochemical Society, 103. 138 (1956). (See also
references therein.)

16. R. Morris and W.H. Smyrl, AIChE J., M.. 723 (1988).

17. R. Morris and W.H. Smyrl, J. Electrochem. Soc., 136, 3237 (1989).

18. 1. W. Halley, General Motors Technical Report, 1992.

19. P. B. P. Phipps and D. W. Rice, in G. R. Brubaker et al., Eds., Corrosion Chemistry, ACS
Symposium Series, 90, Washington, DC, 1979, p. 235.

20. R. Morris and W. H. Smyrl, 1. Electrochem. Soc., 136. 3229 (1989).

21. G. Chandra, Mat. Res. Soc. Symp. Proc., 203. 97 (1991).

22. C. E. D. Chidsey, in D. R. Baer, C. R. Clayton, and G. D. Davis, Eds., The Application of Surface
Analysis Methods to Environmental/Materials Interactions, The Electrochemical Society, Pennington,
NJ,1991.

23. S. Snyder and H. S. White, Anal.Chem., M.. June 1992.

24. M. F. Toney and O. R. Melroy, in H. Abruna, Ed., In Situ Studies of Electrochemical Interfaces,
VCH Publications, New York, NY, 1991.

25. D. G. Wiesler, M. F. Toney, O. R. Melroy, C. S. McMillan, and W. H. Smyrl, in A. Davenport and

J. Gordon, Eds., X-ray Methods in Corrosion and Interfacial Electrochemistry, The Electrochemical
Society, Pennington, NJ, 1992.

26. D. G. Wiesler, M. F. Toney, O. R. Melroy, C. S. McMillan, and W. H. Smyrl, Surface Science, 268.
57 (1992).

27. H. You, Z. Nagy, C. A. Melendres, D. 1. Zurawski, R. P. Chiarello, R. M. Yonco, H. K. Kim, and

V. A. Maroni, in A. Davenport and 1. Gordon, Eds., X-ray Methods in Corrosion and Interfacial
Electrochemistry, The Electrochemical Society, Pennington, NJ, 1992.

28. J. Kruger, G. G. Long, M. Kuriyama, and A. I. Goldman, in M. Froment, Ed., Passivity of Metals
and Semiconductors, Elsevier, Amsterdam, The Netherlands, 1983.

20-20
29. L. Bosio, R. Cortes, A. DeFrain, and M. Froment, J. Electroanal. Chem., 180,265 (1984).

30. W. E. O'Grady, E. McCafferty, P. M. Natishan, A. E. Russell, K. I. Pandya, and D. Ramaker, in

A. Davenport and J. Gordon, Eds., X-ray Methods in Corrosion and Interfacial Electrochemistry, The
,Electrochemical Society, Pennington, NJ, 1992.

31. J. Ross MacDonald, Ed., Impedance Spectroscopy, Wiley Interscience, New York, NY, 1987.

32. F. Mansfeld and U. Bertocci, Eds., Electrochemical Corrosion Testing, ASTM Special Technical
Publication 727, ASTM, Philadelphia, PA, 1981.

33. R. S. Lillard, P. J. Moran, and H. S. Isaacs, J. Electrochem. Soc., 139, 1007 (1992).

34. J. Newman, Electrochemical Systems, Prentice Hall, New York, NY, 1991.

35. J. W. Halley, M. Mrchalewicz, and N. Tit, Phys. Rev. B, ~ 10165 (1990).

36. J. W. Halley, M. Kozlowski, M. Michaelwicz, W. Smyrl, and N. Tit, Surface Science, 256. 397
(1991). '

37. C. C. Streinz, J. W. Wagner, J. Kruger, and P. Moran, J. Electrochem. Soc., 139, 711 (1992).

3~ .. H. S. White, D. J. Earl, J~ D. Norton, and H. Kragt, Anal. Chem., g, 1130 (1990).

39. C. P. Smith, D. C. Fritz, M. TIrrell, and H. S. White, Thin Solid Films, 198,369 (1991).

'40. M. A. Butler and A. 1. Ricco, Appl. Phys. Lett., ll. 1471 (1988).

41. M. A. Butler, A. 1. Ricco, and R. J. Baughman, 1. Appl. Phys., g 4320 (1990).

. ,

42. E. Betzig, J. K. Trautman, T. D. Harris, J. S. Winer, and R. L. Kostelak, Science, 251, 1468 (1991).

43. C. Lu and A. W. Czanderna, Eds., Applications of Piezoelectric Quartz Crystal Microbalances,

Elsevier, Amsterdam, The Netherlands, 1984.

44. W. H. Smyrl and K. Naoi, in G. Prentice and W.H. Smyrl, Eds., Perspectives on Corrosion, AIChE
Symposium Series 278, M. New York, NY, 1990.

45. W. H. Smyrl and M. Lien, in N. Masuko, T. Osaka, and Y. Fukunaka, Eds., New Trends and
Approaches in Electrochemical Technology, Kodansha Scientific Ltd., Tokyo, Japan, 1992.

20-21
 21. BATIERIES AND FUEL CELLS

Ross Lemons, Los Alamos National Laboratory, Chairman

James Eberhardt, DOF/Office of Transportation Materials
Albert Landgrebe, DOFJElectric and Hybrid Propulsion Systems
Don MacAurther, CHEMAC International Corporation
Robert Savenell, Case Western Reserve University
S. Swathirajan, General Motors Research
Dane Wilson; Oak Ridge National Laboratory
Mahlon Wilson, Los Alamos National Laboratory

ABSTRACT

Electrochemical energy systems are dominated by interfacial phenomena. Catalysis, corrosion,

electrical and ionic contact, and wetting behavior are critical to the performance of fuel cells and batteries.
Accordingly, development of processing techniques to control these surface properties is important to
successful commercialization of advanced batteries and fuel cells. Many of the surface proces$ing issues
are specific to a particular electrochemical system. Therefore, the working group focused on systems that
are of specific interest to the DOE Office of Conservation and Renewable Energy. The systems addressed
were:

• Polymer electrolyte membrane (PEM) fuel cells

• Direct methanol oxidation (DMO) fuel cells
• Lithium/polymer batteries.

The approach used by the working group for each of these systems was to follow the path of the
current through the system and to identify the principal interfaces. The function of each interface was
specified together with its desired properties. The degree to which surface properties limit performance
in present systems was rated. Finally, the surface processing needs associated with the performance-
limiting interfaces were identified. This report summarizes this information.

I. INTRODUCTION

For identifying and prioritizing the research needs and opportunities in its topical area, the working
group on Batteries and Fuel Cells focused on electrochemical energy systems that are of specific interest
to the DOE Office of Conservation and Renewable Energy. The systems addressed were:

• PEM fuel cells

• DMO fuel cells
• Lithium/polymer batteries.

The approach used by the working group in each of these systems was to follow the path of the
current through the system and to identify the principal interfaces. The function of each interface was
specified together with its desired properties. The degree to which surface properties limit performance
in present systems was rated. Finally, the surface processing needs associated with the performance-
limiting interfaces were identified.

21-1
II. PEM FUEL CELLS

A. Introduction to PEM Fuel Cells

Fuel cells offer a means of electricity production with a higher·efficiency and a lower pollutant
emission than other technologies. Basically, a fuel cell converts the chemical energy in hydrogen and
oxygen to electricity with water as the by-product. The oxygen can be supplied directly as air, and the
hydrogen is available from a broad range of energy resources. These resources include reformed organic
fuels such as methanol or natural gas, reformed biomass, solar-electric-driven electrolysis, wind-powered
electrolysis, and other renewable resources.

Phosphoric acid, molten carbonate, and solid oxide fuel cells are being developed for stationary
power plant applications. However, for transportation and a broad range of other applications such as
private homes and small businesses, remote site generation, and some industrial uses, compact, efficient,
low-cost fuel cells are needed.

The PEM fuel cell has a combination of characteristics that are particularly attractive for these
applications. It provides high power densities. It can tolerate CO2 in the fuel stream, allowing the use
of reformed organic fuel. It can be self-starting at temperatures above - 20°C. Low-cost structural
materials can be used because of the low operating temperature and reduced corrosion, and the solid
c11aracter of the electrolyte facilitates .sealing and safety of the fuel cell stack. The limitations of the
technology have been high platinum content, expensive membranes, poor carbon monoxide tolerance,
water management problems, and difficulty in thermally integrating the fuel cell with a reformer. Several
of these problems can be solved by modifying or improving the surface properties of the materials and
components of the fuel cell.

B. Surface Processing Aspects of PEM Fuel Cells

Figure 1 shows a genenilized cross-section of a polymer electrolyte fuel cell. To emphasize the
surface processing aspects, each of the elements of the fuel cell is shown separately. In real fuel cell
designs, two or more of these elements may be combined in a multifunction element.

In considering the surface processing aspects of the fuel cell, two classes of surfaces must be
considered. The first class includes the interfaces between the elements, such as the interface between the
anode and the membrane. The second class involves surfaces within an element, such as the pore surfaces
within the gas diffusion structure.

The \\,orking group evaluated each of the elements shown in Fig. 1, moving from left to right.
The function each element must provide was specified, and the properties that would be desired to achieve
that function were identified. Each of these properties was then evaluated to determine whether the
property is dominated by the surface. Finally, the importance of improving the surface properties was
rated as high, medium, or low. This information is summarized in the tables below. For those interfaces
that currently limit the performance of the fuel cell, suggestions for specific research and development
efforts are indicated.

· 21-2
 Table 1. End Plate/Gas Separator Interface

Surface Problem
Function Desired Properties Dominated Severity
Mechanical compression Uniform pressure No Low

Corrosion resistant Yes . ·Low

Electrical contact Low contact resistance Yes Low

Long-term stability Yes Low

The interface between the end plate and the gas separator does not present a significant limitation on
performance.

Table 2. Gas Separator/Gas I?istribution Interface

Surface Problem
Function Desired Properties Dominated S~verity

~/02 isolation Gas' impermeability Possible Low

Corrosion resistant Yes Medium

Electrical contact Low contact resistance Yes Low

Long-term stability Yes Low

Note: In many designs, the function of the gas separator and the gas distribution plate are combined in
a grooved impermeable plate.

Performance and design flexibility of this interface would be increased by

• Developing corrosion-resistant, electrically conductive coatings or

• Developing surface modification for enhanced corrosion resistance.

21-3
 Table 3. Gas Distribution!Anode Gas Diffusion Interface

Function Desired Properties Surface Problem

Dominated Severity

Gas distribution across electrode Low pressure drop No Low

Good fuel utilization No Low

Electrical contact Low contact resistance Yes LOw

Corrosion resistant Yes Medium

Performance and design flexibility of this interface would be increased by

• Developing corrosion-resistant, electrically conductive coatings or

• Developing surface modification for enhanced corrosion resistance.

Table 4. Gas Diffusion!Anode Interface

Surface Problem
Function Desired Properties Dominated Severity

Gas distribution across electrode Low gas diffusion resistance Possible Medium

Minimize CO2 diffusion barrier Possible Medium

Electrical contact to anode Good electrical contact to catalyst Yes Medium

Corrosion resistant Yes Medium

Performance and design flexibility of this interface would be increased by

• Improving the characterization of the interface

• Modeling the gas composition within the pores as a function of operating conditions
• Using surface treatment to improve the electrical contact

21-4
 Table 5. Anode·Electrochemical Interface

Function Desired Properties Surface Problem

Dominated Severity
Rapid hydrogen oxidation High gas permeability Possible Medium

Good electronic contact Yes Medium

Good ionic contact Yes Medium

High catalytic activity Yes Medium

CO tolerant Yes High

Resistant to other poisons Yes High

Corrosion resistant Yes Medium

Note: In a fuel cell, the -hydrogen is catalytically oxidized at the anode. This reaction requires the
catalytic site to be in contact with hydrogen gas, an electrical conductor, and a hydrogen ion conductor.
In the PEM fuel cell, the hydrogen ion conductor is a hydrated ionomer. The water content of this
ionomer must be maintained over the full operating range of the fuel cell. Moreover, the catalytic reaction
is strongly affected by the water concentration at the catalytic site. Poisoning from CO or other
contaminants in reformed organic fuels is also a severe problem.

Performance and design flexibility of this interface would be increased by

• Improving water transport to the catalytic sites

• Developing catalysts with improved impurity tolerance
• Modeling the ionic and electronic propertie~ of micro-porous composites
• Improving the understanding of hydrogen oxidation kinetics at ionomer/catalyst interfaces.

21-5
 Table 6. AnodelIonomer Membrane Interface

Surface Problem
Function Desired Properties Dominated Severity
H+ ion conduction from anode Good ionic contact Yes Medium

Maintain water balance at anode Possible High

Long-term stability Yes Low

Prevent gas diffusion between anode Gas impermeability Possible Medium

and cathode

Performance and design flexibility of this interface would be increased by

• Determining the role of membrane surface properties

• Improving the control of the surface functionality by chemical surface modification
• Developing an iOnically conductive adhesive that could be' used to bond the anode to the membrane.

Table 7. Ionomer Membrane/Cathode Interface

Surface Problem
Function Desired Properties Dominated Severity
H+ ion conduction to the cathode Low ionic contact resistance Yes Medium

Maintain water balance Possible High

Prevent gas diffusion between anode Possible Medium

and cathode
Long-term stability Possible Medium

Performance and design flexibility of this interface would be increased by

• Determining the role of membrane surface properties

• Improving the control of the surface functionality by chemical surface modification
• Developing an ionically conductive adhesive that could be used to bond the cathode to the membrane.

21-6
 Table 8. Cathode Electrochemical Intelface

Function Desired Properties Surface Problem

Dominated Severity
Rapid oxygen reduction High oxygen permeability Possible Medium

Good electronic contact Yes Medium

Good ionic contact Yes Medium

High catalytic activity Yes High

Rapid product water removal Possible High

Resistant to poisons Yes High

Corrosion resistant Yes Medium

Note: In a fuel cell, oxygen is catalytically reduced at the cathode. lbis reaction requires the catalytic
site to be in contact with oxygen gas, an electrical conductor, and a hydrogen ion conductor. In the PEM
fuel cell, this reaction is usually the kinetically limiting reaction. Platinum or platinum alloys are the only
catalysts found so far that show high reaction rates in this environment lbis catalytic reaction is also
strongly affected by the water concentration at the catalytic site. Removal of product water from the
catalytic site is critical to sustaining high performance. .

Performance and design flexibility of this interface would be increased by

• Developing alternatives to platinum as an oxygen reduction catalyst

• Improving the understanding of hydrogen oxidation kinetics at ionomer/catalyst interfaces.

A DOE-sponsored workshop on oxygen electrocatalysis was held October 29-November 1, 1991.

Detailed recommendations for research and development on the fuel cell cathode can be found in the
proceedings of that workshop [1].

21-7
 Table 9.. Cathode/Cathode Gas Diffusion Interface

Surface Problem
Function Desired Properties Dominated Severity

Gas distribution to catalyst Rapid oxygen diffusion · Possible Medium

Electrical contact to catalyst Good electrical contact to catalyst Yes Medium

Corrosion resistant Yes Medium

Performance and design flexibility of this interface would be increased by

• Determining the effects of potential cycling on corrosion of this interface

• Determining the microscopic effects of pressure
• Developing improved contact by surface treatment.

Table 10. Cathode Gas Diffusion Layer-Internal Surfaces

Surface Problem
. Function Desired Properties Dominated Severity

Gas distribution acrDSS electrode Low gas diffusion resistance Possible Medium

N2 removal Possible Medium

Product water removal Hydrophobic Yes Medium

Good water droplet transport Yes High

Long-term stability Yes High

Performance and design flexibility of this component would be increased by

• Improved surface treatment to maintain hydrophobicity ·over long periods

• Tailoring of the porosity to facilitate gas exchange
• Modeling of the two-phase transport in porous structures.

The remaining interfaces in the PEM fuel cell on the cathode side are similar to those on the anode side
with similar surface processing issues.

21-8
C. PEM Fuel Cell Summary

The areas of improvement most needed in the PEM fuel cell are lower cost, water management,
and impurity tolerance. Surface processing can make a contribution in each of these areas. Development
of conductive, corrosion-resistant coatings can reduce the cost of the structural materials. Development
of processes to provide pore surfaces with hydrophobic properties that are stable over thousands of hours
of operation can improve the performance and lifetime of the fuel cell. Development of catalysts with
a better impurity tolerance and a lower cost than platinum can improve the fuel flexibility and reduce the
cost of PEM fuel cells.

III . . DMO FUEL CELL

A. Introduction to DMO Fuel Cells

In a DMO fuel cell, methanol is supplied directly to an anode catalyst without the need for
reforming. Although high-temperature systems such as solid oxide fuel cells operating at - lOOO°C and
molten carbonate fuel cells operating at - 600°C have the potential to use methanol directly as a fuel,
DMO fuel cells usually refer to relatively low-temperature systems operating at 25°C to 300°C, in which
the methanol is catalytically oxidized in the presence of water to produce hydrogen ions, electrons, and
carbon dioxide.

The benefits of a DMO/air fuel cell become apparent when it is compared with today's fuel
processing technology. A number of approaches have been used to convert organic fuel, and in particular
methanol, to a hydrogen-rich fuel gas. These include high-temperature reforming, low-temperature
reforming with selective oxidation, and low.,.temperature internal reforming coupled with selective
oxidation within the anode chamber. All of these approaches have significant drawbacks, particularly in
system cost and complexity.

DMO fuel cells, in principal, eliminate the need for fuel reforming and thus offer the potential for
a lower cost and a smaller power plant size. They also offer safety advantages by eliminating the need
to handle hydrogen. Finally, DMO fuel cells may have a better transient response than reformer-based
power systems. The problems with DMO fuel cells are, however, also very difficult

B. Surface Processing Aspects of DMO Fuel Cells

In many respects, the surface processing issues associated with DMO fuel cells are similar to those
associated with PEM fuel cells. However, there are a set Of special problems that are characteristic of
DMO fuel cells that will be addressed in this section. These problems are (1) rapid poisoning of the
anode catalyst by products of the methanol oxidation, such as CO and (2) methanol cross-over from the
anode to the cathode, which poisons the cathode catalyst

There are two primary approaches to solving problem (I). The first is to find a catalyst that
desorbs reaction products such as CO. The most promising catalysts of this type are PtRu alloys, which
may have additional components. Further research to identify a superior DMO catalyst is important to
the dev~lopment of this technology.

The second approach to solving problem (1) is to increase the operating temperature to the point ·
at which products such as CO can be thermally desorbed from the catalyst A temperature of 200°C to
300°C would be desirable for this purpose. However, existing membrane separators are not stable at such
elevated temperatures. The development of a stable membrane with high ionic conductivity would be very

21-9
important to the further development o~ DMO fuel cells. 'This is pri.marily a materials development issue
rather than a surface processing issue, but there may be surface processing aspects to the fabrication of
such a: membrane.

Conventional membrane separators such as Nafion® are permeated by methanol, ~d methanol

that reaches the cathode rapidly poisons the oxygen reduction reaction. One solution to this problem is
to develop a membrane that is impermeable to methanol but retains the other desired properties for a fuel
cell. Again, this is primarily a materials development issue; however, it may be possible to modify the
surface of useful membranes to block methanol feed-through without destroying the other desirable
features. 'This is an important line of research.

C. DMO Fuel Cell Summary

The issues associated with the DMO fuel cell have been dealt with in great detail in a Direct
Methanol Oxidation Workshop held at Georgetown University on May 14-16, 1990. The recom-
mendations from that meeting are contained in the workshop summary [2].

IV. LlTIillJM-POLYMER BATIERIES

A. Introduction to Lithium-Polymer Batteries

Fenton and Wright observed in 1973 the remarkable conductivity of lithium salts in polyethylene
oxide [3]. Armand drew attention to the practical application of these polymer electrolytes in lithium
batteries [4]. Shortly after this work, two groups-one headed by the Harwell Research Laboratories and
the other headed by Hydro Quebec-were established to attempt commercialization of the technology.

In the intervening years, increased understanding of the ion conduction mechanism in the polymers
has occurred. It has been realized that conduction primarily occurs in amorphous phases of the
electrolytes. Simple polyethylene oxide electrolytes are sufficiently amorphous above 80°C to have
conductivities above I<r'W- 1cm-1• For thin fIlms, conductivities above I<r'W-1cm-1 are sufficient to meet
the power requirements of electric vehicle batteries. It is desirable to have this performance from a battery
at ambient temperatures.

Recent work on the polymer electrolytes has resulted in the development of electrolytes that are
amorphous at ambient temperatures and have conductivities in the range of to-3 W- 1cm-1• With this
development, there is now a strong initiative to commercialize the lithium polymer battery.

Another key development, important to the lithium polymer battery, was lithium intercalating
cathode materials, first proposed by Wittingham [5]. With this development, "the physicist's battery" was
possible. In this system, the lithium moves back and forth between the cathode and anode without
undergoing significant chemical reactions to new chemical entities. The electrolyte does not participate
in the charge/discharge reactions, so it can be very thin, as long as it provides separation between the
electrodes.

With these developments, the thin-film solid-state lithium battery is a reality. Typically the
construction is

(1) Pure lithium metal in the range of 2S-mm to SO-mm thick, a graphite carbonllithium intercalation
material, or a lithium-aluminium alloy

21-10
(2) ~ polymer electrolyte in the range of SO-mm to lSO-mm thick

(3) A cathode mixture prepared from a lithium intercalating transition metal oxide powder laminated into
a film approximately lOO-mm thick.

The addition of current collectors and a sealed envelope completes the battery.

B. Surface Processing Aspects of lithium-Polymer B~ries

Figure 2 shows a generalized cross-section of a lithium-polymer battery. To emphasize the surface

processing aspects, each of the elements of the battery is shown separately.

In considering the surface processing aspects of the battery, two classes of surfaces must be
considered. The first class includes the interfaces between the layers, such as the interface between the
lithium-anode and the polymer electrolyte. The second class involves interfaces within a layer, such as
the interfaces between transition-metal-oxide particles and the polymer electrolyte.

The working group evaluated each of the elements shown in Fig. 2, moving from left to right.
The function each element must provide was specified, and "the properties that would be desired to achieve
that function were identified. Each of these properties was then evaluated to determine whether the
property is dominated by the surface. Finally, the importance of improving the surface properties was
rated as high, medium, or low. This information is summarized in the tables below. For those interfaces
that currently limit the performance of the lithium battery; suggestions for specific rese,archand
development efforts are indicated.

Table 11. Current CollectorlLithium Anode

Surface Problem
Function Desired Properties Dominated Severity

Electrical contact Low contact resistance Yes Low

Long-term stability Yes High

The interface between the current collector and the lithium anode is subject to corrosion. Surface
treatments to reduce this corrosion or processing to reduce the activity of the lithium metal would help
solve this problem.

21-11
 Table 12. Lithium AnodelPolymer Electrolyte Interface

Surface Problem
Function Desired Properties Dominated Severity
Li+ ion conduction Good ionic contact Yes Medium

Reversible Li deposition and Yes High

stripping
Long-term stability Yes High

The long-term performance of the lithium/polymer battery can deteriorate due to passivation at the
Wpolymer electrolyte interface. This passivation process is not yet understood. Research is needed to
identify the passivation mechanism and to develop materials techniques that will retard the passivation
process.

Table 13. Polymer Electrolyt~tercalation Electrode Interf~

Surface Problem
Function Desired Properties Dominated Severity
Li+ ion conduction Good ionic contact Yes Medium

Reversible Li+ insertion and Possible Medium

withdrawal
Long-term stability Yes High

Interfaces between the polymer electrolyte and intercalation compounds such as vanadium oxide are also
affected by passivation problems. The resistance of this interface can increase by large factors over a
period of a few hundred hours [6]. Research is needed to identify the passivation mechanism and to
develop materials techniques that will retard the passivation process.

Another stability problem is manifested by capacity decline during cycling. This may be due to
electrical isolation of some of the electrode particles in the composite caused from repeated intercalation-
deintercalation cycles. The changes in particle volume during these cycles may deteriorate the interparticle
contact. This problem is surface related and requires careful characterization to determine the cause.
Surface processing may also provide a potential solution to this problem.

21-12
 Table 14. Intercalation Electrode/Current Collector Interface

Surface Problem
Function . Desired Properties Dominated Severity
Electrlclll contact Low contact resistance Yes Low

Long term stability Yes Low

The interface between the intercalation electrode and the current collector does not present significant
surface processing problems. .

C. Lithium-POlymer Battery Summary

The key problem associated with lithium-polymer batteries is long term stability. The loss in
performance can be due to passivation of internal interfaces or to corrosion. Surface analysis is an
important tool to diagnose the cause of these problems, and surface processing techniques need to be
developed to minimize these effects.

REFERENCES

1. D. Scherson, D. Tryk, D. Daroux, andX. Xing, Eds., Proceedings of the Workshop on Structural
Effects in Electrocatalysis and Oxygen Electrochemistry, Proceedings Vol. 92-11, The Electrochemical
Society, Inc., Pennington, NJ, 1992.

2. A. R. Landgrebe, R. K. Sen, and D. J. Wheeler, Eds., Proceedings of the Workshop on Direct

Methanol-Air Fuel Cells, Proceedings Vol. 92-14, The Electrochemical Society, Inc., Pennington, NJ,
1992. -

3. D. E. Fenton, J. M. Parker, and P. V. Wright, Polymer, H. 589 (1973).

4. M. B. Armand, Polymeric Electrolytes -1, J. R. MacCallum and K. A. Vincent, Eds., Elsevier, I
(1977).

5. M. F. Whittingham, Prog. Solid State Chern., 1141 (1978).

6. P. G. Bruce and F. Krok, Electrochim. Acta,11 1669 (1988).

21-13
 Figure 1. Schematic cross-section of a polymer electrolyte fuel cell

,..transition metal oxide

W'intercalation compound

• carbon particle

I
polymer electrolyte
(doped polyethylene
oxide)

current polymer composite current

collector or Life electrolyte cathode collector
composite

Figure 2. Schematic cross-section of a lithium polymer electrolyte battery

21-14
 22. LUBRICATING AND WEAR SURFACES

Fred A. Nichols, Argonne National Laboratory, Chairman

G. Barber, Detroit Diesel
R. Erck, Argonne National Laboratory
G. Fenske, Argonne National Laboratory
M. Graham, BIRUNorthwestern University
F. Kelley, Cateipillar Inc.
R. McCune, Ford Motor Company
R. Olsen, General Motors
T. VOjnovich, Department of Energy
P. Willermet, Ford Motor Company·

I. IDENTIFIED NEEDS AND OPPORTUNITIES

The working group identified 19 problems related to lubricating and wear surfaces as they apply
to transportation technologies. Because the problems are quite diverse in nature, they are treated as 19
separate issues using the format, in general, of problem, current approach, needs, R&D program
envisioned, time scale, and payoff.

A. High-Temperature Valve Guide/Stem Wear

Problem: Valve guide/stem wear at high temperatures in developmentallow-heat-rejection engine.

Current approach: 4140 steel valves/cast iron guides at 300°-350°C.

Needs: Coating on either or both surfaces to exten~ operating temperature to 500°C and to reduce liquid
lubricant requirement

R&D program envisioned: Investigation of coating/material combinations with high-temperature,

20,OOO-h capability; should provide lubricious interface.

Time scale: 5-7 years.

Payoff: Maintain international competitive advantage, better fuel efficiency, and reduced emissions.

B. Piston RingIBore Tribosystem

Problem: Piston ringlbore tribosystem needs improvement to decrease wear, oil consumption, and
emissions for gasoline, diesel, and alternative fuels.

Current approach: Coated piston skirts and rings/cast-iron or AI bores at -= 150°C for 500,000 miles
(diesel), 100,000 miles (automobile). .

Needs: Heavy-duty diesel-serviceable ringlbore combination at -= 300°C for approximately 1,000,000

miles, 20% increase in cylinder pressure, and reduced friction.

Automotive: Friction reduction at current temperatures for 200,000 miles.

22-1
R&D program envisioned: Identify/develop materials (coatings)/processes for high-temperature
tribological interfaces, e.g., plasma-spray, chemical vapor deposition (CVD)/physical vapor deposition
(PVD). Develop improved piston ring/cylinder wall tribological computer models to guide research.

Time scale: 5-7 years.

Payoff: Maintain international competitive advantage, better fuel efficiency, and reduced emissions.

C. Load-Carrying Capacity: Gears and Bearings

Problem: Need increased load-carrying capacity for gears and bearings in sp~k-ignitedldiesel engines and
vehicular drive trains, as well as in manufacturing.

Current approach: Steel (various) with some type of wear-life-enhancement process.

Needs: Improvements in power throughput capability to allow components with lower cost or smaller size
to be used.

R&D program envisioned: Improved computer modeling of gears and bearings. Investigate coatings or
new surface treatments that offer reduced pitting, scoring, or galling in comparison with conventional
materials.

Time scale: 8-10 years.

Payoff: Enhanced international competitiveness, improved reliability, and design flexibility.

D. Engine Durability with Methanol

Problem: Engine durability with methanol fuels is a current concern. In particular, upper cylinder bore
wear has been observed near the top dead center (TOC) position in some tests. Low-temperature operation
is the most severe mode of operation. Causes cited include formation of formic acid from methanol
combustion, displacement of oilloil additives from the surface by methanol, and poor lubrication due to
emulsion formation.

Current approach: Engines currently designed for rapid heat-up and selection of methanol-compatible oils.
Methanol-compatible oils have higher acid-neutralizing ability and other proprietary features.

Needs: Surface treatments for piston rings andlor bores to provide methanol-compatible coatings for cast
iron and potentially for other substrates.

Payoff: Assured long-term durability for flexible-fueled vehicles, conformance with corporate average
fleet economy (CAFE) requirements, and international competitive advantage.

E. Continuously Vaiiable Transmissions

Problem: Belt and sheave continuously variable transmissions (CVTs), coupled with small-displacement
engines, are currently in operation. Scale-up of this technology has been limited in part by wear of
sheaves and belts. Predominant wear mechanisms include fatigue and plastic deformation under high
pressures and low sliding speeds.

22-2
Current approach: Selection of more fatigue-resistant alloys. Improved surface hardening.

Needs': Fatigue- and plastic-deformation-resistant material, surface treatment, or coating. Improved model
development for optimizing design and minimizing wear.

Payoff: Fuel-economy benefits and improved international competitive advantage.

F. Immersed Electric Fuel Pumps

Problem: Electric fuel pumps operate immersed in fuel. Potential wear areas include the commutator/
brush interface. Concerns include potential abrasion and arcing. The effect of methanol fuel on these
phenomena has not been established Other rubbing contacts are potential concerns because of the poor
lubricating ability of these (low-viscosity) fuels.

Current approach: Issues are in the early stages of investigation.

Needs: Identification of materials/coatings appropriate for commutator, brush, and other applications with
gasoline, methanol, and admixtures.

Payoff: Improved reliability and design flexibility.

G. Tribological Materials Selection from Accelerated Tests

Problem: Accelerated or bench tests used for selection of tribological materials do not always accurately
model the effects of actual service. This deficiency may lead to unrealistic failure modes during testing,
or conversely to unexpected failures during service. No widely accepted, quantitative adhesion evaluation
method is presently available for bond strengths in excess of 69 MPa (10 ksi).

Current- approach: Varies .widely from case to case, ranging from well-defined and verified accelerated
wear tests to arbitrary screening tests for wear and/or adhesion.

Needs: Systematic procedures for defining appropriate tests.

Payoff: Rapid material screening and validation, reduced costs and improved performance, shorter cycle
time.

H. Tribology Data Base

Problem: The need exists for an expanded, user-friendly, readily available tribology data base. Definition
of surface composition required for proposed new applications tends to be "ad hoc" and dependent on
prior experience. This may lead to use of less-than-optimal material or even to component failure during
service.

Current approach: Prior experience and consultation with in-house experts and vendors.

Needs: User-friendly access to information generated by previous research. Perhaps the presently
available ACTIS (a computerized tribology information system) family software package could be
expanded to include a data base on surface processing. Expert systems for surface processing selection
should be explored.

22-3
Payoff: Improved product perfonnance, reduced cost, shorter cycle time.

I. Improved Transmission Performance and Durability

Problem: Optimum shift perfonnance and durability of vehicular transmissions depend on matching
friction materials, fluid properties, and design/operational parameters. No systematic body of knowledge
interrelating these factors is available to p.S. original-equipment manufacturers (OEMs).

Current approach: United States-reliance on vendors and experts, empirical testing. Japan-OEM-
vendor-university research has been ongoing.

Needs: United States-OEM-vendor-university research, perhaps including government laboratories to

define friction material, fluid, and design parameters.

Payoff: Improved vehicle shift perfonnance and durability, international competitive position for U.S.
OEMs and vendors.

J. Adhesive Wear of Injection Plunger Barrel

Problem: Injector plunger-barrel scuffing (adhesive wear) with diesel fuel, but especially with alternative
(low-lubricity) fuels. Potentially also a problem with spark-ignition engines utilizing alternative fuels.

Current approach: Typically, electroplated hard-chromium plunger with hardened steel bore, or nitrided
plunger and bore. Very tight clearances required, e.g., 2.5 ~ (tOO ~n.) diametral. Fuel-lubricated,
approximately 93°C (200 oF). Axial load to 12 kN (2600 lbt), injection pressure == 172 MPa (25 ksi).
Required life > 500,000 miles.

Needs: Injection pressure:::: 207 MPa (30 ksi), up to 1,000,000 miles for heavy-duty engines. Greater
tolerance to low-lubricity fuels (e.g., low S, low aromatics fuel, arctic fuel, methanol, etc.)

R&D program envisioned:

• Develop scuffing- and wear-resistant coatings.

• Develop solid lubricating coatings.

• Evaluate diamond-like-carbon coatings-need improved adhesion to steel.

• Develop coating process for long, narrow bores (lid > 3), e.g., conformal-plasma ion implantation.

• Bench/screening tests and engine tests required.

Time scale: 3-year R&D program to develop and evaluate processes .

. Payoff:

• Improved emissions/fuel economy (higher injection pressure)

• Improved durability and reliability with low-lubricity fuels

22-4
• Improved international competitiveness.

K. Enlargement of Injector Spray Holes (Diesels)

. Problem: Gradual enlargement of injector spray holes of diesel fuel injectors by erosion...corrosion
mechanism, leading to increased fuel consumption, higher emissions.

Current approach: Carburized steel injector cup with multiple holes formed by electrodischarge machining
(EDM). Hole diameter approximately 200 J.UIl (0.008 in). Injection pressure::::: 172 MPa (25 ksi). Diesel
fuel contaminated with sulfuric acid/organic acids/combustion products, 150°-315°C (300°-600°F).
Required life > 10,000 h or 700,000,000 cycles.

Needs: Reduce erosion-corrosion rate by factor of 5.

R&D program envisioned:

• Develop thin PVD coating processes for long, narrow holes (lid> 4); evaluation.

• Develop ion-implantation process for long, narrow holes. Evaluate materials.

• Determine effectiveness of current line-of-sight processes for red~.lCing erosion/corrosion rates.

Time scale: 5-year R&D program.

Payoff:

• Improved durability (fuel economy/emissions)

• Increased fuel-injector pressure capacity (lower emissions/fuel economy)

• Improved international competitiveness.

L. Diesel Fuel Injector Plunger Tip-Cup Seating

Problem: Need to reduce diesel fuel injector plunger tip...cup "beat in," to allow use of higher injection
pressures. Needle and seat of natural-gas injectors also need to survive "beat in" with low-lubricity fuels.

Current approach: Typically tool-steel plunger, carburized steel cup, axial load to 12 kN (2600 Ibf),
approximately 172 MPa (25 ksi) injection pressure. Diesel fuel contaminated with water/organic
acids/combustion gases at 150°C (300°F). Impact velocity of approximately 2.2 mls (85 in/s). Required
life> 10,000 h (700,000,000 cycles). Needle and seat of natural-gas injectors use nitrided steel.

Needs: Increase in injector travel within functional specifications at 207 MFa (30 ksi) injection pressure.
Durable coatings for natural-gas injectors.

R&D program envisioned: Develop hard, thin-film coatings with sufficient ductility and adhesion to the
substrate for this application, yet with low adhesion to counterface. Ion beam assisted deposition (IBAD)
and ion-surface modification (ISM) are possible techniques.

TIme scale: 3 years.

22-5
Payoff: Increased fuel-injection pressure capability (improved emissions/fuel economy). Improved
international competitiveness.

M. Lifetime of Cams and Cam-Roller Followers

Problem: Improved rolling-contact-fatigue (RCF) life of cams .and cam-roller followers is needed.

Current approach: Induction-hardened steel, powder-metallurgy and cast-iron cams, steel or ceramic
rollers. Required life> 500,000 miles (heavy duty) and 100,000 miles (automotive); oil-lubricated. Hertz
stress approximately 1.4-2.0 GPa (200-300 ksi).

Needs: Increase injection pressure 20% without reducing RCF life. Improved lifetime for ceramic rollers.

R&D program envisioned:

• Evaluate thin-film ceramic PVD coatings on cam lobes.

• Evaluate thin-film solid lubricating coatings on roller pin to reduce roller-pin friction, hence cam-roller
traction.

Time scale: 3 years.

Payoff: Increased fuel-injection pressure capability (improved emissions/fuel economy). Improved

international competitiveness.

N. Load-Carrying Capacity and Corrosion Resistance of Bearings and Bushings

Problem: Future designs will result in increased loads on journal bearings (higher cylinder pressure,
higher injection pressure) and increased oil temperatures; hence need to improve load-carrying capacity
and reduce corrosion of bearings and bushings.

Current approach: Typically high, lead-tin bronze bushings cast or sintered onto steel backs, with Pb-Sn
overlay. Oil-lubricated.

Needs: Increase load-carrying capacity by 20%. Increase oil teinperature from = 120°C to = 150°C
(250° -300°F).

R&D program envisioned: Evaluate advanced thin-film solid lubricating coatings as alternatives to current
overlay materials.

TIme scale: 3-5 years.

Payoff: Improved fuel economy/emissions due to higher cylinder pressure, injection pressure. Reduced
friction from (possibly) higher sump temperatures. Decreased Pb in environment Improved international
competitiveness.

O. Self-Lubricating and Scuffing-Resistant Materials

Problem: Surfacing of lightweight materials for self-lubrication and resistance to scuffing. Examples
include aluminum block engine--cylinder bore surface, valvetrain components (valves, tappets, etc.),

22-6
transmission case "hot spots," and lightweight brake rotors, and air conditioning (NC) compressor
hardware.

Current approach: Use of inserts-e.g., bore liners (cast iron), valve seats, etc., and use of heavier,
wear-resistant (usually ferrous) alloys.

Needs: Understanding adhesion of surfacing layers to metals such as aluminum; modeling for mechanical
surface behavior of bimaterials couples; understanding of methodologies for selecting composite surfaces.

Time scale: 3-5 years.

Payoff: Reduced friction and energy consumption; manufacturing Simplification (in some cases).

P. Correlation Between Surface Modification and Perfonnance of Materials in Lubrication Systems

Problem: Lack of understanding of surface-preparation processes of multi phase materials and performance
in lubricated systems. Examples include NC compressors, engine cylinder bores, valvetrain componentry.

Current approach: Trial and error, past knowledge, existing tribomodels for lubricated contacts.

R&D program envisioned: Understanding of the topographic and compositional influence of multiphase
material systems and machining/finishing processes relative to the limits of perfonnance with regard to
boundary lubrication, friction, and such features as noise and vibration. Extensive use of tools suCh as
atomic-force microscopy (AFM), surface spectroscopies, etc., is envisioned.

Time scale: 5+ years.

Payoff: Highly finished, more "forgiving" mechanisms in terms of reliability, durability, and customer-
satisfaction issues such as noise and vibration. Improved product perfonnance, reduced cost, shorter cycle
time.

Q. Lifetime of Nonferrous Die Materials

Problem: The wear life of nonferrous die materials is insufficient for medium-volume applications.

Current approach: Hard-chromium plating is being evaluated; nothing else.

Needs: A wear-life-enhancement process that can be easily applied, can give increased tool life, and can
be repaired, stripped, and retreated if needed.

R&D program envisioned: Hard-chromium plating and plasma-source ion implantation appear to be
potential solutions.

Time scale: Process could be used immediately. R&D program could require 2-3 years.

Payoff: Benefits to U.S. auto-makers and other U.S. manufacturers include obtaining cheaper tooling,
faster time to market, reduced lead time, and products competitive with foreign companies.

22-7
R. Lifetime of H-13 Tool Steel Foundry Patterns Used with Molten Aluminum

Problem: Molten aluminum attacks foundry patterns and core pins made out of H-13 tool steel; this
results in many premature failures.

Current approach: Patterns sprayed with a graphite lubricant before each pour.

Needs: A protective coating that can withstand molten-aluminum temperatures without coming off, and
a method for preventing molten aluminum from wetting patterns and core pins.

R&D program envisioned: Develop/verify coating process .

N01E: Complex geometry is a special problem, e.g., transmission cases.

Time scale: Process could be used immediately. R&D program could require =3 years.

Payoff: Several industries have this problem. Some patterns cost up to $750,000. Doubling life of
patterns would produce large dollar savings and result in significantly enhanced international
competitiveness for U.S. manufacturing industries.

S. Wear Life of Large Ferrous Metal-Forming Dies

Problem: Large ferrous metal-forming dies used in current production break down, resulting in costly
downtime for repairs, scrap, and sometimes poor quality. Only a limited number of cost-effective
processes are available to improve the wear life of large dies.

Current approach: Ion-(plasma) nitriding, hard-chrome plating, and flame-hardening.

Needs: Other surface processing should accomplish the following:

• Improve tool life a minimum of two times.

• Be repairable.
• Be cost effective to apply.
• Be applicable to current tool materials.
• Preferably be a "visual" process.

Time scale: Needed immediately. R&D program might require 2-3 years.

Payoff: Reduced tooling costs, improved part quality, and improved competitive position for all of U.S.
stamping- industries.

T. Modeling of Surface-Coated Wear Materials and Adhesive Coatings

Problem: Modeling of wear of surface-coated materials and adhesion mechanisms of coatings is

inadequate for guiding future developments.

Current approach: Empirical experimental methods, which are unreliable for quantitative understanding
of adhesion or for predicting wear rates of coatings under various application conditions, including particle
erosive wear.

22-8
Needs: Accurate modeling methods and properties of coatings (especially adhesion strengths).

R&D program envisioned: Methods are needed to measure properties of surface coatings and adhesion
strengths of coatings to various substrates. Mechanisms of coating failure need to be developed at both
low and high temperatures. These results should be incorporated into a readily accessible tribology data
base such as ACTIS and would serve as the basis for reasonable model development.

Time scale: 3-5 years.

Payoff: Ability to predict component life and forestall premature failures.

22-9
 23. POLYME~-METAL(OXIDE) INTERFACES

F. 1. Boerio, University of Cincinnati, Cochairman

G. D. Davis, Martin Marietta Laboratories, Cochairman
J. E. deVries, Ford Motor Comp~y
C. E. Miller, General Motors
K. L. MinaI, IBM
R. L. Opila. AT&T Bell Laboratories
H. K. Yasuda, University of Missouri-Columbia

I. INTRODUCTION

Some of the primary objectives of surface processing are to produce strong bonds between
adhesives or coatings and substrates, to enhance the durability of bonds during exposure to service
environments, and to improve the reliability of technologies that involve surface phenomena. These
objectives must be achieved while improving the recyclability of products and reducing costs and
environmental concerns.

The end product of many surface processes is an interface between dissimilar materials. These
interfaces occur throughout the transportation and renewable energy fields and are becoming increasingly
important as performance and lifetime requirements increase. In this paper, we review the needs and
opportunities for technological advances involving interfaces and interphases-the transition zone around
an interface (from a few atomic or molecular dimensions to many thousands) where material properties
differ from those in the bulk. Our initial charter focused on metal(oxide)-polymer interfaces. However,
our deliberations have been intentionally general ·so that they could also include polymer-polymer or
ceramic-polymer interphases and are not specific as to which material is considered the substrate and
which is considered the overlayer. In a particular study, the materials and/or processes must be specified,
but our recommendations are not restricted to a given system.

Interphases are important because they control the performance of adhesive joints, composites, and
coatings. In adhesive joints and composites, stresses are transferred across the interphase. Formation of
an interphase that is mechanically weak or is vulnerable to environmental attack will result in a composite
or adhesive joint that has poor properties or a short lifetime in service. Coatings protect against corrosion
of substrates. If the interphase has poor mechanical properties or is susceptible to environmental
degradation, delamination of the coating will occur, resulting in loss of corrosion protection for the
substrate.

Interphases between polymers and metal(oxides), ceramics, and other polymers are found in
several broad classes of applications listed in Table 1. We identified several generic challenges and
problems facing industry today that can impede product and process improvements (see Table 2).

The initial stage of a new or modified product or process involves design. Among other things,
it is essential to know how the different materials involved interact with each other: Will an adhesive or
coating wet the substrate? Will the two materials adversely react with each other to degrade the
interphase? Do the two materials forming an interphase have different coefficients of thermal expansion
(CTEs) that will result in interfacial stresses during thermal cycling? Will a secondary material, such as
a mold release or unintentional contaminant, find its way to a bonding surface and degrade the interphase?

23-1
 Table 1. Sources or Applications of Polymer-Metal(Oxide),
Ceramic, or Polymer Interphases

Painted metals or plastics

Adhesively bonded structures
Composites
Encapsulants or sealants
Metallized plastics
Microelectronic devices
Sensors

Lifetime requirements for products are increasing. To reduce life-cycle costs and support warranty
policies, accurate lifetime projections based on short-term accelerated aging tests are needed as discussed
in Chapter 25.

Fabrication of a component is the next stage in its life .cycle.· For large-scale production in either
the transportation or renewable energy field, the process must be cost effective. A process that is labor-
or time-intensive might be acceptable for production of hundreds of multimillion dollar airplanes, but not
feasible for millions of multithousand dollar automobiles. Similarly, commercially feasible terrestrial
photovoltaics need much lower production costs than those intended for spacecraft. Process tolerance is
related to cost effectiveness. Stringent process controls and quality rejected components are expensive.
Conversely, broad acceptable windows for process variables allow process variability without affecting
quality. As environmental restrictions become tighter, processes involving environmentally hazardous
materials will become more costly, if not disallowed. Chlorofluorocarbons (CFCs) are scheduled to be
phased out over the next several years, and disposal of chromates and other toxic materials will become
more difficult and expensive. Alternatives to process steps involving such materials must be developed.

At the other end of a product's lifetime, recyclability is becoming a more important issue. There
will be increasing needs and requirements to recycle used automobiles and other products into new items
to conserve limited resources and to reduce disposal needs.

Table 2. Challenges and Problems: Polymer-Metal(Oxide) Interfaces

Design (system/material compatibility, lifetime predictions)

Processibility (cost effectiveness, tolerance to produces variations, environmental
acceptability, recyc1ability)
Performance (durability, strength, toughness)

23-2
 Performance of a component is probably the most straightforward of the items in Table I. Initial
properties are relatively easy to obtain and test Durability, espeCially for components expOsed to
moisture, is generally more difficult to achieve and to predict qualitatively, as discussed above.
Research Needed:

To address these challenges and problems, we have identified seven technology areas in which
there are research needs and opportunities (Table 3). Each of these areas is discussed in detail below.
Two areas (characterization and accelerated testing) are covered in Chapters 25 and 26; here we emphasize
their application for metal(oxide}:polymer interphases.

The identified are.as include basic studies in which advances in fundamental understanding are
needed to foster technological advances. More applied process improvements involving surface treatments
and polymer coating/formation methods will allow cost savings, reduction in environmental burdens,
and/or increased performance and reliability. Finally, process tolerance is specific to individual cases, but
understanding of process sensitivity is critical for product reliability and can directly affect costs.

II. INlERPHASE FORMAnON MECHANISMS

To achieve the goals discussed above, new or improved surface processes must be developed from
a fundamental knowledge of how interfaces are formed between dissimilar materials. Polymer/metal
(oxide) interphases form for many reasons. Metal surfaces are covered by a layer of oxide in which the
oxidation state of the metal ions may differ as a function of distance from the metal. The outermost
surface of the oxide may be covered by a layer of hydroxide and by several layers of adsorbed water.

Table 3. Prioritization of Research Needs (C, Crucial; I, Important; U, Useful)

Technology Areas Fundamental Research Applied R&D

1. Interphase Formation Mechanisms I U
2. Interphase Degradation Mechanisms C I
3. Characterization
a. Surface I U
b. Interphase C I
c. In-process monitoring C C
4. Surface Treatments U I
5. Polymer Coating/Formation Methods U I
6. Testing
a. Adhesion measurements U I
b. Accelerated aging testing I I
7. Process Tolerances U C

23-3
 -
Polymer systems m~y contain polymer molecules with variations in chemical composition
(copolymers and blends) and in physical structure (branches, isomers, molecular weight, and
stereoregularity). They may also contain low-molecular-weight organic compounds such as curing agents,
catalysts, accelerators, lubricants, plasticizers, coupling agents, antioxidants, and ultraviolet (UV) stabilizers
as well as inorganic fillers.

All of these factors contribute to the formation of polymer/metal interphases. Low-molecular-

weight polymeric or nonpolymeric molecules may segregate to the surface of a polymer so as to lower
the surface energy. High-molecular-weight polymer molecules may be preferentially adsorbed onto a
substrate. Low-molecular-weight nonpolymeric components may segregate to the interphase because of
incompatibility with the bulk polymer. If a low-molecular-weight compound segregates to the interphase,
it may react with the oxide, resulting in reaction products that may accumulate at the interface or diffuse
into the polymer. Polymer molecules may be adsorbed onto metal(oxide) substrates through reactive
functional groups. This will result in a lower state of cure at the interphase than in the bulk polymer.
Sputtering of metallic ions from the oxide may occur during plasma polymerization on metal(oxide)
substrates.

In the case of polymer/metal(oxide) interphases, it is essential to determine the surface chemistry

of the substrate. This includes determining the oxidation state of metal ions in the oxide, the way in
which the oxidation state of the metal changes as a function of depth below the surface, and the presence
of hydroxyl groups and water molecules on the outermost surface of the substrate. The nature and extent
of surface contaminants is elipecially important.

It is also essential to thoroughly characterize the polymer. This includes determining structural
characteristics of the polymer such as stereoregularity, isomerism, molecular weight- distribution,
comonomers, and branches. It also includes determining the presence of low-molecular-weight additives
such as curing agents, catalysts, accelerators; lubricants, plasticizers, coupling agents, antioxidants, and
UV stabilizers.

Mechanisms by which complex polymer systems interact with (oxidized) metal substrates must
be determined This includes determining the extent of preferential adsorption of high-molecular-weight
polymers onto oxidized metal substrates and the segregation of low-molecular-weight nonpolymeric
components to the interphase. It also involves determining the effect of structural variables such as
branches, stereoregularity, molecular weight, and isomerization and the effect of chemical variations, such
as comonomers, on preferential adsorption.

We need to determine the nature of reactions between components of polymer systems and metal
oxides. We specifically need to determine the extent to which oxides are etched, the nature of
organometallic compounds that are formed, the extent to which the organometallic compounds accumulate
near the interface or diffuse into the bulk polymer, the solubility of the compounds, and the extent to
which these compounds inhibit cure of the polymer. It is especially important to determine the rates at
which these various processes occur.

It is imperative to determine how processing affects the structure and properties of interphases.
When a polymer is deposited onto a substrate, processing variables such as the solvent in which the
polymer is dissolved, the rate at which the solvent is removed, and the cure temperature of the polymer
may have a profound effect on the structure and properties of the interphase. In some cases, a similar
polymer may be deposited on a substrate by several very different processes. For example, a polyimide
may be deposited onto a substrate by spin-coating a solution of polyamic acid onto the substrate from
solution and then thermally curing the polyamic acid or by vapor-depositing appropriate monomers onto

23-4
a substrate to obtain the polyimide. It is reasonable to assume that the molecular structure of the
interphase and thus its properties are very different in such cases, but little progress has been made in
identifying the differences and determining their effects on the properties of the films.

In some cases, such as plasma polymerization, the polymer is not formed until the coating
operation is carried out. In those cases, the polymer cannot be characterized prior to deposition. It is then
essential to determine the molecular structure of the as-deposited coating. Characteristics such as chemical
bonding between monomers to form polymers, orientation of polymer molecules, preferential sputtering
of metal ions from oxide, extent of thinning of the oxide, and formation and solubility of organometallic
compoundS in the film must be determined:

In the case of metaVpolymer interphases, it is essential to determine the extent of surface

segregation by low-molecular-weight polymeric or nonpolymeric components and the way in which metals
interact with those components.

Research Required:

To understand how interphases are formed and then use this information to improve processing
and products, the foilowing research is needed:

• Characterization of both the substrate surface and the overlayer

• Identification of the mechanisms by which the polymer interacts with the substrate and the changes
induced by these reactions

• Determination of the rates at which these reactions occur

• Determination of how processing affects the structure and properties of the interphase.

m. MECHANISMS OF DEGRADATION

Interphase degradation is an issue affecting all polymeric interphase systems (polymer/metal,

polymer/metal oxide, and polymer/polymer). Degradation is discussed, in general, in Chapter 25; here
we concentrate on degradation of interphases. To design more durable systems, a phenomenological and
mechanistic understanding of the processes involved in degradation is necessary. To achieve this goal,
the following approach should be considered:

Characterization of the interphase chemistry as a function of environments leading to

degradation of the system.

Determination of the kinetics and comparison of the extent of degradation to the time of
exposure.

Correlation of interphase modification/degradation to performance.

Historically, the effect of moisture has been considered the major factor resulting in decreased
system performance. The influence of water initially present and diffusing to the interphase region has
been studied comprehensively on a variety of systems. However, as new materials are developed
(especially regarding polymer/polymer interphases), new avenues for significant research exist.

23-5
Comparison of different polymer chemistries to their inherent susceptibility to interp~ase water infusion
should be correlated to performance. In addition, performance of various polymer chemistries should be
correlated to water initially present at the interphase. To achieve this, quantitation of diffusion rates and
amount of water present at the interfaces should be determined. The resultant interphase chemistry should
be related to performance. Finally, the effects of water are sometimes very localized due to clustering,
necessitating the use of spatially resolved analytical techniques to investigate this phenomenon. The
results of this type of study can be directly related to process studies by relating this information to the
moisture environment occurring in the manufacturing of these materials.

Research should also be initiated exploring the effects of other fluids on the performance of
. polymer interphase systems. A research approach similar to that discussed in the previous section can be
easily applieq to other fluid and gas-induced degradation mechanisms. The "other fluids and gases" that
should be studied are those present in the manufacturing environment, process chemistries, or service
environment. Two specific examples of research needs in this area are: (1) Solvent compatibility to
materials in polymer/polymer interfaces, specifically polymers on plastic substrates, are generally
unknown. What is the effect of solvents on the interfacial chemistry and resulting perfoqnance?
(2) Conformal coatings on sensors and .electronic devices are designed to protect these materials from
various "harsh" environments in automotive applications. What influence do various fuel formulations
and exhaust chemistries have on the interphase chemistry and, in turn, long durability of the interphase?

It has been established for quite some time that the fundamentals of corrosion in polymer/metal
(oxide) systems are based on ionic reactions. Heterogeneous redox reactions at the polymer/metal(oxide)
interphase occur as the metal is oxidized and the polymer system is reduced. Both anodic and cathodic
processes can occur in these systems. In order for these reactions to occur, water must be present within
the system, primarily at the interface. The effects of water and research needs pertaining to this subject
have already been addressed. Ionic corrosion processes are of paramount concern to the trailsportation
industry, because they are the quintessential factors that govern the corrosion life of vehicle bodies.
Extensive research has been accomplished in the study of polymer/steel systems; however, as new polymer
formulations and steel surface treatments are developed, this work should be continued In addition, as
various industries incorporate a greater amount of adhesive bonding into their products, bonding of
dissimilar metals presents new challenges in corrosion research. Dissimilar chemistries of electrically
connected materials form galvanic couples and generally accelerate the ionic reactions occurring within
the system. A systematic approach to ionic-contributing degradation, similar to that proposed in the
section dealing with moisture-induced degradation is needed. The effects of residual ionic content as well
as diffusion of ionic species resulting from environmental exposure need to be addressed.

Numerous studies have been reported concerning UV degradation of polymer and polymer
interfacial systems. This area remains of key interest to a number of industries. The incorporation of
"light stabilizers" has reduced many of the deleterious effects of UV exposure but has resulted in problems
of its own relating to stabilizer segregation and actual alteration of interfacial chemistry resulting in
reduced system performance. Indeed, the extent of degradation is dependent on the film thickness.
Therefore, research can be focused on blocking and reducing the effect of UV exposure through various
additives, modifications, and novel polymer formulations.

Radiation-induced degradation resulting from exposure to electric fields is another area that needs
additional research. Although this type of radiation is not as great a concern at this · time as UV
degradation, the effects have very serious implications to both the energy and transportation industries . .
These effects have not been well characterized, and a systematic approach to characterize the long-term
issues is necessary.

23-6
 The chemistry of the interphase region is highly dependent on temperature considerations. Cure
temperature and service temperature of polymer-related interphases can alter these interfacial chemistries.
Differing temperature schemes result in segregation of additives and components that may affect system
performance. This is increasingly evident in polymer/polymer interphases (such as paint on plastics) in
. which there may be a great difference in cure temperatures of the different paint layers and the plastics.
The result is interphase segregation of aforementioned components in the; system as well as substantial
changes in interphase chemistry. This reveals a relatively untouched field of research that needs to be
addressed.

Another area of research that needs to be addressed is the adhesive bonding of dissimilar
substrates. When bonding substrates with dissimilar heat capacities to be used in a harsh service
environment, such as automotive applications, the temperature differential may cause alteration/degradation
of the interphase chemistry. Long-term durability and system performance as a function of substrate
temperature disparities in adhesive bonding is an area of research that is relatively unaddressed at this
time. More well understood is the effect of substrates having different C1Es. If the adhesive is not
compliant enough to handle the strains induced as the dimensions of one substrate change with respect
to the other, delamination and bond failure can occur. Improved means to prevent such delamination are
also needed.

The degradation of polymer-related interphases can be highly dependent on mechanical factors

such as strain and stress. Although normally the interphase chemistries are not modified by these factors,
the adhesion performance and durability of polymer systems may be greatly affected. In many cases, the
durability will depend on the timing of a load, i.e., a cyclic stress will generally cause bond failure at
lower levels than a continuous stress. Coating and adhesive industries have given considerable attention
to these influences in the past and addressed these issues as mainly an engineering problem. In the scope
of this work, research in the degradation mechanisms should consider what changes in mechanical
attributes such as strain and stress are experienced after interphase degradation induced by these
mechanisms.

Research Required:

Many aspects of the degradation of interphases are not yet understood. The most important of
these are listed below.

• Establishment of interphase degradation mechanisms in typical service environments that include

moisture, ionic solutions and other fluids, radiation, stress, and temperature.

• Detennination of synergistic effects (positive or negative) between different components that affect
either the mechanisms or rates of degradation

• Development of means to retard interphase degradation.

IV. IN1ERPHASE CHARAC1ERIZATION 1ECHNIQUES

All aspects of understanding. engineering, and manufacturing of solid/solid interphases require.the

ability to measure the composition, chemical bonding. and structure of the components of the interphase ·
in all three spatial dimensions. How the composition, bonding, and structure of the interphase change with
time can give insight into the mechanism of interphase formation, the role of surface treatments .and
impurities, information on how interphases degrade, and the effects of processing parameters.

23-7
Unfortunately, current techniques generally pennit only limited studies of model systems or postmortem
analysis of failed interphases. Methods to monitor the formation of interphases during actual manufacture
do not exist. Thus, research into analytical techniques should emphasize nondestructive detennination of
interphase composition and chemistry, surface characterization in ambient environments in real time with
high spatial resolution, and moOitoring of interphases during manufacturing. The background and research
needs for surface and interphase characterization are discussed in more detail in Chapters 1,3-7, and 26.
Here we emphasize the needs concerning metal(oxide)/polymer interphases (Table 4).

Current methods to analyze interphases can be loosely divided into two categories, destructive and
nondestructive. Destructive methods usually utilize traditional surface analysis techniques, after ion
sputtering to the interphase, eroding away the overlayers or causing the interphase to fail mechanically
(e.g., peeling or fracturing). Traditional surface analytical techniques achieve their utility due to the
a
limited penetration length of the probe, either ions or electrons. As result, these methods require that
the overlayer be removed so that the interphase can be studied. Correlation between the mechanical force
to cause the joint to fail and observations of the interphase provide useful postmortem information.
However, the process of destroying the interphase to analyze it always complicates the interpretation of
the results.

Nondestructive techniques to analyze interphases must utilize probes that have long penetration
depths. It is the conflict between the long penetration depths of the probes and the limited thickness of
the interphase that makes development and improvement of these techniques difficult. Despite their-long
penetratio~ depths, these techniques recognize the uniqueness of the interphase, either through the
breakdown in symmetry between two isotropic phases or some unique elemental composition at the
interphase. Certain optical spectroscopic techniques such as second harmonic generation (SHG) and sum
frequency generation (SFG) can be used to study interphases between two isotropic (centro symmetric)
media. At this interphase, two photons of either the same or different energies can be converted to one
photon with the energy equal to the sum of both incident photons. Changes in the SHG or SFG signal
can be related to changes in the interphase, e.g., changes in the vibrational spectrum or changes in the
symmetry of the adsorbate. Surface-eohanced Raman spectroscopy (SERS) uses the enhancement of the
vibrational Raman spectrum in the vicinity of a rough silver, gold, or copper surface to provide distinct

Table 4. Selected Techniques for Interphase Characterization

Destructive methods using conventional surface Uquid and ambient environment methods
analysis Electrochemical impedance spectroscopy
Ion sputtering (EIS)
Abrasion Fourier transform infrared spectroscopy
PeellFracture (FTIR)
Nondestructive methods Near infrared spectroscopy (NJR)
Second harmonic generation (SHG) Spectroscopic ellipsometry (SE)
Sum frequency generation (SFG) Differentially pumped scanning electron
Surface-enhanced Raman spectroscopy microscopy (SEM)
(SERS) Process monitoring techniques
Composition-specific methods Optically stimulated electron emission
Mossbauer spectroscopy (OSEE)
X -ray absorption near edge structure X-ray or ultraviolet fluorescence
(XANES) Dielectrics
Extended X-ray absorption spectroscopy Surface reflectivity
(EXAFS)

23-8
 chemical infonnation concerning organic layers over these metals. Although the use of optical
spectroscopies to probe buried interphases is in its infancy and only well-characterized model systems have
been studied, their promising results warrant more future investigation.

Certain other techniques can take advantage of long penetration depths typical of bulk analyses and
make them sensitive to the interphase. For example, the interphase can be made compositionally unique.
Work has shown that Mossbauer spectroscopy can be used to study the delamination of paint from steel
if the steel surface is isotopically enriched before painting. Unfortunately, Mossbauer spectroscopy is
limited to systems containing tin, iron, or a few other elements. X-ray absorption techniques have shown
promise when a thin (approximately 100 A) layer of metal has a polymer adsorbed on it or is adsorbed
on the polymer. Details in the X-ray absorption edge and the X-ray absorption near edge structure
(XANES) can yield infonnation about the electronic structure of the metal. Similarly, extended X-ray
absorption fine structure (EXAFS) can help describe the local structure around the metal atoms. If the
X rays are energetic enough (the transitions deep enough), these analyses can be perfonned in air.
Unfortunately, analysis of C, N, and 0 is difficult because the penetration depth of these characteristic
X-rays is small. All of these X-ray techniques require the use of a synchrotron to get an intense source
of variable energy X rays.

Certain electrochemical techniques, such as electrochemical impedance spectroscopy, are themsel ves
techniques to study solidlliquid interphases and have been used to examine corrosion at polymer/metal
interphases. Undoubtedly other bulk techniques can be identified and adapted for the analysis of
interphases. Vacuum surface analysis·techniques such as electron and ion spectroscopies (Chapter 1) are
". mature and can provide compositional and bonding information in two dimensions. However, sample
preparation and the vacuum exposure may change the surface properties and may impede the observation
of specific effects as a function of time, i.e., contamination, surface processing reactions. Thus, it is
important to develop surface analytical techniques that can work in ambient environments in real time to
detennine the composition, morphology/structure, and/or chemistry of the surface. In some cases, such
as microelectronics, high spatial resolution will als~ be needed. Many of the techniques described above
for analysis of solid/solid interphases will apply here, but the constraints differ. Some specific examples
of techniques are Fourier transfonn infrared (FTIR) spectroscopy, near infrared (IR), spectroscopic
ellipsometry (SE), and scanning electron microscopy (SEM) operating with the sample under a partial
vacuum, but with a combination of skimmers and differential pumping to reduce the pressure in the
microscope column. Development of techniques like these will have two immediate advantages:
understanding the effects of surface processing and developing process monitors.

The development of process monitors is a neglected area. These monitors provide real-time
infonnation about the.cleanliness of a surface, the coverage or thickness of an overlayer, the degree of
cure of an adhesive, or the composition or chemistry of a reagent Such monitors have to be simple to
use and robust, and must yield unambiguous results. Often simple techniques, such as surface reflectivity,
light scattering from particles, or optical density can be adapted to the manufacturing environment Other
techniques such as optically stimulated emission (OSEE), X-ray or UV fluorescence, and dielectrics have
been successful in monitoring a system and providing real-time infonnation. However, in each case,
limitations of the techniques prevent routine, general use. As with the more sophisticated analytical
methods proposed above, their use might also be extended. As process monitors come into more common
use, better process control will result in more reliable and higher perfonnance products.

23-9
Research ~equired:

Increased understanding of polymer-metal(oxide) interphases and improvements in their performance

require that they be well characterized. Characterization needs include:

• Development of techniques capable of investigating buried interphases nondestructively.

• Improvement of methods to probe solidlliquid interphases in situ.

• Development of process monitors capable of examining surfaces and interphases in ambient

production environments and providing real-time analysis for feedback control.

V. SURFACE TREATMENTS

Surface modification or treatment of a substrate is commonly needed in order to obtain good

adhesion of a coating to the substrate. These treatments are intended to clean the substrate, remove
undesirable material (weak boundary layers), introduce desirable chemical functionalities into the surface,
and render the interphase water-resistant. ..

The optimum surface treatment depends on the nature of the substrate and coating material, the
process used to deposit the coating, environmental considerations, and the conditions under which the
coating-substrate combination will be used. For example, differerit treatments are effective for inorganic
(metal, oxide) surfaces than for organic (polymeric) substrates. Furthermore, the whole area of surface
treatments can be divided into two categories, one in which the surface is superficially modified (e.g., a
chemical etch) and one in which a discrete layer of desired material is intentionally deposited (e.g., use
of a conversion coating or an adhesion promoting layer). Also it should be emphasized here that these
treatments can be wet or dry, vacuum or nonvacuum, simple or complex. Many surface treatments are
available (see Table 5), and there is considerable interest in improving the existing ones or devising new
and improved ways to modify surfaces.

Considerable cost is frequently expended in modifying metals and other inorganic substrates for
bonding purposes, so the need for a desirable surface treatment for such inorganic substrates is quite
obvious. There is also a strong trend in the automotive industry toward using increased amounts of

Table 5. Classes and Examples of Surface Treatments

Chemical
Chemical reactions (oxidation, sulfonation, ozonation, and phosphatization)
Etching
Deposition/adsorption (LB films, coupling agents, and corrosionlhydration inhibitors)
Photochemical
Physical (plasma, UV, X-ray, laser, and ion bombardment)

Mechanical (abrasion, casting against other materials, and surface texturing e.g., lithography)
Metallurgical (cladding)

23-10
plastics. which pose special requirements and challenges for adhesive bonding. Some of the needs and
challenges are listed below:

Treatments should be environmentally acceptable. In the future. strict regulations will be

imposed with respect to disposal of chemicals and recycling treated materials. Surface
treatments should pose minimal disposal problems. and treated materials should be
recyclable.

The effects of surface treatment should persist over a . period of time. It should be
possible to treat the surface of a material. store or transport the material. and use the
material later without the surface treatment losing effectiveness. For example. the effects
of plasma surface modification are lost after a period of time, but the time depends on a
number of factors.

Surface treatments should be fast, cost-effective, simple to perform. and applicable to

large, irregularly shaped parts.

Treatments should be compatible with the mode of deposition of the coating and
processipg conditions involved.

Surface treatments should improve both dry and wet adhesion. They should also render
the bond durable over the life of the coating.

Research Required:
" .
Research efforts should be directed toward exploring alternative surface modification
techniques/processes to supplement or replace those that currently exist but have certain inherent negative
traits. More specifically, research should be directed toward:

• Determination of the characteristics and properties of surfaces before and after treatment

• Evaluation of the effectiveness of various surface treatment techniques

• Establishment of the mechanisms and kinetics by which the effectiveness of a treatment is degraded

• Identification of the mechanisms and optimization of new techniques for surface modification

- UV sensitization

- plasma surface modification

- laser surface treatment

surface modification by microorganisms

- self-assembled monolayers

• Determination of the effects of surface modification by adhesion promoters and the mechanisms by
which adhesion promoters deposited by different methods function.

23-11
 VI. NEW METHODS FOR POLYMER DEPOSmON

To tailor interphases for specific applications. it is necessary to develop new methods for
. depositing polymeric films on metal. ceramic. semiconductor. or polymer substrates. Plasma
polymerization is an extremely attractive technique for such purposes.

A. Plasma Polymerization

Plasma polymerization refers to the vacuum deposition and polymerization process that utilizes
reactive species created in a plasma state and the surface bound reactive species created by the interaction
of the surface exposed to the plasma state. Plasma polymerization has many advantages over conventional
methods of coating or film application. One unique advantage of the technique is its capability for
creating compositionally and structurally graded interphases that bridge two distinctly different materials.
Adhesion of plasma polymerized coatings to substrates is usually outstanding. Since deposition and
polymerization occur simultaneously. a film deposited on an organic polymer substrate is essentially
covalently bonded. Although adhesion to an inorganic substrate (metal. ceramic, and glass) by covalent
bonds is unlikely. tenacious adhesion to such substrates can often be obtained by virtue of interphase
atomic mixing.

hi plasma polymerization. the deposition and polymerization processes are combined so that the
problem of nonwetting of the substrate by the coating or coating solution is eliminated. Plasma
polymerization is a dry process that does not require the use of solvents. Consequently, the process yields
minimal effluents. and the products contain few volatile organic compounds.

Plasma polymerization is usually carried out in a closed environment (vacuum, reduced pressure.
or sealed environment) and can thus be combined with other important processes such as cleaning. etching,
oxidation or reduction of the surface, and functionalization of the surface, into essentially one operational
step. Polymers can be deposited without exposing the cleaned or modified surface to the atmosphere. thus
reducing the chance of recontamination or inadvertent chemical reactions such as oxidation. Furthermore.
polymers prepared by plasma polymerization have significantly different molecular structures than
conventional polymers, which are prepared from the same monomers and applied from solution or the
melt. Most plasma polymers are extensively cross-linked and are thus insoluble and infusible and have
outstanding barrier characteristics.

B. Other Vacuum Deposition Techniques

Although plasma polymerization is a very important alternative to conventional solution techniques

for deposition of polymer films, other techniques, such as parylene polymerization, in which thermal
decomposition of dimers of para-xylylene derivatives is utilized to deposit a film on a substrate, and vapor
deposition polymerization. in which monomers are adsorbed onto a substrate and thermally polymerized,
are also promiSing processes. In parylene polymerization, a discrete, well-defined reactive species is
created by thermal cracking of the starting material (dimer). The mechanism of deposition and
polymerization is believed to be similar to that in plasma polymerization. Because of the well-defined
chemical structure of the reactive species, the resulting polymers are serilicrystalline (in contrast to plasma
polymers, which are amorphous), and contain linear segments of considerable length. Due to
topographical crosslinking, as-deposited polymers are insoluble and infusible in most cases. Because of
their semicrystalline nature and the presence of crosslinks, the polymers have excellent dimensional
stability and chemical resistance.

23-12
 The reactive species have a specific reactivity toward similar chemical structures. Consequently,
adhesion of parylene films to many surfaces is poor. The lack of chemical bonding to a substrate can be
overcome by plasma pretreatment or deposition of a plasma polymer onto an inorganic substrate (metal,
ceramic, glass, and semiconductor). By comparison, parylene deposition results in films that have an
. exceptionally high degree of penetration into small spaces and excellent mechanical anchoring to porous
substrates.

In vapor deposition polymerization, monomers are adsorbed onto a substrate where they react to
form a polymer film or an intermediate, which is then polymerized thermally. This technique, which has
been applied to polyimides and polyamides, does not require the use of solvents. Thus, vapor, deposition
polymerization enables health and safety problems associated with solvents used to cast polymer films to
be eliminated. It also enables problems related to solvents entrapped within solution-cast polymer films
to be eliminated However, vapor deposition polymerization can result in films having molecular
structures that are considerably different from those of films obtained by casting polymers from solution
onto substrates.

Research Required:

Research on plasma polymerization and vapor-deposition polymerization should be directed

toward:

• Development of new methodologies of plasma polymerization to improve:

...
- Distribution of polymer deposition on a large surface

- Deposition in recessed areas

- Adhesion and passivation of surface

- Modification of polymeric substrates without degradation

• Development of low-temperature plasma torches that can be used in robotic spray coating

• Establishment of robotic operation in vacuum

• Determination of the effects of processing variables on the molecular structure and properties of
vapor-deposited films

• Comparison of the structure and properties of vapor-deposited polymer films to those of solvent-cast
films. .

. VII. TESTING

Adhesive bond strengths are commonly measured by tests such as lap shear, peel, T-peel. climbing
drum. button pull. etc .• depending on the materials and the anticipated Stresses on the bonded component.
Several variations of each test have been developed and for many applications. these tests are well
established and adequate. However. these tests do not provide information in two areas of interest:
interphase bond strength and nondestructive bond testing. While the interphase bond strength plays a
factor in all the tests mentioned above. energy dissipation within the bonded materials as they deform also

23-13
contributes to the measured value and, in many cases, can dominate the measurements. To improve our
understanding of interphase fonnation' and degradation mechanisms, a means to measure and/or predict
interphase bond strength based on the chemical and physical bonding occurring at the interphase is needed.
Such knowledge would allow improvements and optimization in bond perfonnance from first principles
instead of the empirical approach currently used.

In the best of worlds, a means to measure bond strength without disrupting the bond would be of
great advantage-actual bonded components could be tested prior to being placed into service to assure
bond performance. The state of the art of testing will need significant improvements before such
inspection becomes possible. A more feasible, but not currently possible, inspection would be the
detection of weak and kissing unbonds in which the two materials are in intimate contact with each other,
but whose bond will not allow significant transfer of stresses from one to the other. Current
nondestructive evaluation (NDE) techniques, such as ultrasound, radiography, eddy current, and
thermography, rely on a separation between two materials and detect the gap between them. Weak and
kissing unbonds do not have a gap and, hence, are not detected until they separate. If this happens during
service, failure of the bonded component may occur. Detection of weak and kissing unbonds in the
production facility would increase reliability of the component and potentially could allow weight, size,
or cost improvements as product variability is decreased.

The projected lifetime of a bonded structure or the durability of an adhesive joint is commonly
determined using accelerated aging tests. For most components, lifetime requirements are too great and
material/process advances too rapid to allow real-time testing. Several accelerated tests are available to
allow real-time testing. These are discll..')&ed in another chapter and will not be reviewed here. Rather,
we will briefly present some of the issues pertinent to polymer-metal(oxide) interphases.

The key potential danger in an accelerated test is that the degradation mechanisms will differ from
those experienced in the service environment. A classic example is an egg-if a hen incubates her egg
for 21 days at 103°F, a chick reSUlts, but if the same egg is placed in boiling water for 10 minutes at
212°F, a hard-boiled egg results. Thus, it is crucial to ensure that the degradation mechanisms in the
service environment and in the accelerated test are similar.

Screening tests of materials are perhaps the simplest types of tests. As a system is fabricated and
becomes more complicated, test conditions become more critical. Does one component affect the
degradation of another? An example of a beneficial effect would be paint reducing the degradation of the
metal substrate; an example of a detrimental effect could be road salt reacting with the galvanized steel
in a car to deteriorate nylon fuel lines.

The configuration of a part can lead to locally severe environments under typical service
conditio~. _Crevices or cracks where moisture can accumulate provide a more severe local environment
than a vertical flat surface where water runs off. Stresses experienced by one part must also be
considered as part of the overall environment In general, a stressed component will fail before an
unstressed component, and a cyclically stressed component will fail before a statically stressed one.

Improvements in the ability to rapidly determine relative lifetime ranking of components would
be a valuable but incremental .advance in technology. The ability to accurately determine the (minimum)
lifetime of a structure would be a major advance in technology for a wide range of industries.

23-14
Research Required:

The research needs in accelerated testing are presented in more detail in chapter 25. From the
perspective of polymer-metal(oxide) interphases, the testing needs include:

• Development of methods to measure interphase bond strength or toughness with contributions from
the bulk materials.

• Development of methods to nondestructively measure bond strength or, at least, detect weak and
kissing unbonds

• Development of methods that accelerate the aging of an interphase without changing the degradation
mechanisms

• Establishment of a means to determine the acceleration factor of a test.

VIn. UNDERSTANDING EFFECTS OF PROCESS VARIABLES ON INTERPHASE PROPERTIES

Processing variables commonly control the physical and chemical properties of an interphase and,
hence, the performance of a structure. Interests in processing have both basic and applied aspects. From
a fundamental point of view, a process controls how an interphase is formed. When a polymer is
deposited onto a substrate, processing variables such as the solvent in which the polymer is dissolved; the
rate at which the solvent is removed, and the curing temperature of the polymer can have a profound
effect on the structure and properties of the interphase. In some cases, as we have seen, similar polymers
may be deposited on a substrate by several very different processes. It is reasonable to assume that the
molecular structure of me interphase and thus its properties are very different in such cases, but little
progress has been made in identifying the differences and determining their effects on the properties of
the films.

From a manufacturing point of view, processing is the key to production: Processing governs the
performance of the system, its reliability, and its cost. Knowing how changes in a processing step or a
processing variable affects each of these, allows an engineer to optimize the process for a particular
application. Major factors determining the fabrication cost and the capability to manufacture a part are
the limitations for each process variable; a process that requires stringent controls on a process variable
will be more expensive than a tolerant process. Table 6 lists some of the parameters that might need to
be monitored to ensure adequate control of the process.

Table 6. Process Parameters with Potential Monitoring Needs

Substrate cleanliness Moisture content

Degree of cure Solid/vehicle ratio
Thickness Appearance (glosS/color)
Uniformity Solution pH
Viscosity Material contamination
Mix ratio

23-15
 Inevitably, there will be instances when the process falls outside the process window. In most
cases, when this occurs, the engineer has insufficient information for proper disposition of the part. Is the
performance so degraded that the part must be scrapped? Is the resulting performance still adequate for
use? Can the part be reworked to obtain adequate performance?

Historically, it has been common practice to establish the magnitude of process parameters
empirically, and once the product attributes appear satisfactory, no further systematic studies are made to
explore the limits and interactions of the process parameters. Thus it is not known if performance falls
off dramatically at a certain point or if performance remains constant or slowly degrades as the process
parameter varies further from specifications. Additionally, it is likely that process interactions depend on
multiple variables so that an acceptable process window for one variable will depend on other variables.
The empirical approach often results in unnecessarily rigid process specifications and often impacts the
competitive capability of the product.

Optimum use of process windows once they are established involves process monitoring with
active feedback control to control and verify that the process variables are within acceptable limits.
Potential techniques and requirements for monitoring were discussed under characterization earlier in
Section IV and in chapter 26 on surface characterization.

Research Required:

The ability to determine the strength and other mechanical properties of polymer-meta1(oxide)
interphases is critical to improvements in their performance. Some research needed in this are~ !s

• Development of an understanding of how changes in processing affect interphase formation and

degradation

• Development of an understanding of how process variables, either singularly or in concert, change

the performance of a given system

• Development of the means to monitor the important variables and provide feedback to the process
to optimize performance, reliability, and cost

IX. SUMMARY AND CONCLUSIONS

Interphases between polymers and metals or their oxides, ceramics, and other polymers are
commonplace in the transportation and renewable energy fields. The properties of these interphases can
govern the performance of the structures and devices that contain them. We have identified several
challenges and problems limiting improvements of these properties~ Technology areas in which research
is needed to advance interphase properties include: interphase formation and degradation mechanisms,
interphase characterization, surface treatments, polymer coating/formation methods, testing, and process
tolerance to variability. Each of these areas has been discussed in detail and prioritized with regard to
fundamental research and applied research and development

23-16
 24. TIlE IMPACT OF SURFACE PROCESSING ON TIlE FABRICATION AND
PERFORMANCE OF THIN-FILM, MULTILAYER SOLAR COLLECTORS

R. Nuzzo, University of lllinois at Urbana-Champaign, Chainnan

C. Duke, Xerox Webster Research Center
K Chaffee, Edwards Air Force Base
M. Kassner, Lawrence Livermore National Laboratory
R. Pitts, National Renewable Energy Laboratory

I. INTRODUCTION

The purpose of this chapter is to provide a context for selecting research and development
activities to achieve national goals in solar energy production. The details of these goals appear elsewhere
[1]. Specific considerations in this session deal with issues in thin-film, multilayer solar collectors, which
include photo voltaic (PV) solar cells, glazings, and reflector materials. Expanded descriptions of these
components and goals for their development have been described previously [2-5].

The scope of our considerations encompasses the impact of surface processing on the fabrication
and performance of encapsulated multilayer components for use in solar power generation and energy
conservation. "Performance" is a generic term encompassing several figures of merit:

• Functionality (e.g., fill factor, efficiency for a solar cell)

• Cost

• Lifetime.

"Components" consist of two types:

• Electrically active = active (e.g., p-n junction)

• Electrically inactive = passive (e.g., mirror, encapsulant).

"Power generation" encompasses both the solar thermal and solar electric (PV) systems.
Photochemical systems are described in Chapter 28 of this volume.

"Energy conservation" encompasses devices for thermal energy management [6].

The following sections describe the technical context, research strategy, and technology trends
relevant to thin-film, multilayer solar collectors. Promising oppormnities for the application .of surface
processing to the fabrication of multilayer devices are discussed next. Finally, a synopsis of the
opportunities that exist in this technology area and typical examples are presented.

II. mCHNICAL CON1EXT

Active components (ACs) involve the photogeneration and electric field induced motion of
charges. In a PV cell, the active components are those in which a photovoltage is induced by the
absorption of light. This encompasses only a part of the total structure of the cell, as is illustrated in
Fig. 1. In electrochromic devices, the active components are those that participate in electron ion motion

24-1
and the associated changes in optical properties. These changes are induced by an external electric field.
A representative device is illustrated in Fig. 2.

The passive components (pes) we are concerned with include, among other items, mirrors, lenses,
windows, and encapsulants. For PV arrays, PCs include the structural components of the modules
themselves (Fig. 3). For mirrors, they include the flexible reflector films, but not the mechanical support
structures (Fig. 4).

A central concept pertinent to the role of interfaces in active multi component structures is the
profound effect of small amounts of trapped charge at these interfaces on device perfonnance. For
example, small amounts of corrosion at the metal-semiconductor contact may contribute a significant load
to the cell, destroying its capability to meet design criteria (Fig. 5). Another example is the scavenging
of ions in electrochromic windows by interfacial defects, which leads to a loss of optical switching
(Fig. 6).

Multiple classes of pertinent phenomena in these systems are:

• Diffusion among contiguous layers (e.g., metal/semiconductor contacts), where diffusion barriers can
be constructed

• Recombination centers at heterojunction interfaces in PV cells

• Grain boundary diffusion

• Ion trapping at interfaces in electro chromic cells.

A strong emphasis of our discussions was addressing how research could directly aid the
development of engineering prototypes nearing commercialization. The critical issues affecting the future
development of these technologies, including questions of design, materials selection, cost, and long-term
perfonnance, are well suited for designation as targets for basic and engineering research. We feel an
overarching strategy for portions of this research program should be to identify the microscopic origin of
macroscopic failure modes and, hence, surface processing means for mitigating these failures.

As for passive components, a central concept is to identify chemical (atomistic) phenomena that
limit the life of the component (over times of the order of decades). The degradation is exacerbated by
"hostile" environments (ultraviolet (UV), elevated temperature, O2, ~O, pollutants, soilants, hail, thennal
cycles, etc.). For example, the PV module must be able to withstand the mechanical stresses of hail
impact, and the optical surface must not be degraded by wind, soil, rain, and snow. Reflector materials
and interfaces within them must not corrode over the service lifetime. Oasses of pertinent phenomena
are interdiffusion, mechanical damage (including residual stresses and installation damage), and chemical
stability.

The research strategy is the same as for the active layers. The microscopic origin of macroscopic
failure modes must be understood, and the fundamental limitations of choices of materials systems (glass
versus polymer versus metal versus multilayer metal, etc.) must be determined so that the degradation
mechanisms can be mitigated over the lifetime of interest.

Opportunities for improvement in both the active and passive components may exist as a result
of recent progress in technology. Examples of such technical advances are the fabrication of superlattices,

24-2
 plasma-deposited network glasses (a-C), liquid crystalline polymers, and rapid thermal (surface specific)
processes.

III. NEEDS AND OPPORTUNITIES FOR RESEARCH

A. Interface Modification

Perhaps the greatest opportunities for research lie in the general area of rational interface
modification. The identification of specific component failure modes will often require modifications to
. be made that do not involve directly the bulk materials employed. Specific examples are presented in the
areas of both active and passive components. PV devices can interact adversely with the lIletallization
layers. Rational methods for modifying the metal-device contact are suggested by the hierarchical
approaches now commonly employed in microelectronic device and multichip module assemblies. Signifi-
cant opportunities exist for developing nonelementary multilayer metallizations that will improve lifecycle
characteristics of the active components in a system architecture [6]. The design rules for PV systems are
likely to be modest by the standards defined by microelectronics technologies and, as a result, considerable
simplification may be possible that can help meet the cost constraints under which viable commercial
technology must operate. .

Assembled system architectures will likely involve numerous interfaces with polymeric materials
(present either as structural andlor mechanical mediators, package constituents, and barrier layers) [3,4,5,7].
These latter materials are likely to be selected on the basis of bulk properties (e.g., resistance to gas
permeation, viscoelastic properties, etc.). Significant improvement of the durability of multilayer
architectures will require significant progress in improving the adhesion properties of the relevant
interfaces [7]. Powerful methods are available for the rational modification of organic material interfaces
with an objective of improving adhesion (this volume, Chapter 9) . . Gas plasma or chemical treatments are
well-known methods in this regard Microstructural modifications of materials interfaces by molecular
self-assembly and adsorption methods also offer great promise for constructing thin interfacial layers of
desired function and structure, layers imparting the desired adherent properties to heterogeneous interfaces
without obviating the intrinsic advantages inherent in the bulk material properties (this volume,
Chapters 17, 18, and 29). Indeed, an improved general understanding of adhesion in metal-organic,
organic-inorganic, organic-organic, metal-metal, me~-inorganic, and other solid-solid interfaces is an area
of considerable national need, having implications far beyond the specific technologies with which this
report is explicitly concerned [7]. Surface processing and related sciences offer the potential of making
dramatic contributions in these very important areas.

B. Patterned/Selective DepoSition

Current methods of microelectronic device fabrication can be defined as being largely extractive;
materials are deposited nonselectively and removed from areas where they are not wanted. Considerable
process simplification and elimination of elements of the waste stream could be realized if cost-effective
methods of selective deposition could be developed. These processes, once initiated, are chemically
amplified by the complex mechanistic processes that define the reactive ·solid-ambient groWth surface.
The least expensive selective depositions currently use electroless plating (this volume, Chapter 10), a
process typically limited to metals (e.g., Cu, Ni, and Ag). The specific requirements of a system
architecture may require or be enhanced by depositions that can only be effected from the vapor phase.
Surface processing concepts could powerfully enable process designs conceived around selective chemical
depositions. Progress in this area will require that progress be made both in identifying novel chemical
precursors, which cleanly and efficiently yield the desired solid phases, and in defining strategies that ~ill
effectively initiate their spatially defined deposition.

24-3
C. Electrochromic Windows

Electrochromic windows are active devices for effecting energy conservation and management [3].
Considerable progress has been achieved in devising suitable applications for such technologies in both
buildings and transportation systems. Current designs for such systems, an example of which is shown
in Fig. 7, have effectively negated any prospects for commerCialization in less than 5 years. As shown
in the figure, electrochromic windows are comprised of a multilayer thin-film architecture supported on
architectural glass. The very aggressive electrolyte incorporated in this design suggests the considerable
need existing to find better and safer materials for the construction of such devices. The myriad of
interfaces that are present in such devices also suggest that considerable research effort is needed to
understand the importance of interfacial properties ill: the performance and durability of these systems.

D. Novel Reflector Materials

Forming multilayer supeclattices is a recent research area of potential importance for solar
collectors. Supeclattices have been widely studied for their unique electrical and mechanical properties.
By fabricating multilayer metal fIlms of suitable composition and thickness (e.g., alternating layers of a
good reflector like Ag and reactive transition metals), it should be possible to generate highly reflecting
films exhibiting exceptional mechanical and chemical stability.

Eo Enhanced Stabilization of Polymeric Materials for Solar Energy Applications

Materials failures in the bulk can be accelerated by species derived from ·surface reactions. There
are many well-known examples in which the dissolution of metal ions (the ions generated reactions with
H20 and O2 , for example) into a polymer can catalyze its decomposition in bulk [8]. Polymeric substrates,
overcoats, and superstrates figure centrally in current high-performance, low-cost reflector designs [9].
The analysis of chemical reactions occurring at the buried interfaces presents a significant experimental
challenge toward which research might reasonably be directed [10]. Additional research needs and
opportunities atpolymer/metal (oxide) interfaces are given in Chapter 23 of this volume.

F. Surface Processes of Active PV Components

•
One of the major issues that needs to be resolved in developing specific device properties is the
control of electron-hole pair recombination velocities as a function of the device material processing. The
presence of defects, either in the bulk or at the device interfaces, can provide trap sites that will diminish
the electron-hole pair lifetime and decrease the carrier density. Although the problems of internal traps
are best solved by the semiconductor growth processes optimized to control intrinsic lattice defects and
impurity materials, the surface traps, because of the accessibility of the surface, exhibit the possibility of
control by chemical removal. For example, surface traps on a GaAs (100) surface can be dramatically
reduced by reaction with sulfide ions, and recent work indicates that reaction with organosulfur compounds
offers additional possibilities [11]. Plasma treatments also provide passivation. Surface modifications are
thus expected to make important contributions to the enhancement of active component properties,
including such notable benchmarks as cell efficiency.

G. Novel Materials for Solar Power Applications

Considerable opportunities exist to adapt new high-performance materials derived from other
technologies to .systems for solar energy production and management. Particularly intriguing examples
are offered by such items as protective coatings obtained by the plasma polymerization of network glasses
(e.g., amorphous carbon) or the greatly enhanced barrier properties and toughness afforded by liquid

24-4
crystalline polymers. The latter materials, representative of broader classes of high performance polymers,
have significant potential to improve the performance of thin-film architectures, given the great flexibility
of molecular synthesis. The cost impact of these material choices can be mediated by employing them
as coherent, high-quality thin films (Le., films of low mass coverage). The engineering associated with
such applications is not broadly understood, especially with respect to chemically and topographically
complex substrates, and will require the collaboration of interdisciplinary efforts to find solutions to
problems of materials choice and manufacturability.

H. Mechanical Stability of Solar Multilayers

The use of multilayer structures for solar reflectors, PV devices, electrochromic windows, etc.,
implies the use of vapor-deposited thin films on dissimilar materials. Examples are silver deposited on
polymethylmethacrylate (PMMA) for reflectors, and amorphous siliconlpolycrystalline-metal interfaces in
PV devices. One important consideration in the use of multilayer structures is the existence of stresses
that can lead to damage or time-varying performance [12]. The stresses can be residual stresses
Originating from the fabrication process or stresses arising as a result of thermal excursions during service.
Depending on the nature of the interface, residual stresses may arise from coherency or from the service
temperatures being different from the fabrication temperatures. Finite-element-method (FEM) analysis of
adherent thin films subjected to thermal excursions reveals that significant in-plane shear and axial
(perpendicular to the bonding plane) stress may develop as a consequence of different coefficients of
thermal expansion.

The residual stresses may cause time-dependent plasticity failures at ambient as well as at elevated
temperatures. This mode of failure may occur by (although it is not restricted to) time-dependent plasticity
leading to cavitation and ductile microvoid coalescence. Residual stresses can also lead to enviro.nmentally
induced fracture such as stress corrosion cracking (SCC), hydrogen embrittlement (HE), or metaI-induced-
embrittlement (MIE). An additional mechanical complication may occur with repeated thermal excursions
during service of the multilayer (consisting of bo~ active and passive components). The differences in
thermal expansion coefficients of the components will lead to alternating mechanical stresses. These
alternating stresses can lead to the failure processes described above for "monotonic" loading. More
insidiously, the cyclic loading may lead to plastic deformation within the interlayers or interfaces that leads
to lower stress fatigue-type failures.

The vulnerability of multilayers to these failure mechanisms can, of course, be determined

experimentally, a process that may require lengthy and extensive'testing to verify reliability for a variety
of candidate multilayers, environments, thermal histories, and processing conditions. A useful complement
to a purely experimental approach is comprehensive stress analysis. Residual stress analyses (perhaps
using X-ray measurements) together with a prediction of the variation of the thermal stresses with
temperature permit an estimate of the stress state evolution during service. Estimates of the vulnerability
to environmentally induced and brittle fracture are possible. Naturally, plasticity relaxes the stress and
can lead to other damage. Constitutive relationships for multilayer components could predict the stress
relaxation and plastic strain levels, thus providing insight into the potential vulnerability to failure by
monotonic and cyclic loading.

We emphasize that because the interfaces are vulnerable to failure, some form of modification of
the interfaces may lead to longer lifetimes. Strategies for enhancing durability while maintaining
performance should be examined.

24-5
1. In Situ Diagnostics for Manufacturing Processes

The impact of surface processing on the materials used in technologies for energy production and
conservation needs to be monitored in situ in a nondestructive way to provide process control. The
important criteria for adhesion, electrical properties, and nucleation and growth of adlayers are the
morphology or structure and composition of the surface. Another critical area in multilayer devices is the
role of the individual component films (structure-function relationships) in determining the overall
mechanical integrity of the device.

The structures of concern here are generally layers deposited and modified in vacuum by ion beam
and/or plasma techniques (this volume, Chapters 12, 13, 15, and 16). The process control parameters to
be considered include surface preparation, temperature, bias voltage, plasma composition, residual gas
composition and base pressure, and deposition pressure and rate. (Implicitly included is reactor design.)
Through manipulation of these parameters, the surface and thin-fIlm properties can be adjusted in a
controlled way to yield complex structures with specifically designed properties. Thin films of polymers
are .also likely to be of considerable interest, and the analysis of coating and bonding processes will
present different but equ3:lly demanding challenges.

Research opportunities exist in two areas. The first of these is the development of manufacturing
diagnostics based on surface and plasma analysis techniques that operate both in real time and in situ.
The characteristics of the probes will depend very strongly and sensitively on the class of material or
deposition process being monitored. In the second area of research, the techniques developed above must
be integrated into automated process controls for manufacturing. Specific directions and evaluations of
trends for automated process control are given in Chapter 26 of this volume.

J. Accelerated Life Testing (ALT)

Accelerated life testing is essential for exposing weaknesses in thin-film multilayer solar collectors.
It serves a number of functions such as securing a relative ranking of several competitive designs or the
comparative stability of the same design and fabrication by different manufacturers. Mechanistic work
at a molecular level is an essential complement to ALT. The needs and opportunities in ALT and how
they relate to this chapter are given in Chapter 25, this volume.

REFERENCES

1. Photovoltaics Program Plan, FY I99I-FY 1995, DOFJCH10093-92, DE 91002139, October 1991.

(Available NREL, 1617 Cole Blvd., Golden, CO 80401).

2. G. Cook, L. Billman, and R. Adcock, Photovoltaic Fundamentals, DOFJCH10093-117, DE 91015001,

September 1991, and references therein; NREL preprints for the 22nd IEEE PVSC, E. Nelson, Ed,
NRELITP-210-4567, October 1991. (Both available as in Ref. 1.)

3. A. W. Czanderna and C. Lampert, Evaluation Criteria and Test Methods for Electrochromic
Windows, SERI!IP-255-3537, July 1990 (available as in Ref. 1); Large Area Chromogenics:
Materials and Devices for Transmittance Control, C. Lampert and C. Granqvist, Eds., Vol. IS 4.
SPIE, Bellingham, W A, 1990.

4. Basic Research Needs and Opportunities at Interfaces in Solar Energy Materials, A. W. Czanderna
and R. Gottschall, Eds., Mat. Sci. Eng., 53, 1 (1982).

24-6
5. Solar Energy Materials, .1 1 (1980); A. W. Czandema, Solar Energy Materials, .2., 349 (1981);
Silver/Glass Mirrors for Solar Thermal Systems, SERIlSP-271-2293, June 1985 (available NTIS,
Springfield, VA).

6. 1. R. Arthur, Jr., et al., op. cit., Ref. 4, p. 137.

7. F. M. Fowkes, et al., op. cit., Ref. 4, p. 125.

8. H. H. G. Jellinek and H. Kachi, Eds., Degradation and Stabilization of Polymers, Elsevier,

Amsterdam, The Netherlands, 1989.

9. P. Schissel, G. Jorgensen. and R. Pitts, in M. E. Arden, S. M. A. Burley, and M. Coleman, Eds.,

Proc. 1991 Solar World Congress, Vol 2, Part n, Pergamon Press. Elmsford. NY, 1991. p. 2076.

10. S. Gaarenstroom et al .• Chapter 26, this volume.

11. S. R. Lunt, G. N. Ryba, P. G. Santangelo, and N. S. Lewis, 1. Appl. Phys., 1Q, 7449 (1991).

12. P. S. Alexopoulos and T. C. O'Sullivan. Mechanical Properties of Thin Films, Annu. Rev. Mater.
ScL, ~ 391-420 (1990).

24-7
 J8_~-Light ---+fI(

Antireflection coating - - - - - ,

Junction formed between

two semiconductor
materials of opposite
conduction types
Substrate-----'
Ohmic contact --~----'
Bottom p-type "Absorber'--_---' L - - -_ _ _ Top n-type "Window"
layer formed by second layer formed by first
semiconductor material semiconductor material

Figure 1. Typical photovoltaic solar cell

Glass/plastic substrate
-
+
I

Transparent conductor. e-
I
I

Low
Electrochromic e- A+ l
v'oltage Ion conductor/ Bleaching Coloring
electrolyte
source
Ion storage A+

Transparent conductor
-
+
I

Glass/plastic substrate

Figure 2. Schematic of an electrochromic window

24-8
 MODULE DESIGN AND DEGRADATIVE REACTIONS/PROCESSES
Photo-thermal degradation of polymers (pottants, covers,
screens, adhesives)

®--e Cover Catalyzed degradation polymerslM or oxides; interdiffusion.

Penneation ofH 2°,°2, other gases, into the

2 module.
M
-
Electrochemical corrosion, corrosion, Einduced or e-
injected pottant degradation, delamination of M or other
components.

® Accelerated aging and lifetime predicti<?D.

o Cover plate modification

® Soiling of cover plate

Module encapsulation
system design. fabrication.
and evaluation.
® Electrical isolation of cell string and other module
components.
@ Module prototype development

Figure 3. Cross-section of a solar cell in an encapsulated PV module and some key durability issues
 Front
coating Paint

m
8
(!) Silicon
6
(a) Grain
Moisture i
... ..41 I.-.I~
1000 A
r
Temperature I' 1-- 2
1.
Ambient gases
0.1
mm
Airborne

- particulates ii
Polymer
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at Sll....
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en
o
Hail
Metal
Adhesive
en (b) Grain
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Fe FeFelM ..
C AIKll
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Harmful
radiation SIO \.M"
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°KLL

Hard Back o 400 800 1200 1800 2000

coat coating Electron Energy (eY)

Figure 4. Schematic of a silvered polymer mirror Figure 5. Impurities at grain boundaries in silicon used for
PV cells
 ').. (nm)
3105 1035 621 444
3.2 0
;n
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Single crystal "'
0
2.8 (9
<
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0.8

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0
0.4 1.2 1.6 2.0 2.4 2.8
E(eV)

Figure 6.. The transmittance of an electrochromic window in the bleaehed and darkened states

Figure 7. Contemporary two-pane glass window in which a Lo E coating is deposited on the #2 surface.
In future energy-saving windows, the coating may consist of semitransparent PV materials
and/or an electrochromic device.

24-11
 Low-e Coating
- .-'\

I..J,I--- Zinc oxide (35 nm)

C/)
C/) a4--- Silver (10 nm)
til
C)
f'*---Zinc oxide (35 nm)

Lv'
80 nm

Thin Film a-Si PV Cell

Transparent conductor (500 nm)

p-type a-Si (10 nm)

Ul At-::==:-=E:=:::::::::::~~3-- Intrinsic a-Si (500 nm)

Ul
co ---
a -It":-=-=---=--=-_- -=-=-=-1;;;;;;;;;l-
---
n-type a-Si (1 0 nm)
,D---:=---=~~--=--_--jj~:I---- Aluminum (100 nm)

'~------~v~----------~/
1120 nm

Thin Film, Two-Terminal, Multijunction PV Cell

7)77;o=:~t:~~~~~§~~~~- Transparent conductor (500 nm)

AI=====+';;;;::;====+";;=~~~~=F=r- p-type a-Si (10 nm)
1=~~~~~P~~§:~Cl3-lntrinsic a-Si (200 nm)
Ul
Ul (300 nm)
co
a 1==j:::~~::t~~===-~~~~- n-type a-Si (10 nm)
==
1===t====:tb~~~~~=t-lntrinsic a-Si 1 _xGe x (500nm)

L-1:~~~~a~E~~~t~8~~~~t- Aluminum (100 nm)

\lr--------------'
1640 nm

Electrochromic
Coating

7~t====t-1====:f~~~~t-- Transparent conductor (450 nm)

t=====r-t:====~7~~:t- Electrochromic layer (400 nm)
Ul
Ul
co t - - -- ----1 +=========j:4~L,L.:.L,.4-- Ionic conductor (1 00 nm)
a
t:=~~~~~~4- Counter electrode (400 nm)
~'-7'-+-- Transparent conductor (450 nm)

\~--------------~\lr--------------~'
1800 nm

Figure 8. Relative thicknesses and typical components in Lo E glass, a-Si:H PV, and thin-film PV
multilayers, and an electrochromic window

24-12
 25. ACCELERA'IED LIFE 1ESTING OF DEVICES WI1lI SIS, SIL, AND SIG INTERFACES

Richard M. Fischer, 3M Company, Cochairman

Warren D. Ketola, 3M Company, Cochairman
Jonathan Martin, National Institute of Standards and Technology
Gary Jorgensen, National Renewable Energy Laboratory
Elaine Meetzel, B F Goodrich
Udo Pernisz, Dow Corning Corporation
Gene Zerlaut, SC-International Inc.

I. INTRODUCTION

The mission of the task group on accelerated life testing was to "Identify those areas in a service
life predicting methodology used in a natural weathering environment that require additional resources."
The efforts of this task group support the overall goals of the other Task Groups in the Surface Processing
Workshop.

The "natural weathering environment" includes the primary weathering stresses of light, heat, and
water plus the effects of airborne particulates (dust and dirt), pollutants, acid rain/dew, and biological
agents (mildew, algae, etc). No particular device or material was emphasized in these discussions, but
rather an overall evaluation of the current state of service .life predictions for materials, in general, was
considered. ."

Because emerging advanced materials demonstrate ever increasing lifetimes, new approaches to
service life prediction are necessary. For example, significant improvements in the lifetimes of polymeric
materials-up to 10,20, or 30 years-are anticipated.

The use of "natural" weathering at exterior exposure sites to establish service life is no longer
viable for these long-lived materials. Recent generation automotive coatings have exhibited substantial
gloss loss and, sometimes, color shift in 1 to 2 years of Florida exposure. With the advent of "base
coat/clear coat" technologies, automotive coatings now show little change in 5 to 10 years of similar
exposure. The introduction of fluorocarbon paint systems may well increase lifetimes to 20 to 30 years
as they have in architectural coatings. To have a reasonable economic payback compared with current
energy alternatives, solar energy devices will require lifetimes of 20 to 30 years plus.

Obviously, this means that accelerated test methods will become even more important in the near
future than they have been in the past Unfortunately, many material scientists have been disillusioned
in their attempts to predict material performance in exterior environments from the results obtained from
accelerated aging tests.

The flfst part of this chapter will discuss the reasons for some of the frustration of lifetime
prediction and, therefore, the need for new approaches to service life predictions. These new
methodologies will require significant resources and a multi disciplined approach to address this complex
and"very difficult problem. These new approaches and information gaps will be described and research
areas will be identified that will be needed to make these new methodolOgies workable.

25-1
II. SERVICE LIFE METHODOLOGIES

A. Linear Model

'This method has been and is still being used to "correlate" accelerated tests to natural exposure
environments. The typical approach is to test a material both outdoors and in an accelerated test.
Assuming similar failure modes, the time to reach a predetermined property change is determined for both
tests. These two times are related through a linear (zero intercept) equation.

where: l:..:cct = time in accelerated test

t..cnw = time in exterior or field environment
Ie. = constant

Rearranging this equation gives the more common form in which Ie. is often referred to as an acceleration
factor.

k.=--t
actual
tacc:el

Many of the accelerated weathering specifications that control commerce for both industry and
government are established using this approach. Unfortunately, most of the time, these aCceleration factors
are determined from experiments using only one material and a single point exposure in each environment.
Typically, there is no replication for the accelerated test or outdoor exposure. 'This means the Ie. factor
is often fraught with undefined sample, property measurement, exposure test, climatic, and seasonal
variations. Once a Ie. h~ been established for a material, it is often erroneously extrapolated to other
materials that inherently have a significantly different acceleration response in the same accelerated test.

Simms [1] has described the problems associated with linear correlation models and has proposed
a methodology for determining valid "accelerated shift factors." Many sample replicates (both accelerated
and real environments) are required for these calculations, and each material will require the calculation
of the material-dependent Ie.. Even the calculation of a statistically valid Ie. does not really define the
performance of the same material during a re-exposure because of the high variability of both accelerated
and outdoor exposures [2,3]. In any single test, premature or delayed failure may be the product of test
variability and not true material performance. In addition, using an approach that requires the exposure
of a material to both accelerated and real service environments, in order to establish test validity, is of
questionable usefulness because the length of the experiment is always controlled by the duration of the
outdoor experiment

B. Nonparametric Statistics

During the early 1980s, the use of nonparametric statistics to relate accelerated to real weathering
tests started to grow in popUlarity. The impetus for this methodology was originally attributed to the high
variability of exterior exposure results (year-ta-year climatic differences at a single site). .

The nonparametric approach does not assign an absolute level of performance (or failure) to a
single material, but ranks the performance of a series of materials. In correlating accelerated and real
exposure tests, the rank performance of a series of materials exposed to both environments is compared,
and the strength of the association between the tests is established. This is shown in Table 1.

25-2
 Table 1. Example of Rank Performance

Rank in Rank in
Material Accelerated Test Exterior Exposure

A 1 1
B 2 2
C 3 3
D 4 4
E 5 5
F 6 6

The ranks can be determined from actual material property measurements such as physical or
chemical properties, subjective observations, or time to a defined property change or failure. The ·above
example would be the ideal case of perfect correlation. Several measures of nonparametric correlation
have been described by Conover [4]. Spearman rank correlation coefficients (rJ are most commonly used
for relating weathering tests.

where d; is the difference in the ranks for each material in each test and n is the number of materials
tested.

Values for r. ~ange from I, indicating perfect agreement between the accelerated aging and outdoor
exposure rankings, to -I, indicating a perfect reverse ranking. A correlation coefficient·of zero indicates
that the accelerated and outdoor exposure rankings were random or showed no agreement.

Spearman's ra is a measure of the tendency for "reversals" between the two tests. Ranking sample
performance ignores the effect of test variability caused by differing primary stress levels. Round-robin
studies indicate that nominally similar tests can cause significantly differing failure rates [5], but rank
performance for a series of materials is quite reproducible between laboratories. In these cases, differing
stress levels do not affect the failure ranking of materials, just the time required to achieve failure. .
Ignoring the effect of stress level on failure rates means that actual service life predictions with associated
confidence levels cannot be achieved. This is possibly the biggest weakness of the nonparametric
approach. Service life of new materials can only be "ranked" relative to materials with known service
lives, i.e., more or less-compared to the known material.

Another weakness of the nonparametric approach is in defining "What is good correlation?" Non-
parametric methods were developed to evaluate, generally,low-Ievel correlation between cause and effect.
High levels of correlation (even 0.9 and above) can still allow significant, individual sample reversals to
occur, especially in large sample sets.

Spearman rank correlation has most successfuUy been used in accelerated test development [6].
Accelerated test conditions are modified until rank correlation to exterior exposure is maximized. If high

25-3
 rank correlation accelerated tests can be developed for a broad range of material types, one may assume
that this test has a "better chance" of properly ranking new materials.

'Through the use of nonparametrics, unrealistic stresses, such as short-wavelength ultraviolet (UV)
radiation not found in terrestrial sunlight or unrealistically high temperatures, have been eliminated. 1bis
has led to longer accelerated test periods-not the right direction to be heading for today's more durable
materials. Accelerated test speed and high rank correlation are diametrically opposed. As the stresses in
the accelerated test approach service conditions, the rank correlation coefficient will approach unity, but
the test is no longer accelerated. .

Ill. PRIORITIES FOR VALID SERVICE LIFE PREDICTIONS

The following sections will describe an idealized approach to service life predictions for highly
durable materials and devices. The working group identified five priorities:

• Adopt a new service life prediction methodology for weathering environments

• Develop appropriate models for predicting "real" service life from accelerated tests

• Quantify the stresses in exterior environments

• Define and understand degradation mechanisms and their relationship to weathering stresses

• Establish data bases for quantified climatic stresses and material responses to these stresses.

The task group members are not naively presenting this proposal as being easily within reach.
This is, by no means, a short-term or simple answer to the problems inherent in "weathering" service life
predictions developed by current practices. Substantial resources and time will be required to predict
effectively the service life of a new material or device with a high degree of confidence and, more
. importantly, with accuracy. >

A. Service Life Models-Life Distribution Methods

A distribution of failures from worst to best is required to get a truly useable estimate of service
life. Often when exposure tests are performed outdoors or indoors, single samples or, at best, duplicates
or triplicates are tested, and an estimate of mean performance is obtained. In·actual use, often the fIrst
few failures are the most important in satisfying consumer expectations or setting reasonable warranty
periods.

Nelson describes several parametric statistical approaches that allow actual lifetime distributions
to be established [7]. Confidence levels can also be determined for the distribution. All of these
approaches require that many sample replicates be tested. This apparent disadvantage is offset by the fact
that test times can be significantly shortened. 'Through "censored" data analysis techniques, only the fIrst
few failures have to be observed to get an estimate of the total service life distribution.

Two life distribution methods that seem most appropriate are the log normal distribution and the
Weibull distribution. The log normal distribution is

25-4
 F(t) = <I>{(1og(t)-J.l)/a}

where F(t) is the cumulative fraction failed, t is the time, <I> is the standard normal cumulative distribution
function, J.l is the scale parameter, and a is the shape parameter.

and the Wei bull distribution is

F(t) = l-exp[ -(t/a)II]

where F(t) is the fraction failed, t is the time, a is the scale parameter, and j3 is the shape parameter.

The strength of the proposed technique is that one should be able to predict the early times to
failure and to establish a functional relationship between shape and scale parameters and the kinetics of
degradation. This will facilitate the extrapolation and interpolation of these predictions to other service
conditions. In addition, statistical discrimination among factors (material, processing, application, design,
and environmental) may identify the factor or factors responsible for causing the unexpectedly short time
to failure. Along with the early failures (infant mortality), normal wear out can also be modeled. Life
distribution models can also handle multiple failure mOdes; this becomes more important when more
complex systems or devices are tested. Martin and McKnight have demonstrated the utility of the Weibull
distribution in rapidly describing the service life of various coating/metal substrate systems in corrosive
environments [8]. .. .

Computer software packages are commercially available for these maximum likelihood methods,
which can provide product life distribution estimates and confidence limits for specific test design stresses.

B. Models for Relating Real Life and Accelerated Tests

The most difficult challenge will be in the development of life-stress models that will "convert"
accelerated test-life distributions to real life distributions. Single stress models have been successfully
used on many occasions, most notably the Arrhenius relationship for relating failure rate to exposure
temperature, i.e.,
(failure) rate = Aexp( -E/kT)

where E is the activation energy, A is the pre-exponential constant relating to test conditions and material
characteristics, k is the ideal gas or Boltzmann's constant depending on equation units, and T is the
te~perature in degrees Kelvin.

In the more complex (multistress) world of weathering, an Arrhenius-type extrapolation was used
to predict the failure of automotive interior materials exposed to various temperatures and solar radiation
levels [9]. Most often, successful models in weathering will require accounting for a minimum of three
stresses-light. temperature, and moisture.

The generalized Eyring model can be used to describe failure rates relative to temperature and one
additional stress variable [7].

25-5
 Product lifetime = (A[T)exp(B/kT)exp{ V[C + (D/kT)])

where V is the additional stress variable and A, B, C, and D are the constants estimated from the data.

Often, the additionally modeled stress has been humidity. Murray used a modified Eyring model
to predict the service life distribution of magneto optics at various temperatures and humidities [10].

If a material or device being weathered is primarily sensitive to only two stresses; tlie Eyring
model may indeed be adequate. Exposures in desert regions could use this model with "light" being the
V stress while ignoring the effects of moisture. Carlsson suggests that for "electromagnetic stresses," the
acceleration factor should be described as (I1I.l, where I is the intensity of photoreactive light, I., is a
reference intensity, and P is a constant [11].

Most often, one would expect that models with three. or more stress variables will have to be
developed. Nelson describes ' generalized log-linear relationships for predicting multiple stress
environments, but simple linear relationships will probably not be adequate [7]. Tobias and Trindade
describe the addition of a third exponential multiplier to the Erying model equation to accommodate three
stresses [12]. .

An added complexity arises because weathering involves nonconstant or cycling stress levels. This
may require the development of a cumulative damage (exposure) model to relate the cyclic outdoor
stresses to the "more constant" accelerated test. .

.Whatever form and complexity the modeling equations take, the stress levels, both outdoors and
in accelerated tests, will have to be quantitatively characterized in a manner that facilitates comparisons
between outdoor and accelerated exposure results.

C. Quantify Stresses in Exterior Weathering Environments

Proper accelerated weathering tests cannot be developed nor can real weathering environments be
modeled without a thorough understanding and quantification of the stresses that cause material/device
failure. Unfortunately, the United States is taking backward steps in gathering climatic data in a number
of exterior envirorunents.

Consistent methods of stress measurement, especially UV radiation, have not been established.
The comparison of solar irradiance data from neighbOring commercial, exterior exposure sites in both
Florida and Arizona indicates that much work is needed in standardizing measurement techniques and
calibration procedures for radiometers. Much better characterization of terrestrial solar UV, especially
around 300 nm, will be needed for long-range lifetime predictions.

Temperature must be measured in a way that will quantify the thermal influence on both photo-
initiation and subsequent thermally controlled reaction rates. Surface and internal temperatures, rather than
ambient air temperature, of materials and devices would be more relevant to predicting failure rates.
Determination of the efficiency of photodegradation as a function of temperature during exposure could
lead to development of a UV radiation/thermal stress unit Somewhat analogous to a heating degree day,
this "thermal dose" might be helpful in establishing cumulative damage models for variable condition
exterior exposures.

25-6
 The various forms of water stress should be measured. The effects of dew and rain could be
quantified by time of wetness (TOW) as is now done at a number of commercial sites that conduct
exposure tests. Several TOW methods and devices are readily available. Relative, or more appropriately,
absolute humidity (both during photo- and thermal-stress periods and dark periOds) and total liquid
precipitation can be easily quantified. It is also essential to understand the effects of moisture on surface
and bulk degradation. In other words, we must know which form of water is most important-water
vapor, .condensation (dew), or rain.

Pollutants in several forms need to be characterized and quantified. Both dry deposited NOx, SOx,
and acid rain or dew can have significant impact on material failure rates. Airborne particulates can either
accelerate or retard photo-induced degradation. High altitude and terrestrial ozone levels impact solar
spectral energy distributions and material oxidation rates, respectively.

The task group recommends that a coordinated, publicly funded program be developed through
a single agency to monitor climatic stresses. Important aspects of this study might include:

• Three years of continuous stress measurement

• Six to 10 sites of various climatic classifications (desert, subtropical, high altitude, temperate, urban-
polluted, marine)

• Identical, standardized, controlled, and calibrated stress measurements must be conducted at each site
for the following: ...

- Ught: Total and spectral UV radiation at latitude angle

Total global radiation at latitude angle
Narrow band measurement at 310 run

- Temperature: White and black panel at latitude angle

Ambient temperature

- Water: Time of wetness

Total liquid precipitation/frequency
Humidity

- Pollutants: NOx, sax levels

. Total suspended particulates.

Continuous or long-term measurements of the specific climate factors listed above will allow for
the development of models that can be used to estimate the stresses for many geographic locations based
on more limited data collected at those sites. However, the efforts for precision characterization of
climatic stresses should be combined with simultaneous exposures of a variety of materials at the same
sites in order to model the effects of specific climatic stresses on polymer degradation. See Section E for
more detail.

D. Defining and Understanding Material Degradation Mechanisms

This is probably the most critical area requiring extensive research before valid service life
predictions can be made for a variety of materials. Once climatic stresses are defined, their impact on
material failures must be fully understood. This will require characterization of materials before, during,

25-7
and after exposure to weathering stresses. The task becomes even more complex when materials are
combined to make components and devices. -

It is not the intent nor necessarily the expertise of this task group to recommend specific
characterization methods or analytical techniques that should receive special emphasis. Several applicable
techniques are discussed in Chapter 26 on Interfacial Microchemical Characterization Needs in Surface
Processing. An exhaustive review of analytical procedures particularly relating to coatings has been
written by Anderson [13].

Surface characterization is extremely important for understanding the processes that occur at
exposed surfaces and unexposed interfaces. Therefore, techniques that emphasize surfaces and interfacial
boundaries will be especially useful.

Understanding the mechanisms and quantifying the kinetics of degradation reactions have several
important benefits. If these processes are understood for materials in a natural weathering environment,
the design of appropriate accelerated tests is made much easier. Accelerated tests can be modified until
they produce degradation processes similar to those that occur in exterior weathering. The simulated
stresses can be increased until maximum acceleration is achieved while still maintaining a service life
failure distribution that can be modeled relative to an outdoor environment.

Ideally, if the basic failure processes are understood, and the defects or sites for failure are
initiation are identified, the accelerated test may not be necessary. Service life could actually be predicted
from results of material or product characterization by appropriate analytical techniques. Analogous to
genetic code, all the information to predict service life is inherently contained in each individual specimen,
if only it can be extracted and understood.

E. Climatic Stress and Material Response Data Bases

The climatic stress data that would be gathered from the general program described earlier should
be maintained by a central, controlling agency. In conjunction with the climatic stress data collection, a
broad selection of appropriate materials/systems should be exposed simultaneously at the same sites.
Material response to these stresses should be measured and stored to aid in accelerated test design and
ultimate service life projections.

Proper design of a comprehensive stress measurement and material response study is extremely
critical. At the very least, the following points should be considered:

• Structure or composition of specimens

• Test conditions for sample mounting, exposure type, and exposure angle

• Initial material properties in which the measurement technique to characterize properties is a

standardized procedure for making meaningful data comparisons between sites

• Material properties during and after exposure

• Corresponding cumulative stress levels at times of property measurement or material failure.

If properly planned and executed, the above weathering stress/material response data base could
serve as the basic structure for an ever-growing national repository on weathering and materials. In

25-8
 general, most of the data on material response to weathering environments is held captive in the private
sector, although some information specific to solar energy materials has been reported [14,15]. There is
a need for a centralized data base on materials and weathering. A data base manager would be required
to maintain and update information. The data base information could be segregated into material types
or, possibly, end uses, such as protective coatings, optical materials, pottants, etc. Certainly,
standardization of stress and property measurement would be extremely critical for this to be a useful
source of information.

REFERENCES

1. 1. A. Simms, 1. Coat. Techno!., 2!. 45 (1987).

- 2. R. Fischer, W. Murray, and W. Ketola, Progress in Organic Coatings, J2., 151 (1991).

3. R. Fischer, W. Ketola, and W. Murray, Progress in Organic Coatings, J2., 165 (1991).

4. E. J. Conover, Practical Nonparametric Statistics, 2nd Edition, John Wiley and Sons, Inc., 1980.

5. ASTM G 53-84 Round Robin Test Report-February 10, 1987, Conducted by ASTM Committee G-3
on Durability of Non-metallic Materials, Subcommittee G03.03-Simulated and Controlled
Environmental Testing, report available from ASTM, 1916 Race Street, Philadelphia, PA 19103.

6. R. Fischer, SAE Tech. Pap. Ser., 841022 (1984).

7.· W. Nelson, Accelerated Testing, John Wiley and Sons, Inc., 1990.

8. J. Martin and M. McKnight, J. Coat. Techno!., R 39 (1985).

9. Y. Watanabe, SAE Tech. Pap. Ser., 821120 (1982).

10. W. Murray, Archival Life Expectancy of 3M Magneto-Optic Media, J. Magn. Soc. Jpn., to be
published Fall 1992.

11. B. Carlsson et al., Solar Materials Research and Development; Survey of Service Life Prediction
Methods for Materials in Solar Heating and Cooling, BFR-D-16-1989; DE90 748556, Swedish
Council for Building Research, Stockholm, 1989.

12. P. Tobias and D. Trindade, Applied Reliability, Competitive Manufacturing Series, Van Nostrand and
Reinhold, New York, 1986.

13. D. Anderson, Anal. Chern., £!, 33R (1989).

14. J. Gilligan et al., Handbook of Materials for Solar Energy Utilization (Low Temperature
Applications), DOElCHl90034-T1, lIT Research Institute, Chicago, n.., April 1980.

15. G. Zerlaut and T. Anderson, Commercial Solar Materials Exposure Studies, DSET-R2658, DSET
Laboratories, Inc., Phoenix, AZ, February 1989.

25-9
 26. IN1ERFACIAL MICROCHEMICAL CHARACTERIZATION
NEEDS IN SURFACE PROCESSING

Stephen W. Gaarenstroom, General Motors

Richard 1. Anderson, Sandia National Laboratories-Livermore
Ronald 1. Baird, Ford Motor Company
Phillip L. Coduti, Inland Steel
Michael Liehr, mM
Robert A. Mayanovic, University of Notre Dame
Gerald C. Nelson, Sandia National Laboratories-Albuquerque
Cedric 1. Powell, National Institute of Standards and Technology
Peter M A. Sherwood, Kansas State University
Matthew 1. Zaluzec, Ford Motor Company

ABSTRACT

Interfacial microchemical characterization is required for all aspects of surface processing as

applied to transportation and utility technologies. Corrosion protection, fuel cells and batteries, wear
surfaces, polymers and polymer-oxide interfaces, thin-film multilayers, photoelectrochemical systems, and
organized molecular assemblies are a few examples of interest to these industries. A number of materials
and processing problems, both related to fundamental understanding and to monitoring manufacturing
operations, have been identified in which our microchemical characterization abilities are lacking. More
than 20 areas for research are identified in which progress will contribute to improved understanding of
materials and processes, improved problem-solving abilities, improved manufacturing consistency, and
lower costs. Some of the highest priority areas for research include: (1) developing techniques and
methods with improved chemical specificity at interfaces, (2) developing fast, real-time surface and
interface methods, and (3) improving the cost and reliability of manufacturing monitors. Increased the
collaboration among university, industry, and government laboratories will be required for progress to be
made in a timely manner.

I. INTRODUCTION

Interfacial microchemical characterization plays a crucial role in both developing and improving
surface processing of materials for the automotive and utility technologies. Within the automotive
industry, there are a number of driving forces that demand that new materials and new kinds of material
interfaces will be used. These driving forces include the need for reduced emissions, improved fuel
economy (including lighter weight materials), improved safety, reliability, durability, and lower cost
Some specific automotive or utility interfaces might include a surface-modified engine cylinder bore; a
composite body panel adhesively bonded to an ·automotive frame; the topcoat, primer, and conversion
coating layers on a galvanized steel body panel; and multilayer films on a photovoltaic cell.

In this report, we have organized the issues involved in interfacial microchemical characterization
needs as a 2 x 3 matrix, as shown in Fig. 1. On one axis, issues can be divided as pertaining either to
fundamental and applied laboratory studies or to monitoring of manufacturing operations. TlDle-scale
considerations are important here. Some studies to increase our fundamental understanding can take years.
Other problem-solving studies (including failure analysis on field returns) may involve a couple of days.
Characterization work related to material acceptance might take minutes or hours. Finally, in situ
monitoring of a manufacturing line and accompanying process feedback take place on a time scale of
seconds. We will discuss later the strong need to shorten all of the above time scales. In this report,·we

26-1
 deal with improvements and extensions of existing techniques and methods. No attempt is made to be
clairvoyant or to predict major breakthroughs. For example, the discovery of an inexpensive, easily
processed, room-temperature superconducting material would rather dramatically change the course of both
automotive and utility technologies.

The other axis in our organization matrix divides issues into three categories: (1) the motivating
problems related to materials and processing, (2) the limitations of our current techniques and methods,
and our needs to improve the situation, and (3) issues relating to information or infrastructure subjects,
which go beyond the more narrowly focused subject of interfacial microchemical characterization. The
issues, needs, and proposed areas of research we list in this report are meant to lead to near-term
improvements in surface processing for automotive and utility applications. There is another workshop
report that is still timely that discusses more basic research opportunities in interfacial microchemical
characterization [1].

n. MA1ERIALS AND PROCESSING PROBLEMS

A. Fundamental and Applied Laboratory Studies

The variety of material interfaces that impact automotive. technology is impressive. Interfaces can
be solid-solid, solid-liquid, and solid-gas. Material types can be metals, oxides, inorganics, organics,
. polymers, and semiconductors. Some typical systems are given in Table 1, and the surface and interface
tools we use to characterize these systems are given in Tables 2 and 3. Every material interface has a
number of attributes that are critical to the performance of that interface, attributes such as chemical
composition, chemical structure, defects, morphology, and roughness. These attributes in turn govern other
material properties, such as corrosion resistance, hardness, diffusion, stability, and other interactions with
the environment.

Significant interface problems involving materials and processing are listed in Table 4. One of
the most important problems deals with so-called buried interfaces. These are solid-solid interfaces that
are too deep for our wide variety of surface analytical tools to probe without resorting to intricate
specimen preparation or model systems. We need to know a good deal about these solid interfaces (see
the list above regarding composition, structure, defects, etc.). We also need to characterize these interfaces
on a variety of spatial scales, ranging from a mm. scale to a J.UIl scale and even sometimes a nm scale. .
Ideally, we would like to have a nondestructive characterization tool to allow the interface to be examined
following (or during) successive processing treatments or environmental exposures.

A second class of important interface problems deal with impurities. defects, and diffusion at
interfaces. Impurities and defects are important because these features usually initiate interfacial failures.
The investigator needs to determine the identity of an impurity (or defect), to determine how much is
present, and to determine the spatial distribution. For studies of diffusion and interdiffusion; the
investigator determines the type of diffusing species, the rates of diffusion, and the effect of the diffusion
on the interface. Representative automotive technology examples are (1) the diffusion of methanol-
hydrocarbon fuel mixtures at surface-treated polymeric fuel tanks, (2) the diffusion and intermetallic
compound formation at layer interfaces of journal engine bearings, and (3) interdiffusion across metal-
semiconductor interfaces of integrated circuit sensors subjected to the elevated temperatures of the
underhood environment.

Another interfacial problem is nonideal surface (and interface) topography. Manufactured surfaces
have roughnesses that make the application of our conventional surface science tools difficult or

26-2
 Table 1. Typical Material Interface Systems in Automotive and Utility Technologies

Solid-solid Metal-metal - galvanized steel

- brazed aluminum radiators

Metal-oxide - electrically heated windshield

Metal-inorganic - phosphate conversion coating on steel

- chromate coating on aluminum
.- Pt electrode on zirconia exhaust gas oxygen sensor

Metal (oxide)-organic - adhesive on surface-modified metal

Metal-semiconductor - ohmic contact on an integrated circuit (Ie) device

Semiconductor- - diode (e.g., GaAs on Si)

semiconductor

Polymer-polymer - paint system on thermoplastic part

- adhesive on sheet molding compound

Fiber-matrix - carbon fiber-reinforced epoxy

Solid-liquid Metal-electrolyte - lead-acid electrochemical cell

Polymer-organic -surface-treated polymeric fuel tank

Solid-gas Oxide-gas - Sn02-type combustion gas sensor

26-3
 Table 2. Listing of Techniques for Microcharacterization
of Solid Surfaces and Solid Interfaces

Inherently XPS X-ray photoelectron spectroscopy

Surface UPS ultraviolet photoelectron spectroscopy
Sensitive AES Auger electron spectroscopy
SIMS secondary ion mass spectrometry, including ion
microprobe (IMP), time-of-flight (TOF), secondary
neutral mass spectrometry (SNMS), and other post-
ionization methods
STMIAFM scanning tunneling microscopy, atomic force microscopy,
and other proximal probe microscopies
LEEM low energy electron microscopy
ISS ion scattering spectrometry
LEEDIRHEED low energy (and reflected high energy) electron
diffraction
SEXAFS surface extended X-ray absorption fine structure
HREELS high-resolution electron energy loss spectroscopy
IDS thermal desorption spectroscopy
FIM/FEM field ion/emission microscopy
FE fracto-emission
WM wetting methods

Less SEMIESEM scanning electron microscopy, environmental SEM

Surface TEMIAEM transmission electron microscopy, analytical EM
Sensitive RBS Rutherford backscattering spectrometry, and other
energetic ion methods: nuclear reaction analysis
(NRA), proton-induced X-ray emission (PIXE), heavy
ion backscattering (InBS)
EPMA electron probe microanalysis
TR-XRF total reflectance X-ray fluorescence spectroscopy
SAW surface acoustic wave

Bulk IR infrared spectroscopy

Methods Raman Raman spectroscopy
SE ellipsometry, spectroscopic ellipsometry
SHG/SFG second harmonic generation, sum frequency generation
EXAFS extended X-ray absorption fine structure
XRF. X-ray fluorescence spectroscopy
XR.D X-ray diffraction, also neutron diffraction
ESR electron spin resonance spectroscopy
LAMMA laser microprobe mass analysis
SPAS, PET slow position annihilation spectroscopy, positron
emission tomography

26-4
 Table 3. Techniques for the Solid-Liquid Interface

- Optical (photon) methods, including nonlinear (laser) spectroscopies,

light scattering, X-ray scattering, absorption spectroscopy
Various proximal probe microscopies STMIAFM
- Spectroscopic ellipsometry
- Attenuated total reflectance infrared spectroscopy, also reflectance IR, ATR-IR
Raman
- (X-ray with glancing angle techniques) XRF, XRD
- (By "backside" RBS technique) RBS

- Electrochemical potentiometry

- Zeta-potential

- Contact angle, air-bUbble contact angle

- Surface acoustic wave SAW

- Total reflection EXAFS TR-EXAFS

Table 4. Major Interfacial Characterization Problems

Related to Materials and Processing

Fundamental and Applied Laboratory Studies Monitoring Manufacturing

"Buried" interfaces "Buried" interfaces
Defects, impurities, and interdiffusion at interfaces Impurities at interfaces
Surface topography Rapid real-time measurements
Stability, degradation, properties, and morphological Surface contamination
phase of interfaces and thin :films

26-5
impossible. A final interfacial problem deals with numerous issues involving thin films. including
stability. degradation, properties. and the morphological phase. The rates of chemical change need to be
measured as well as the effect of a chemical change on the properties of the material or device. Often
an in situ or nondestructive technique is required, but frequently no suitable technique is available.

B. Monitoring Manufacturing Processes

The most significant materials and processing problems involving manufacturing operations are
listed in Table 4. Many of the same problems that appeared on the Laboratory Studies list also appear
on the Manufacturing list. Furthermore, in the manufacturing environment, we have additional constraints
concerning the time scale within which the measurement must be made and the requirement that the
measuring probe must be nondestructive and nonperturbing. .

Dealing with buried interfaces again makes the list of important needs. Currently, there are many
instances in which information is required on the chemistry, morphology, or structure of a buried interface,
but no monitor exists to provide the information. Obviously, development of new techniques and sensors
t<:l meet our monitoring requirements will be ranked as a high priority later in this report. A related
matter, in-service testing monitors, would likewise benefit from any developments in new interface
monitoring sensors. An in-service testing example involving utility technology is the testing of
photovoltaic devices in a working array.

Other needs on our list include monitoring impurities at interfaces and surface contaminants.
Again, frequently no suitable manufacturing monitor exists. The requirements here are (1) the detection
of an impurity or contaminant, (2) its quantification, and sometimes (3) the characterization of an unknown
impurity or contaminant An example involving steps (1) and (2) is surface carbon contamination on steel,
in which carbonaceous deposits interfere with the phosphate conversion coating operation. Finally, the
high line speeds of many manufacturing operations pose a real challenge to developing suitable interface
monitors that are capable of operating in "real" (that is, .!mlliD real time. For instance, an
electrogalvanizing line for coiled steel operates at tens of meters per minute.

III. CURRENT LIMITATIONS AND NEEDS

A. Fundamental and Applied Laboratory Studies

A list of interfacial characterization needs is given in Table 5. We rank our needs into three
categories: crucial, important, and useful. The first crucial need is for techniques and methods with
improved chemical specificity at surfaces and interfaces. Chemical specificity includes chemical bonding
information, ~nsitivity to hydrogen. ·and characterization of organics and macromolecules (includes
conformation, isomerization, and cross-linking). A number of current techniques in common use are
capable of chemical specificity (X-ray photoelectron spectroscopy [XPS] core and valence, secondary ion
mass spectrometry [SIMS]/secondary neutral mass spectrometry [SNMS], high resolution electron energy
loss spectroscopy [HREELS], infrared [IR]/Raman, sum frequency generation [SFG], thin-film X-ray
diffraction [XRD], extended X-ray fine structure spectroscopy [EXAFS]/surface extended X-ray fine
structure spectroscopy [SEXAFS], temperature programmed desorption [TPD]). These techniques also have
the potential to detect hydrogen (except core XPS) and to characterize organics. However, a number of
restrictions exist the potential of the technique depends on (1) the problem addressed, (2) whether the
. specimen is a single phase or a mixture, (3) whether the specimen is stable under the particular probing
beam of the technique, (4) whether the specimen is stable in the analyzing environment of the technique
(vacuum environments may lead to loss of waters of hydration, decompositions of hydroxides, alterations

26-6
 Table 5. Current Limitations and Needs in Interfacial Microchemical Characterization

Fundamental and Applied Laboratory Studies Monitoring Manufacturing

Crucial: Crucial:
_ . Chemical specificity (including bonding, - New, nondestructive techniques
hydrogen, organics)
- Real-time techniques for dynamic measurements - Improved cost and reliability of
in process environments monitoring methods
- New technique development
Important: Important:
- Specimen preparation - To extract information
- Nondestructive methods - Reference materials
- 3-D characterization - Improved optical methods, coupled with
optical fibers
- Extract maximum information
- Reference materials Useful:
- Model systems - "Monolayer" detection on-line

of crystalline/amorphous morphologies), and (5) the requirement for unambiguous identification among
closely similar species or contaminants. As' a consequence of these restrictions on our current methods,
any improvements in our ability to provide chemical specificity for material interfaces will be very
beneficial.

The next need, which we ranked as crucial, was for the development of fast, real-time techniques
for dynamic measurements in a process (in-situ) environment Frequently, we need to monitor rapidly
changing surface and interface features during a processing reaction (or for a model system of a technical
process). Examples include diffusion, corrosion, film growth, wear, and catalysis. Some current
techniques employed for real-time, in-situ work include SFG (J.1S time scale), environmental transmission
electron microscopy (1EM)/scanning electron microscopy (SEM) « 1 ms time scales), scanning tunneling
microscopy (S1M)/atomic force microscopy (AFM) « 1 ms), ellipsometry (20 ms), IR (500 ms), and
other, slower methods. Many other techniques might be appropriately engineered for rapid, in situ
measurements, but the expense is very high. One "hybrid" instrument that may be useful for this topic
is a combined environmental-SEMlenvironmental-AFM. Another proposed hybrid instrument is a
combined SEXAFS/X-ray standing wave instrument

The third crucial need is for the accelerated development of some recent new techniques. Included
here are AFM, STM, near-field imaging, X-ray optical methods, and fiber-optic-based light microscopy.

There are six other needs that we rank as important The first is for improved specimen ·
preparation methods and reduction of experimental artifacts. Novel specimen preparation or experimental
setup may enable us to substitute a classic "ex situ" method for a sophisticated, expensive "in situ" method
with no loss of information. When multiple techniques or sequential techniques are used, the location of

26-7
the analyzed region must be correctly identified. Beam damage and temperature effects must be
minimized, or we risk invalidating the study. Refinements in preparation of cross-section specimens for
lEM will extend this critical tool to more material interfaces to characterize defects, topography, and
interfacial phases. Some current specimen preparation (or experimental setup) methods used to examine
solid-solid interfaces with surface science tools include ion sputter-etching, mechanical sectioning (ball
craters, radial sections), and in situ fracture. Some non-destructive experiments are also used, where the
"take-off' angle is varied or the beam energy is varied. Improved methods would be welcomed.

The next important need is for improved nondestructive evaluation methods. As mentioned earlier,
the need is to characterize a specific material surface or interface before ~d after a processing step, in
order to determine the effect of the processing. Some of the light-based optical methods mentioned
elsewhere in this report appear promising here. The relatively new positron annihilation techniques, such
as slow positron annihilation spectroscopy (SPAS) and positron emission tomography (pET) are also worth
mentioning. A third need is for improved three-dimensional (3-D) characterization, with high spatial
resolution and chemical bonding information. Some leading tools that will undergo further improvement
include 3-D SIMS mapping, 3-D XPS and Auger profile/mapping, X-ray tomography, analytical electron
microscopy (AEM), and confocal · light microscopy. One of the challenges with the data-rich 3-D
techniques is dealing with data collection, analysis, and diSplay. This is discussed later in our report. The
fourth need is to use tools to extract maximum information from the experimental data. Often only a
small fraction of the information that the analyst has expensively acquired is used, with the remainder
discarded. Multivariate analysis methods are well established for improved data processing, but are not
as widely used as they ought to be. Perhaps an expert system approach is required here. Included in this
fourth need is the improvement of existing methods for quantification, specification, artifact removal, and
the need to improve detection limits. Progress here will require improved measurements of some
important physical parameters and improved knowledge pf physical phenomena. The fifth need is for
improved reference materials. Because we are dealing with material surfaces and interfaces, there are
significant preparative challenges here, but we will improve our ability to calibrate our instruments and
identify and characterize complex material systems. The sixth and final need is the development of better
model systems. An appropriate model system is far easier to deal with in understanding a particular
surface-processing phenomenon than dealing with the actual, more complex system; such model systems
nevertheless have to be validated.

B. Monitoring Manufacturing Operations

Because of the additional constraints imposed on monitors in a manufacturing operation (simple,

reliable, nonperturbing, low cost, rapid, etc.), the task of doing interfacial characterization in the
manufacturing environment seems more difficult than in the laboratory environment One saving factor,
compared with laboratory studies, is that usually only specific information for a single parameter of an
interface is required, not a full characterization. There are a limited number of monitors currently in use
for dealing with surface processing and material interfaces. They include thickness measurements (by
numerous techniques), mass spectrometry, X-ray fluorescence, thermography, glossimetry, radiography,
ambient photoemission probe, and IR. Additionally, there are many monitors that perform measurements
in an "off-line" mode to support manufacturing. Frequently the lack of a suitable monitor means that no
measurement is done, and the control of the processing step is uncertain. Thus, we list the need for new,
nondestructive techniques for rapid monitoring during manufacturing as a crucial need.

The other need listed as crucial is for improved cost and reliability of monitoring methods. Most
of our surface science tools are too expensive and otherwise inappropriate for a manufacturing
environment. Other measurement concepts from chemistry, physics, remote sensing, and nondestructive
testing disciplines should be looked at as potential sources for improved monitors. Since the cost of

26-8
computing hardware continues to decline, we will be able to process a great deal of information
inexpensively. Methods with improved cost and reliability are likely to be computationally intensive, but
to utilize simple probes, analyzers, or detectors.

We have ranked three other manufacmring needs as important. The first two, the need to extract
maximum information from a measurement and the need for improved reference materials, also· appeared
on our laboratory studies list Benefits to the manufacturing operations will include more accurate and
more robust measurements. The third important area for development is in improved, light-based optical
methods, coupled with optical fibers. This technology is especially suited to the constraints of a
manufacturing monitor Oow cost, high speed, ruggedness, flexibility, small size).

A final manufacturing need that would be useful is monolayer detection on-line. Some critical
operations have a requirement for high sensitivity on a rapid basis. Our common schemes that have
monolayer sensitivity (electron spectroscopy, SIMS, and others in Table 5) are usually unsuitable for a
process environment. New approaches should be investigated.

IV. INFORMATION AND INFRASTRUCTURE ISSUES

A. Fundamental and Applied Laboratory Studies

A number of the needs that our group identified while looking at interfacial microchemical
characterization needs for surface processing cannot be defined as projects for an investigator to develop,
so they did not appear on the lists in the previous section. Instead, they are needs that must be more
globally addressed by all investigators and their institutions for progress to be made. These issues, which
appear in Table 6, are again ranked as crucial, important, and useful.

Table 6. Information and Infrastrucmre Issues

Fundamental and Applied Laboratory Studies Monitoring Manufacturing

Crucial: Crucial:
- Collaboration of University, Industry, and - Collaboration of University, Industry, and
Government Government
- Availability, sharing, and effective use of - Compressed time scale for method
equipment and instrumentation development
- Availability, sharing, and effective use of
expertise and knowledge
Important: Important:
- Compressed time scale for studies - Expert system development
- Greater use of existing knowledge
- Availability and sharing of data
Useful: .
- Techniques for data visualization

26-9
 The first crucial need is for increased collaboration among university. industrial. and government
and federally funded laboratories. As our requirements become more complex, or interdisciplinary, or
systems-oriented, more teamwork is required to develop an improved method or technique. Our imposed
and our unconscious barriers that limit interactions among investigators will slow the development of
solutions to the problems we are facing. There is also a prevalent "single investigator" frame-of-mind in
many instances that hampers a team approach. The benefits from further collaboration include the
generation of new ideas and approaches, more effective and efficient utilization of experts in different
laboratories, and potentially shorter times for task completion.

The next crucial need, which is partially a subset of our increased collaboration discussion,
concerns the availability. sharing. and effective use ·of equipment and instrumentation among the
institutions listed earlier. Many surface and interface science tools are expensive. Further, many problems
require information contributed by a variety of instruments to be successfully resolved. We recommend
increased sharing of instruments and instrument time on a variety of levels, from lengthier joint research
projects to quick problem-solving exercises. Compensation between institutions should be flexible,
ranging from joint project agreements, to per-diem cost reimbursement, to informal reciprocal instrument-
time agreementS and mutual assistance.

The final crucial need, also partially a subset of increased collaboration, is to increase the
availability. sharing. and effective use of expertise and knowledge. A list of action strategies, which is
far from all-inclusive, includes (1) exciting student interest in interdisciplinary aCtivities by exposing
students to industrial problems; (2) regular exchanges among faculty, industrial scientists, and government
scientists through sabbaticals, summer programs, and short visits, and (3) more involvement in planning
at all institutions by scientists from all three groups.

We ranked three more issues as important. First, we need to compress the time scale of our
studies. We spend too much time to complete our fundamental and applied studies, and future
applications are delayed. Second, we must make greater use of existing knowledge. In the case of
numerous applied studies and problem-solving exercises, time and effort is expended for unnecessary
laboratory characterization work when the necessary information is already available from the published
literature, colleagues, consultants, or other resources. In other cases, a useful technique may not be
applied to a problem because its utility is not widely understood. For instance, valence band data are
rarely acquired in XPS studies, even though considerable bonding information can be discovered using
it. More training in using the existing methods of valence band interpretation is needed. Third, we should
increase the availability and sharing of data (including material property and performance data, as well
as chemical and analytical data). A wide range of data needs to be shared, not only to aid in the analysis
of a specific problem, but to provide generally available data that may prove of value to other groups,
including theoreticians and modelers. Institutions should work to minimize the requirements for
proprietary data. Additionally, our research communities should agree on electronic formats for the easy
exchange of information and data, and should encourage the formation and growth of national and
international data bases.

A final, useful need is for more use of techniques for data visualization. Certain techniques,
especially 3-D techniques like 3-D SIMS profiling/mapping, generate huge amounts of data. There are
now some newer data visualization software packages that work well on engineering work stations and
these packages will satisfy this need when their usage is more widespread. Additionally, some standard
presentation formats may have to be agreed on. For instance, the images produced by STM and AFM ·
experiments can be misleading when the data are massaged to simulate a photograph produced by light
microscopy or electron microscopy. Thorough explanations of the data processing steps, and perhaps a

26-10
sequence of intermediate processing images, may be required to adequately explain the information in an
image.

B. Monitoring Manufacturing

For the manufacturing side of interface characterization issues, we again list a crucial need for
.collaboration of university. industry, and government and federally funded laboratories. For many years,
there has been an inadvertent cultural barrier separating projects in pure science from manufacturing-
related projects. As greater attention is focused on manufacturing-related projects from different sources,
fresh approa:ches will result. The second crucial need is to compress the time scale for method
development. If a process monitor takes months to set up, it probably won't be done. There is a cost
associated with the delay in process monitor development Another time scale associated with process
monitors is the time between the data acquisition and the processed result. No process action can be taken
until the information is fully processed, so data proceSSing and response time should also be as short as
possible.

A final, important need for monitoring manufacturing is for more expert system development.
This approach is useful because it appears that there are many more needs than there are experts to solve
them. Despite some pitfalls in this approach (the interface between the "expert" and the "software writer"
is not always smooth and seamless), the benefits obtained by leveraging the experience of the expert make ·
this approach worth pursuing.

REFERENCE

1. J. Silcox, P. H. Holloway, K. R. Lawless, D. Lightman, D. G. Meisenheimer, L. E. Murr, and

C. 1. Powell, Basic Research Needs and Opportunities for Characterizing the Microstructure of
Interfaces, Materials Sci. Eng., no
149 (1982).

Fundamental and Applied Monitoring

Laboratory Srudies Manufacturing

Problems:
Materials 4 issues 4 issues
and Processing
Limitations 9 needs: 6 needs:
and Needs 3 crucial 2 crucial
6 important 3 important
1 useful
Information and 7 needs: 3 needs:
Infrastructure 3 crucial 2 crucial
Issues 3 import3nt 1 important
1 useful

Figure 1. Matrix of interfacial microchemical characterization issues and needs

26-11
 27. CONDUCTING POLYMERS IN ENERGY AND TRANSPORTATION lECHNOLOGIES

M. Aldissi, Champlain Cable Corporation, Chairman

R. H. Baughman, Allied-Signal
J. M. Ginder, Ford Motor Company
H. H. Kuhn, Milliken Research Corporation
H. Neidlinger, SBH
S. Ventura, SRI International

SUMMARY

The area of conducting polymers has been intensely investigated for more than a decade, with
efforts focusing on materials synthesis and characterization and, more recently, on processibility and
environmental stability. Only during the past few years have applications oriented research and
development work been similarly emphasized-the challenge is to translate the versatility of conducting
polymers into components or devices. The role that these polymers can play in energy and transportation
technologies is substantial, and to this end various objectives must be achieved to produce optimized
materials and devices.

An introduction to the area of conducting polymers, focusing on the importance of surfaces and
interfaces in the realization of several major applications, is given first, followed by the objectives of this
paper. The section that follows discusses various energy and transportation-related application areas and
includes redox-type applications such as batteries, fuel cells, electromechanical actuators, displays, smart
windows, and supercapacitors; EM! shielding, radar absorbers, etc.; photovoltaics and electroluminescent
devices; chemical, thermal, pressure, and radiation sensors; energy transmission; and nonlinear optics.
Materials processing, stability issues, and product characterization are treated in separate sections, and the
last section of this paper gives a tabulated summary of research needs and priorities.

Examples of the importance of interfaces in conducting polymers include the:

• Effect of the nature of interfaces between polymer electrodes and electrolytes on rate limitation, cycle
life, and cycle rate

• Effects of dimensional changes on interfaces

• Effect of interfaces on those electronic and photonic processes in which the complex interactions at
interfaces need to be understood

• Surface energetics between films/coatings and substrates and the need to address the adhesion issue

• Importance of surface perfection in optical applications

• Influences of inter-particle interfaces in bulk polymers on interchain hopping and interface

modification on the incorporation of dopants

• Orientation effects on crystallite interfaces

27-1
• Effect of interfaces in composites and their influence on processing techniques and percolation
thresholds.

I. INTRODUCTION

lhis overview describes the status of conducting polymers and the role they could play in energy
technologies. Focus is provided by the importance of interfaces for the applications of conducting
polymers and the importance of improved abilities to manipulate the properties of interfaces, which can
result in performance improvements. Years of basic research have led to the development of several
products, some of which have started to reach the market, and to the fabrication of experimental, bench-
scale applications. The numerous applied research results in the open liter.ature, as well as proprietary
information, need to be taken advantage of by the private sector, which has the challenge of introducing
this new technology into its products and of designing applications unique to conducting polymers. In
all the facets of this technology, reproducibility, reliability, and effectiveness are of importance to the
potential user. There are common concerns that need to be addressed for all applications incorporating
conducting polymers. Processing conducting polymers is an important aspect of materials development
or device fabrication, because processing conditions often greatly affect the morphology and the surfaces
of the polymer as well as interfaces. Therefore, process reliability and reproducibility is very important
in any materials production-utilization scheme.

The issues of importance in the area of conducting polymers are related to materials properties
and fabrication processes. Among the issues that need to be addressed are stability (of the polymer and
the consequent reliability of its function in a given application), conductivity, adhesion, mechanical
properties, and resistance to hostile environments, such as in automotive (under hood) and photo voltaic
applications, soiling, interface properties, and performance/cost-effectiveness issues. Surface modification
and passivation techniques that apply to conducting polymers and surface characterization of these
polymers will be described briefly to help develop the commercialization of conducting polymer
technology.

The research community has so far contributed a great deal toward the ultimate goal: the use of
this technology by producing materials and bench-scale applications accompanied by a characterization
effort that uses a wide variety of techniques. Systems optimization is a must for any future uses and
therefore, the private sector can take advantage of the optimization process toward establishing
performance windows and tolerances on processes, products, and applications produced on a large scale
and thus establish a cost-effectiveness/performance correlation that justifies pursuing a specific application.

As we outline the various application areas of interest, specific questions and needs will be
presented in some cases, while in other cases, general or common concerns will be mentioned. In all
cases, the scientific and engineering communities need to work together to determine the most logical
ways of pursuing this technology to define areas and directions for further development.

The properties of materials alone or in applications are largely influenced by intrinsic phenomena
inherent in the bulk polymer. However, overall performance is influenced by materials morphology at
the macroscopic (surfaces and interfaces) and microscopic scales. The former is of importance because
of the polycrystalline character of conducting polymers.

In addition to the common processing effects on surfaces and interfaces in polymers in general,
doping/dedoping processes add to the complexity of conducting polymers whose interfaces are affected
by the diffusion of the dopant. This complexity stems from the dimensional changes that take p.ace

27-2
simultaneously as the polymer is doped or dedoped. However, advantage can be taken of these
dimensional changes" as will be mentioned later.

Among the areas recommended for study in this paper are redox-type applications, shielding, and
sensor applications. '

II. OBJECTIVES

The objectives of this paper are (1) to outline the importance of interfaces in the technological
applications of conducting polymers and (2) to improve, based on the characterization-optimization
process, the methods for manipulating the properties of conducting polymers at interfaces and their
stability for maintaining high performance in the various applications.

III. AREAS FOR CONDUCTING POLYMER APPLICATIONS

A. Energy Storage and Energy Conversion

The first commercialization of conducting polymers was by Bridgestone-Seiko for polyaniline

button cell batteries. Such batteries use a polyaniline cathode, a lithium-containing anode, and an
electrolyte in which dopant ions are stored in salt form. These rechargeable batteries display excellent
shelf life with respect to charge retention and high cycle life, but suffer from inherent limitations on both
energy storage density and power density. Allied-Signal researchers have shown that much higher energy
storage densities can be obtained for high cycle life conducting polymer batteries if the conducting
polymer is used only as an additive for an alkali-metal-alloy anode of a battery that has an inorganic
cathode. Such use of conducting polymers takes advantage of the ability of selected donor-dopable
conducting polymers to dramatically increase the cycle life of alkali-metal-alloy anodes. Prototype A-size
batteries were constructed (using either polyacetylene or poly[p-phenylene] having about 70 W/kg
capacity, compared with achievable storage capacities of about 45 W/kg for NilCd cells, < 10 W/kg for
the Bridgestone-Seiko button cells, and an inherent limitation of about 35 W/kg for larger polyaniline
batteries of similar design.

Recent commercialization activity has also focused on the use of conducting polymers in
supercapacitors. One design, commercialized in Japan, uses a conducting polymer with a compositional
gradient for a metallic conductor, as well as for an electrolyte. Higher capacity, but decreased frequency
response, resulted for another design of a conducting polymer capacitor, which is said to be near
commercialization in Japan. This second type of capacitor is basically a high charge-discharge rate battery
that uses the region of a discharge curve for a conducting polymer in which voltage is strongly dependent
on dopant concentration.

Preliminary research suggests that conducting polymers provide interesting materials for the direct
transformation of electrical energy to mechanical energy via the dimensional changes induced by oxidation
and reduction. Conducting polymer electromechanical actuators should have more than an order of
magnitude advantage over competing piezoelectric and magnetostrictive materials in work density per
cycle, but they have major disadvantages in both cycle life and cycle rate compared with these alternative
materials.

There is a commonality of problems that limit performance of conducting polymers in the battery,
capacitor, and electromechanical actuator applications. In each case, device performance is measured in
capacity per cycle, cycle rate, and cycle lifetime, and in each case, interfaces can provide important
limitations on performance.

27-3
 For example, cycle rate can be optimized by minimizing diffusion distances through the use of
very thin electrodes. In the thin-film limit. the interface between electrode and electrolyte represents an
important rate-limiting element, as well as the preferred site for chemical degradation that limits cycle life.
Also, dimensional changes during redox can create interfacial stresses that limit cycle life.

B. Ionica}ly Conductive Polymers

Research has expanded consider"ably in the development of solid polymer electrolytes for
applications in high-energy-density batteries, supercapacitors, fuel cells, chemical sensors, and electronic
displays. Specifically, advanced polymer electrolytes are key components in the development of solid
state rechargeable batteries and fuel ceUs for transportation applications. Electrical vehicles, made possible
by the development of high-performance batteries, provide one possible way to meet the demanding zero-
emission mandatory regulations that will be applied in Southern California in the next few years. Similar
strict environmental regulations are currently under discussion in several other states.

Polymer electrolytes offer significant advantages in comparison with liquid electrolytes. They
combine in one material the function of electrolyte, separator, and binder for the cathode materials, thereby
reducing the battery complexity. Polymer electrolytes cannot leak out of the battery, and they preclude
the possible dangerous pressure buildups of the volatile liquid electrolytes. These characteristics make
polymer-electrolyte, solid state devices safer and more adaptable to hostile environments. Moreover,
polymer electrolytes can be fabricated as thin films and allow space-efficient designs of batteries or other
electrochemical devices. The flexibility of polymer electrolytes also allows volume changes in the
. electrochemical cell without physical degradation of the interfacial contacts.

Wright and coworkers originally observed the ionic conductivity of complexes of alkali metal salts
with poly(ethyleneoxide) (PEO). Armand and coworkers developed a detail understanding of the ionic
conductivity of PEO and poly(propylene oxide) (PPO) salt complexes and proposed their use as polymer
electrolytes in high-energy-density batteries. For the PEO-salt complexes, it has been suggested that the
alkali metal cations reside in the helical tunnel otPE~, which is in a (T2GT2G) conformation. This
structure is similar to that for the complexes between Li+, Na+, K+, and crown ethers. However, PEO and
PPO complexes exhibit suitably high ionic conductivity only above 100°C. In the past few years, a
significant research effort has been devoted to the synthesis and evaluation of novel polymer electrolytes
having the necessary structural properties to ensure high ionic conductivities at room temperature, good
mechanical stability, and minimized interfacial resistance at the electrode/electrolyte interface.

Based on these goals, SRI International has recently developed unique single-ion polymer
conductors with ion conductivity as high as 1.0 x 10-3 S cm- 1 at room temperature. Single-ion polymer
conductors allow greater depth of charge and discharge, and therefore better use of the electrode capacity
by minimizing polarization effects at the electrode/electrolyte interface, a serious drawback of bi-ionic
conductors such as PEO or PPO.

Applications of polymer electrolytes to electrochemical solid state devices will take significant
advantage of the understanding of electrode/electrolyte interfacial phenomena and the development of ways
to minimize interfacial resistance. With less resistance, we will achieve higher capacities, optimum cycling
in polymer rechargeable batteries, ultrahigh capacity at the complex electrode/electrolyte interface of super-
capacitors, higher charge/discharge rates, faster kinetics at the electrode/polymer electrolyte/catalyst
interface of fuel cells, faster switching rates in electrochromic displays, and faster response times in
chemical sensors.

27-4
C. Applications to Photonics

Photonics-the generation, manipulation, transmission, and detection of light-has enjoyed

tremendous growth since the advent of diode lasers and optical-tiber-based telecommunications. To take
advantage of propagation speeds and massive parallelism inherent in photon-based communicationS,
information storage, and computing, fast optoelectronic and all-optical modulators are needed; devices
based on highly nonlinear materials are ideal candidates for these and other applications.

. Conducting polymers, and generally all 1t-electron containing and conjugated polymers, exhibit
large third-order optical nonlinearities due to the high density and delocalization of 1t-electrons along the
polymer backbone. For example, optical waveguide devices that exhibit all-optical switching and
intensity-dependent transmission have been fabricated from several crystalline polycUacetylenes. These
optical non-linearities can be further enhanced, for example, by dispersing small particles into the
polymers (e.g., as with semiconductor-doped filter glasses or metal particles embedded in glassy or
polymeric hosts). In addition to these nonresonant (negligible absorption) effects, conducting polymers
also exhibit large, metastable changes in optical absorption (photochromism) due to the formation of in-
gap energy levels associated with backbone distortions around localized photogenerated charges. These
resonant optical effects can be used for optical limiting and optical information storage, e.g., as has been
proposed for the conducting polymer polyaniline.

While most present applications of photonics do not appear . to involve the transportation and
utilities industries, the increasingly complex sensor and actuator systems required to measure and optimize
the performance of automotive and aerospace vehicles and to power generation facilities, may obviate the
need for optical sensors, communications, and information processing. Photonics may actually simplify
some systems: for example, the central vehicle lighting concept replaces the electrical wiring, switches,
sockets, and incandescent light bulbs currently used for automobile signals and headlights with a central
high-intensity light source and a light-pipe distribution system, reducing complexity and weight while
increasing reliability.

Most of the nonresonant nonlinear optical effects mentioned require high optical intensities
(0.1 MW/cm2) and long optical path lengths (of the order of 1 cm) to be useful; fortunately, the optical
fibers and planar waveguides used in coherent optical communications provide these conditions. Surfaces
and interfaces clearly play an important role in such devices, because it is imperative to reduce the optical
losses resulting from scattering by crystallites, cracks, or other defects in the surface and near-surface
regions of the waveguides. As yet unknown is the role of strain at the waveguide boundaries in affecting
the polymeric structure and thus the optical nonlinearity.

D. Electroluminescent Devices

Another photonic application of conducting polymers is the generation of light through electro-
luminescence. The Cambridge group first demonstrated that diodes using semiconducting poly(p-phen-
ylene vinylene) can emit visible light when reverse-biased current is passed through them. The spectrum
of the emitted light matches that produced from photoluminescence, suggesting that the electrons and holes
injected from the electrodes combine to form neutral excitons before decaying to produce light

Subsequent studies have achieved higher light emission efficiencies through the use of metallic
elements having lower work functions in the electron-injecting electrode, as well as through chemically-
induced enhancements in electron mobility in the polymer layer. Surface characterization and modification
are clearly as important in conducting polymer-based electroluminescent devices as they are in their
inorganic predecessors.

27-5
E. Applications in Displays

Conducting or electroactive polymers exhibit dramatic color changes associated with the chemical,
electrochemical, or optical doping of the polymer backbone, leading to self-trapped states that induce new
electronic levels in the semiconducting bandgaps of .these materials. For example, thin films · of the
insulating leucoemeraldine form of polyaniline are colorless, while electrochemical oxidation to the
conducting form produces green fIlms, and further oxidation yields insulating blue fIlms. The colors
produced can be quite different for other families of conducting polymers, depending on the size' of the
bandgap as well as the solitonic, polaronic, or bipolaronic nature of the species responsible for charge
storage. Moreover, the ability to attach to the polymer backbone a wide range of derivatizing molecules
allows color tuning within a particular family.

These electrochromic changes permit the construction of optical displays, windows, and light
valves. Control of the electrochemical potential of the conducting polymer by an individually addressable
electrode array can be used to produce a flat-panel display. Individual conducting polymer electrochemical
cells have exhibited submillisecond optical switching times, sufficiently short for display app~cations.
The transportation and utility industries could be greatly impacted by the use of so-called "smart
windows"-conducting polymer/electrolyte/counterelectrode sandwich cells-to lower the solar heat load
on automobiles, aircraft, office buildings, and homes.

Other automotive applications of electrochromics include variable-transmission sunroofs and

variable-reflectivity rear-view mirrors. In these window applications, the time required to switch from a
transparent to an absorbing state is less critical. Electrochromic windows could also be used in various
other non-imaging applications such as in light valves in central lighting systems.

Central interfacial issues include the electrochemical polymerization or the spin- or spray-coating
of very uniform, adherent polymer films on conducting glass electrodes. Critical to the success of imaging
applications is the absence of haze due to scattering from crystallites or surface imperfections in the
conducting polymer. Thelong-term stability of the polymer-electrolytelcounterelectrode sandwich against
delamination or more subtle performance degradation due to the accumulated effects of doping':'induced
strain is also important. Studies of the stability of conducting polymer films against solar-radiation-
induced photochemistry are also important, particularly given the facile photoproduction of long-lived
doublet and triplet spins in many of these materials.

F. Electromagnetic Shielding

The large doping-induced changes in the complex dielectric permittivity of conducting polymers
extend from the ultraviolet and visible regions of the electromagnetic spectrum, through the microwave
and radio frequency regimes, and down to direct current (DC). Doped conducting polymers such as
polyaniline, polythiophene, polypyrrole, and polyacetylene possess microwave loss factors that compare
favorably with the inorganic materials now used commercially for shielding of electromagnetic interference
(EMI). Conducting polymers may provide significant advantages in EM! applications given the wide
variety of ways they can be used. Coatings can be applied by electrochemical or solution techniques to
the object to be EM! shielded, or the object itself can be form~ from materials that incorporate
conducting polymers (even at low loading levels)' in the form of blends, composites, or interpenetrating
networks. For example, EMI shielding of lightweight electronic equipment is possible. Electrochemical
conversion between the doped and undoped forms of the conducting polymer allows the EMI shielding
or screening to be switched on and off at will, a potentially useful feature in some applications.

27-6
 The utility of conducting polymers in electromagnetic shielding extends to the DC limit. Even
relatively low conductivity, partially-doped conducting polymers can be used in antistatic applications.
The wide range of processing techniques and processed forms can provide many useful materials: textiles
for antistatic clothing or mats, as well as conducting coatings or composites for the entire fuel line in
vehicles-fuel tank filler neck, gas tank, fuel line, and fuel filter. Static dissipation applications in the
microelectronics industry include polyaniline films for reduction of charging in electron beam lithography.

The flexibility afforded by control of the derivatization and doping level of various conducting
polymers allows the production of potentiallow-emissivity window coatings transparent in the visible,
absorbing in the near-infrared, and transparent in the mid-infrared. The emissivity could be controlled via
electrochemical techniques to allow tuning of the radiative properties of the windows.

G. Energy Transmission Applications

Research efforts in the last few years focused on increasing conductivity and anisotropy in
conducting polymers by increasing chain orientation and chain perfection using various techniques. Some
of these techniques led to the synthesis of, for example, polyacetylene, whose room-temperature
conductivity parallel to the orientation direction is near that of copper. Other conducting polymers have
provided chain direction conductivities that are about an order of magnitude lower than those reported for
polyacetylene.

Advantage lpight be taken of the high conductivity and high anisotropy in electrical transmission
wiring, particularly in aerospace applications in which weight is a critical issue. Oriented polyacetylene
with a conductivity of the order of lOS Stcm, a capacitance of few pFtm and an insertion loss (attenuation)
of < 0.1 dBtm would perform as a good transmission wire for some low current applications. However,
the poor environmental stability of this particular polymer would require an insulation that would act as
a good oxygen barrier because of the reactivity of the polyacetylene in air. Also, stable n-type dopants
that provide high electrical conductivities need to be developed

Energy transmission applications will become a reality only if the thermal stability of
polyacetylene is improved to the same extent that it has been in other conducting polymers. These
applications require more development work to find adequate processing techniques that would yield
highly conducting fibers of polyacetylene. Other polymers, such as poly(phenylene vinylene), whose
conductivity is approximately l(f Stcm, have been processed in the form of films and fibers. However,
conductivities need to be higher for an efficient signal transmission in wiring applications in which signal
insertion loss and return loss are critical. With a density of approximately one-sixth that of copper or
copper alloys, conducting polymer usage in wiring applications could result in major weight savings.

Conducting polymers in the form of composites (with lower conductivities) could be used in
ignition cable applications if the material is thermally stable in high-temperature environments.

H. Sensor Applications

Because conducting polymers undergo dramatic changes in electrical and optical properties on
doping, dedoping, and dopant compensation, conducting polymers provide unique materials for sensor
applications. For example, dopant-induced changes in polymer conductivity can readily exceed thirteen
orders of magnitude-thereby providing the basis for highly sensitive indicator devices.

Remotely readable, in-box indicator devices for product monitoring during shipment have been
patented by Allied Signal. These indicator devices result from the combination of conducting polymer

27-7
technology with the commercially available technology of radio frequency and microwave frequency
antitheft devices. Device operation depends on the coupling of conducting polymers with the antennae
of the antitheft device to provide a remote, readable signal that' measures the effect of selected ambient
variables on the conductivity of a conducting polymer. .The antitheft targets and hand-held transmitter and
receiver needed for this application are inexpensive (about $O.03/target and $300 for the remote monitor.
Additionally, the targets can be quite small, about one;.in. square film-like devices.

Using various device designs, a variety of indicator devices have been demonstrated. The
remotely readable devices include time-temperature indicators, temperature limit indicators (freeze and
defrost), humidity indicators, irradiation dosage indicators, mechanical abuse indicators, and chemical
release indicators. Such devices can be especially useful for applications in the transportation industry's
handling of products, which can be adversely affected by environmental factors during shipment. The
device can be located in the shipping container so that both product and indicator are exposed to the same
environment and can be remotely read without opening this container.

Suitably designed devices respond to the effects of ambient variables in the same way as the
ambient variables affect product quality. Successful design of such devices critically depends on
knowledge of the effects of interfaces on the transport of doping agents and/or dopant compensation agents
to the conducting polymer.

Conducting polymers are generally obtained by dQping conjugated polymers with various electron
donors or acceptors. Therefore, exposure of a polymer in its undoped state to one of these dopants,
particularly electron acceptors, increases its conductivity to a level that depends on the amount of exposure
to the dopant. In this respect, these polymers could be good sensors .for halogens, Lewis acids, and
protonic acids in their vapor phase or in solutions. Such applications could be useful for detecting trace
amounts of these materials in working areas, in disposal areas, and in shipping.

Because conductivity is thermally activated in conducting polymers, these polymers could be used
in thermal sensing devices. Because the activation' energy varies with the doping level, polymers can be
tailored to fit specific thermal sensing needs, based on the temperature increments to be monitored. Also,
the conductivity of conducting polymers varies with pressure. This variation is influenced by morphology
of the polymer, inter-particle resistance, and temperature.

For their semiconducting or undoped states, conjugated polymers respond to various radiations by
an increase of their resistance. On removal of the radiation source, the resistance returns to its initial
value. Therefore, conducting polymers can be good candidates for incorporation in radiation-monitoring
devices relevant for the monitoring of radioactive waste storage and transportation.

IV. MA'IERIALS PROCESSING

Conducting polymers can be obtained and processed in various forms, some of which are outlined
below.

A. Films and Coatings

Highly conductive polymers such as polyacetylene, poly(p-phenylene), polypyrrole, etc., are

intractable powders in their doped conductive form. Most of these polymers can, however, be produced '
by electrochemical oxidation in appropriate electrolytes as freestanding films with useful electrical and
mechanical properties. Thus polypyrrole fIlms are produced commercially under the trademark LUtamer®

27-8
by BASF in Germany. Also, polyaniline, which is produced under the tradename "Versicon" by Allied-
Signal Inc., can be solution-processed in either film or fiber form from either doped or undoped states.

Chemical and electrochemical polymerization of pyrrole and aniline can be conducted on support
ftlms such as polyvinyl alcohoi), poly(vinyl chloride), polyacrylonitrile, polycarbonate, and others to yield
composite structures combining the physical properties of the support structures with the electrical
properties of the conductive polymer. Such products are commercially produced by Bayer in Germany
and several companies in Japan.

A special in situ polymerization 'of pyrrole and aniline has been reported on materials having a
large surface area such as membranes, textiles, or fIllers (mica, clay, etc.). Commercial products based
on polypyrrole coated textiles (fibers, yarns, and fabrics) are available in the United States under the
trademark Contex™ from Milliken & Co. Products based on coated fillers are available from Cookson
Inc. in England. These products show very uniform coherent coatings of conductive polymers around
fibers and, in the case of ftllers, particles. Similar to the properties of coated films, the coated textiles .
combine the basic mechanical properties of the substrate fabric with the electrical properties of the
conductive polymers. in contract to the case of coated films in which a surface resistance of only several
thousand ohms per square can be attained, textiles with a sheet resistance as low as several ohms per
squ:p-e can be produced.

Dispersions of polypyrrole and polyaniline suitable for producing coatings on various substrates
have also been obtained. Commercial products of this nature have been offered in the United States by
Polaroid and recently by Solvay in Belgium.

Another approach to achieve conductive polymers suitable for films and coatings is the synthesis
of a tractable intermediate polymer that can be transformed by heat or other reaction into the intractable
conductive polymer. Thus .coatings or films are produced from the soluble or meltable intermediate and
later transformed into the conductive form.

Soluble conjugated polymers can, however, be produced by the incorporation of often bulky side
groups into the monomers. Such incorporation of side groups usually lowers the specific conductivity of
such compounds. Solubility of polypyrroles, polythiophenes, polyanilines, and other polymers can be
achieved by this method, and even water soluble products have been reported. Most of these products,
however, are only soluble in their undoped form and have to be doped after the coating operation. A
product of this nature is the polyalkylthiophene produced commercially by Neste Corporation in Finland.

Conductive coatings are usually produced in layers less than l-IJID. thick. A deterioration of the
electrical properties may be reasonably anticipated if the coatings are exposed to harsh environments. This
deterioration may be on the microscopic level, such as formation of cracks and interruption of the
continuity of the coating, or on the molecular level, such as disruption of the conductivity by oxidation
or substitution. In many cases, the deterioration of the electrical properties has to be prevented by
protective coatings or other encapsulations of the conductive polymer. There are, however, applications
in which a limited high-temperature stability is sufficient for a commercial use, for instance, in static
dissipation in which a difference in conductance even of several magnitudes, may be immaterial. In other
applications such as in generators, motors, and transformers in which semiconducting materials are needed
to eliminate certain side effects such as eddy-currents, performance with minimum variations under severe
conditions of high temperature and high electric field are needed over a period of 50 years. Present
conductive polymers are far too unstable for such appliCations at the present time.

27-9
 New possibilities may also be offered through the use of multilayer conductive structures.
Transportation and utilities technology areas that will be impacted by these structures include optical films
(e.g., optical waveguides), protective layers (coatings and encapsulants), sensors, transducers, modified
surfaces (adhesion, friction, wear, and lubrication, as well as biologically and chemically active substrates),
membranes, microlithographic materials and modified electrodes and electronic devices. The potential for
spin-offs to other technology areas is enormous.

Of particular interest are organized molecular assemblies (OMAs), which are thin-film arrays that ·
can (via the influence of the substrate) possess cooperative properties different from the individual
molecular components. There are a number of key scientific principles operating in molecular films that
we do not understand and that · prevent us from developing and using these structures. A dominant
scientific issue is understanding interactions at the OMA-substrate interface, between the chains, and at
the ambient interface. To gain this understanding, improved quantitative methods are needed for
characterization. particularly of film defects. Additional needs include theories relating surface properties
(e.g .• wetting) to surface molecular structure. synthetic protocols to make highly patterned, multifunctional
surfaces. and controlled pore size and pore distribution films.

B. Conducting Polymer Compo~ites

Conducting polymer composites with insulating polymers provide a variety of application possibil-
ities, especially in EMI shielding and electrostatic charge dissipation. Major advantages in processibllity
and/or achievable conductivities result for such composites in high performance applications (such as EMI
shielding) compared with the case of conventional carbon black or metal-filled composites. For example.
conductivities of 0.1 Stcm are achievable with difficulty for carbon black composites and are too low for
use in high-performance EMI shields. while available polyaniline composites have sufficiently high
conductivities (about 1 Stcm and above) that such composites are quite attractive for EMI shields. The
. EMI shielding application in housings is especially important for preventing electromagnetic interference
for communications, computational. and transportation equipment

A special advantage of the conducting polymer is the achievement of percolation at near zero
loading levels for gel-processed polymers and at less than 8% for melt-processed polymers. .The
performance of such composites is strongly dependent on interfacial effects, such as interparticle contact
resistances and the occurrence of percolation. Advances in understanding the chemical and structural
nature of interfaces and the development of improved methods for modifying these interfaces are expected
to provide further performance improvements.

C. Adhesives

The existence of readily derivatizable polymers possessing high conductivity suggests the potential
for obtaining conducting polymer adhesives. For example, polyaniline derivatives have been developed
as thermosetting resins for aerospace applications. Other applications include that proposed by the Ohio
State University group for microwave welding of structural polymers using conducting polymers in film.
composite. or powder form applied to the interface of the objects to be jointed; the strong microwave
absorption of the conducting polymer causes local heating and flow -at the interface. A better
understanding of the interfacial processes involved-interdiffusion, entanglement, and chemical cross-
linking of the polymer chains-may help optimize interfacial properties.

27-10
v. LONG-1ERM PERFORMANCE AND STABILITY OFMUL1TI..AYER CONDUCTIVE nnN-FILM
STRUCTURES

The possibility of preparing inexpensive, lightweight structures of conducting materials into

configurations with unique electrical properties depends critically on successfully addressing key research
issues such as stability, durability, intennolecular interactions between layers or phases, purity, bonding,
structure, defect concentration, and interface definition.

Widely available materials must be identified, certified, or in some cases, developed specifically
for use in conducting structures.

Some of the important parameters, physical properties, and technologies required for conductive
polymers in these structures include the following:

• Conductivity and its temperature-dependence in low- and high-temperature regimes

• Dopants used to obtain conductivity

• Environmental and chemical stability in air and ~O

• Thennal stability

• Commercial availability

• Preparation, processing, and handling

• Processibility and deposition methods

• Mechanical properties, including coefficients of expansion and stability after repeated temperature
cycling

• Adhesion to inorganic and organic materials

• Contact resistance to adjacent layers

• Traceability with varying topographies of different adjacent materials.

Two major impediments to the use of conducting polymers-poor environmental stability and
processibility-have been considerably improved in recent years through the exploration of the following
routes:

• Polymer composites

• Electrodeposition

• Ion implantation

• Solution processable systems

• Chemical vapor depoSition.

27-11
 However, further exploration and a more detailed understanding of mechanistic and kinetic aspects of these
processes are needed.

The study of degradation (mechanismlkinetics) and stabilization of multilayer conductive structures

will be crucial in improving durability of products and in predicting lifetime accurately. The primary
focus of degradation/stabilization studies should relate the decline of conductivity to both external stresses
(e.g., thermal cycling, photon flux, humidity, O2, or pollutants including synergistic effects) and internal
stresses (e.g., interdiffusion and mismatch in mechanical and chemical properties).

VI. PRODUCT CHARACTERIZATION

We encourage developing both new macroscopic and microscopic methods and modification of
existing techniques that will make materials and interface behavior more easily accessible. Problems and
constraints in this regard are expected to be similar to the ones experienced with other materials. Of
particular interest is the dependence of the electrical properties for conductive layers that are only a few
monolayers or less in extent Relative enhancement of interfacial molecular properties (structural and
dynamic) as opposed to molecular bulk properties is expected to be of great interest and importance. It
will also be important to understand exactly the meaning of the experimental parameters measured or cited
for films of various thicknesses. Characterization tools may have to be specifically designed for thin
multilayer films.

The question of composition is clearly more complicated for layered materials than it is for bulk
samples and will tend to be more subtle, e.g., concentrating on how composition varies with position
(either in-plane or perpendicular to the plane). Intramolecular structural issues will center around how
. bonding occurs at a surface or interface, while structure on the supermolecular size scale will tend to
address how orientations are correlated over dimensions greater than the few molecular diameters.

Diagnostic techniques and methodologies (e.g., FTIR-RA, XPS, SIMS, ISS, GPC, ellipsometry,
surface plasmon resonances) need to be further developed and improved to investigate relevant research
issues in conducting multilayer stacks, such as adhesion, delamination, interdiffusion, changes in interface
composition, and degradation of polymers. Unfortunately, a thin-film probe with the power that NMR
has for bulk samples is still not available.

Attention should also be paid to the issue of sensitivity and the effect of the characterization probe
on the characteristics of the thin-film structure. The ability to provide in situ information is of utmost
importance, because the chemistry, microscope organization, and thus the function of the surface-bound
species in OMAs can be very dependent on the specific chemical environment in which they are situated.

VII. SUMMARY OF TECHNICAL GOALS AND R&D NEEDS

A summary of R&D needs is proposed in Table 1 as a guide for future efforts.

27-12
 Table 1. Summary of Technical Goals and R&D Needs for Conducting Polymers

Goals R&D Needs

A. Increase achievable electric~l conductivity. Develop processes that decrease interparticule

resistances and induce percolation of crystallites
with optimal orientation.

Improve orientational order, e.g., by oriented

substrates.
B. Develop conducting polymers with Develop the understanding required for the
improved conductivity without decreasing manipulation of interparticle interfaces so as to
convenient processibility. achieve high conductivities in bulk polymers and
low percolation thresholds in composites.
C. Achieve improved environmental and Explore the application of surface modification
thermal stability. techniques for improving thermal and
environmental stability of coatings and multi-
layer structures.

Apply passivation techniques known for other

polymers.
D. Develop processing methods suitable for Develop substrates for thin-film applications.
the various materials and applications.
Develop dispersion techniques to achieve high
conductivities at low percolation thresholds in
composites.

Improve solubility ~d melt processibility of the

bulk polymers with high molecular weights.
E. Optimize ionic conductivity and Find ways to minimize interfacial resistance
mechanical properties of polymer between the polymer electrolyte film and the
electrolytes. electrode.
F. Optimize. substrate surfaces in which Achieve control of the polymer synthesis and
interface properties are critical for good the subsequent surface treatment necessary for a
performance in device applications. given application.
G. Achieve transparent conducting polymers. Improve thin-film fabrication and develop
materials with suitable bandgaps.
H. Achieve strong adhesion of conducting Develop an understanding of surface energetics.
polymers onto various substrates.
I. Fabricate polymers with useful mechanical Determine the of effect of increased molecular
properties, such as high tensile strength and weights and molecular weight distribution on the
flexibility. mechanical properties.

27-13
 28. PHOTOELECTROCHENUCALSYSTEMS

Barry Miller, AT&T Bell Laboratories, Chairman

Stuart L. Licht, Clark University
Mark E. Orazem, University of Florida
Peter C. Searson, Johns Hopkins University

SUMMARY

Photoelectroche~cal systems encompass numerous applications involving semiconductor/electro-

lyte interfaces. A major goal has been solar energy conversion. Double-digit efficiencies have been
reached with two different forms of semiconductor-electrolyte photojunction, directly excited or dye-
sensitized. Impressive performance with even polycrystalline semiconductor substrates is attainable in
these devices and makes them promising in photovoltaics and photoelectrosynthesis for efficiency and cost.
Achieving improved stability and further advances in output and economics depend on further progress
in understanding and modifying solidlliquid interfaces. Related developments have produced numerous
spin-offs of substantial importance to solid state devices, processing technology, and surface chemistry.
Further progress toward significant applications of interest to utility, electronics, and transportation
industries, in energy conversion, and toward a host of specialized opportunities from sophisticated etching
of microstructures to water purification, requires a serious effort to support and strengthen the fundamental
underpinnings of the field These needs are categorized in the conclusion of this overview.

I. INTRODUCTION

Photoelectrochemistry, for our puqJOses, involves systems in which light excitation at a semi-
conductor-electrolyte junction causes charge separation and transfer to occur, with consequent chemical
reaction at the interface. Light to electrical energy conversion may be one outcome, when the junction
is coupled into a cell to complete a circuit.and has held the pivotal attraction. However, the chemical
aspects lead to many other applications of increasing importance. Interest in phenomena at semiconductor-
electrolyte junctions is historically coincident with the invention of the solid state photovoltaic solar cell.
Both areas have advanced from the base of understanding in solid state physics. A junction coupled to
bulk phases exists in both solid state and solid-liquid devices, and the study of these interfacial regions
has been an important theme for physics and chemistry in the last 40 years.

In the 19708, the experiments of Fujishima and Honda [1], showing the feasibility of solar produc-
tion of hydrogen fuel in a semiconductor-electrolyte cell, and Gerischer's basic concept [2] of a power-
producing semiconductor-photoelectrochemical device led to rapid progress in the direction of energy
conversion. With parallel growth in understanding of the active interface, the field has also evolved
widely, and there have been a multitude of imaginative extensions outside·of energy problems. We will
briefly outline the scope of these developments and summarize the research needs required for further
translations into effective technology.

We treat the subject in five parts: Energy Conversion; Fabrication of Interfaces and Structures;
Characterization; Synthesis, Detoxification, and Degradation; and Fundamental Issues. Funding of related
research has been reduced since the early 19808 along with the diminished overall effort toward solar
alternatives. Some of the promise for solar energy conversion has been dulled by generally unresolved
long-term stability issues attributable to the chemistry at the solid-liquid junction. Yet it is important to
realize that the energy conversion research has been synergistic to the numerous other applications these

28-1
efforts have spawned. We conclude with a list of needs for research, standards, and methodologies in this
field that must be met to have substantial impact on surface processing and related technologies.

II. ENERGY CONVERSION

A. General FeatUres

An illuminated photoelectrochemical (PEC) cell bears a formal resemblance to a traditional

Schottky barrier photovoltaic (PV) device, with the metal layer contacting the semiconductor replaced by
an electrolyte containing an appropriate redox couple. For both PEC and PV junction devices, light above
bandgap energy excites carrier separation in the semiconductor, driving electronic charge (electron or hole,
for p- or n-type, respectively) into the semiconductor bulk. Translating this into a current in a PEC
requires charge transfer chemistry to occur both at the semiconductor electrode surface and at a second
surface, or counterelectrode. The solidlliquid interface and the coupled chemistry impact cell function,
design, and applications. Both striking opportunities and some inherent disadvantages for long-term
energy conversion result, when compared to the PV counterparts.

A semiconductor/electrolyte junction forms spontaneously and has continuous contact between the
two phases. With excitation and charge collection at such junctions occurring close together, solidlliquid
devices usually provide better performance with polycrystalline materials than solid state devices because
a more complete junction is formed by liquid wetting the polycrystalline grains. Since the PEC electrolyte
is continuously available to the active junction, the interface may be modified to accomplish stability and
enhance solar to electrical conversion. Many other useful aspects of the liquid junction system follow
from these features. It is of considerable importance that the semiconductor may be in the form of
discrete particles. Then the photocathodic (for p-type) or photoanodic (for n-type) reactions at th~
semiconductor· surface are carried out vicinally to the respective anodic or cathodic reactions at an
electronically coupled local counterelectrode. Fuel or other synthesis products may be generated in this
mode, rather than having direct power conversion ~ugh an external circuit

Power conversion efficiencies comparable to those of solid state cells have now been achieved in
a variety of photoelectrochemical cells. The knowledge base derived from these advances has furthered
other applications, such as microfabrication of solid state devices, sensors, photocatalysis, and environ-
mental improvement schemes, as elaborated in subsequent sections.

B. Light Absorption and Charge Transfer Schemes

In photoelectrochemical systems, the absorption of photon energy yields electronic energy in the
form of excess electron-hole pairs in semiconductors or in excited electronic states in molecules. Without
a mechanism of charge separation, this initial electronic energy would be lost as heat through recombina-
tion. Two distinct mechanisms of converting an excitation process into charge separation (currents) have
been applied in designing efficient photoelectrical systems. At semiconductorlliquid interfaces, an electric
field (the space-charge layer) forms at the semiconductor surface with charge/ion redistribution at the
liquid interface. If the photons are directly absorbed in the semiconductor to produce electron-hole pairs,
this electric field impedes recombinative processes by oppositely accelerating and separating these charges,
leading to minority-carrier injection into the electrolytic redox couple and photodiode behavior. This con-
cept of carrier generation is illustrated in Fig. la (for an n-type semiconductor).

Homogeneous photodriven molecular redox reactions are conceptually an alternative conduit for
photoelectrochemical energy conversion, leading to photoexcited products that migrate and inject their
charge into separate anodic and cathodic electrodes. However, such coupled charge separation and

28-2
 transport processes are too slow to inhibit recombination or other efficiency-destroying events, unless the
excited molecules are directly adsorbed on the semiconductor to act as a charge mediator. In this latter
dye sensitization mode, light absorption occurs in the dye, and the photogenerated majority carrier is then
injected into a wide bandgap semiconductor, as illustrated in Fig. lb.

Development of dye-sensitized semiconductors was slow because of the limited fraction of light
that could be harvested by a monolayer of dye and by competitive chemical degradation pathways for the
excited dye, considering the large number of turnovers of the injection process required for long-term
stability. The first example of a dye-sensitized device with efficiency comparable to those achieved by
direct excitation (Fig. la scheme) was recently demonstrated through the use of a novel high-surface-area,
thin-film nanostrueture of n-TI02 (produced by sol-gel routes), which is coated with an energetically
matched trimeric ruthenium complex of high photostability and immersed in 'an iodide/iodine-containing
electrolyte. The unusually high surface area of the transparent semiconductor, coupled to the spectral
characteristics of the dye, harvests a high proportion of the incident insolation [3].

Surface stability severely limits the life of electrolytically immersed semiconductors, and
photocorrosion is of particular concern. A semiconductor or dye thermodynamically well matched to the
solar spectrum may be intrinsically reactive in the PEC electrolyte. These factors restrict the choice of
suitable electrolytes and require inventive chemistry.

C. PEC Developments

Photoelectrochemical energy conversion is thus a hybrid field encompassing electrochemistry,

spectroscopy, and solid state physics. Solar energy incident onto a variety of semiconductors can drive
electrochemical reactions and result in the production of not only electrical, but also chemical or
electrochemical energy. In both Figs. 1a and Ib, the photoelectrode is coupled to a metallic counter-
electrode to generate electricity regeneratively, I.e., with no net chemical change. Examples of cells with
high solar to electrical conversion efficiencies are summarized in Table 1.

These efficiencies approach those of more mature solid state photovoltaic devices. Efficiency may
also be expressed in terms of the power saved in carrying out chemical fuel production. In one such cell,
power savings for hydrogen generation at platinized p-1oP have been realized by utilizing up to 12% of
, the incident sUnlight [12].

Finally, the components of a PEC cell are analogous to those in a conventional battery and,in
principle, the charge produced by the cell can also be electrochemically stored by the addition of a third

Table 1. Regenerative PEC Solar to Electrical Conversion Efficiencies

Year SolldlReacting Ion Efficiency, % Ref.

1991 nano n-TI02(dye)/r -8 3
1990 n-CdSe/[KFe(CN)J3- -16 4
1987 n-GaAs(Os~/Se2o -15 5
1985 n-Cd(Se,Te )/S2 o -13 6
1982 n-CdlnS~lIo -9 7
1982 n-WS~o -10 8
1981 n-MoS~lIo -9 9
1981 p-InPN3+ -12 10
1978 n-GaAs(Ru3+)/Se2o -12 11

28-3
electrode and an appropriate separator, instead of being stored in a product fuel. Figure 2 shows one
configuration of a PEC cell combining such in situ electrochemical storage with solar conversion capa-
bility to yield a continuous output that is insensitive to daily variations in illumination. The practical
system shown combines a Cd(Se,Te)/S-2x based conversion half cell and a SnlSnS storage electrode to give
a single cell operating at an overall efficiency of 11.4% [13]. Under illumination (Fig. 2a), photocurrent
is used partly to drive an external load and partly to reduce metal cations in the storage electrode. Then,
in darkness or at low light levels, the storage compartment can take over power delivery (Fig. 2b) by
metal oxidation.

D. Economic Considerations

Practical terrestrial energy conversion requires inexpensive, efficient, and stable devices.
Inexpensive systems require low-cost materials, ease of fabrication, simple chemical steps, and a means
of handling the chemical fuel produced, if the latter is the desired product. For any kind of photovoltaic
device, synthesis of single-crystal material is often time- and energy-intensive, and the process will
normally be limited to forming smaller cross-sectional area cells at high cost A variety of techniques can
provide cheaper forms of polycrystalline or amorphous thin-film semiconductors to consume relatively
small amounts of material while covering large surface areas. Modes of film preparation include slurry
techniques, chemical vapor deposition, casting of polycrystals, radio frequency (RF) sputtering, vacuum
co-evaporation, sol-gel processing, chemical bath deposition, hot pressing, and electrodeposition, among
others. These techniques have been variously used to prepare thin-fIlm electrodes of n-CdS, n-CdSe,
n-CdTe, n-GaAs, p-InP, n-Si and p-Si, and n-Ti02 for PEC 'cells [3,14] ..

A particular advantage of electrodeposition (Plating) techniques is the possibility of a one-step

chemical synthesis of a semiconductor without employing a great deal of heat energy to form the eventual
electrode, thus reducing the energy payback time, as well as initial cost, compared to virtually every other
scheme of synthesis. Future developments in both solid state and liquid junction photovoltaics will benefit
from a variety of commercial thin-fIlm techniques being developed for materials such as a-Si:H, CuInS~,
CdS, CdTe, and GaAs. . .

The performance of photoelectrochemical solar cells can degrade with time, typically significantly
faster than is observed for solid state cells. Corrosion and passivation of the solidlliquid interface and
degradation of the electrolyte can occur. Countering the degradation processes requires controlling kinetics
through the photoelectrochemical interface and developing alternative stable combinations of semiconduc-
tor and electrolyte. A loss of efficiency is generally observed for polycrysta11ine materials compared to
single-crystal forms. These losses are generally attributed to kinetic origins, e.g., recombination at grain
boundaries. It is of interest that thin-fIlm PEC structures have sometimes exhibited greater stability than
single-crystal counterparts, which have better initial efficiencies. This phenomenon has been attributed
to lower microscopic photocurrent density. The longest lifetime PEC device demonstrated to date, slurry-
deposited thin-film n-Cd(Se,Te) electrodes immersed in modified polysulfide solutions, has operated
outdoors for approximately 1 year. In this system, photoelectrode and electrolyte stability was achieved
by systematic optimization of the solution composition [15]. Efficient dye-sensitized devices, with a
2-month-equivalent sunlight lifetime, have been demonstrated. This advance reflects a substantial reduc-
tion in the quantum yield to degradation reactions with Ru-based dye complexes compared with previous
all-organic light absorbers.

Ill. FABRICATION OF INlERFACES AND STRUcruRES

Many fabrication procedures developed for PEC cells apply to other areas. Exploitation of light-
induced chemistry of the semiconductor at an electrolyte junction includes surface tailoring, etching, and

28-4
other manipulations of the morphology and surface composition of semiconductors. Since all of these
efforts relate-to the surface processing of semiconductors and to the same underlying theory implicit in
our discussion of photoelectrochemical cells, they will also benefit from better understanding of the
fundamentals of this technology.

A. Etching

The etching of semiconductors, with and without the action of light, is critical to the cleaning and
texturing of surfaces for device fabrication and formation of geometric shapes and interconnects in
integrated circuit and wafer-level technology. Covering the range from preparing uniform, smooth sur-
faces with low recombination velocities, through anisotropic processes for patterned pits or holes, to light-
assisted drilling of vias, these applications of semiconductor/electrolyte interfaces have become familiar
to modem processing. The net chemical reaction generated at any local area of a semiconductor surface
by a flux of light is usually proportional to the local intensity of absorbed light. Some of the most
interesting applications have been ones in which the incident light has been spatially patterned in electro-
lytes compatible to the accompanying dissolution chemistry and kinetics. A sampling below of some of
the more sophisticated light-assisted etching techniques that have had impact on semiconductor technology
illustrates the versatility of photoelectrochemical processing.

Symmetrically graded intensity has been used to fabricate lenses directly on emitting surfaces of
semiconductor lasers [16], diffraction patterns from a pair of light beams have inscribed holograms [17],
and laser beams of ultraviolet (UV) frequency have drilled holes in semiconductors [18], all through
photochemical processes. Gratings can be made with v-grooves etched through resist patterns [19], and
surfaces can be textured to be matte and nonreflective for photothermal methods, as well as for PEC or
PV efficiency improvement [11]. Etching can be controlled, either througft light generation of carriers
or through charge injection by the redox system, under circumstances appropriate to the redox potentials
and the substrate band edges in the redox medium. Many open questions remain in these areas that have
to do with chemical processes (dissolution mechanisms, passivation), light channeling, and solid state
diffusion -lengths, charge transfer kinetics, and crystal face faceting and etch-stopping phenomena. The
interactions between chemistry and solid state transport that lead to structures of extreme anisotropy and
phenomena of high contemporary interest, such as luminescent processes in porous silicon, are not yet
understood. Many improvements in the efficiency and reproducibility of PEC and PV converters have
resulted from etching processes that provide more ideal surfaces with fewer surface states and reduced
recombination.

Forming complex wafer-level structures requires demanding processing steps to carry out either
anisotropic or isotropic material removal, as necessary. Both "wet" and "dry" (chemical solution and
plasma etching) methodologies are required for the full range of problems, although the plasma methods
are more adaptable to the anisotropiC etch needs of fine line patterns. Mechanistic understanding of the
wet chemical processes has lagged. Kinetic interpretation has advanced further in the study of the
competitive substrate corrosion processes in PEC cells than in the area of understanding purposeful etching
itself.

Commonly achieved submicron dimensions are placing greater demands on the quality of sub-
strates as dielectric layers become thinner and breakdown mechanisms are more severely tested. This
requires interpreting surface roughening from chemical treatment in much more detail than earlier
technology required. Development progresses, but generally through empirical studies. The selectivity .
of dissolution rates for different semiconductors or alloys, as in ill-V laser fabrication, is an example.
Considerably less effort has been expended on systematic studies of differences between related materials,
or of different crystal faces in the same pure (or alloy) semiconductor.

28-5
 Significant accomplishments have been made through these sophisticated means of what amounts
to micromachining of surfaces. Modeling here is difficult because of the complex interactions. Better
mechanistic understanding is needed because of the diversity and attraction of the applications and the
dependence of semiconductor and laser device fabrication on the control of many such techniques.

B. Deposition

Reference has already been made to the deposition of thin films by a variety of means to form
semiconductor substrates for energy conversion devices. Electrochemical techniques have long been
attractive for such substrate synthesis, i.e., additive processing schemes as opposed to the subtractive ones
of the etching section. Large-area devices can be formed electrochemically and economically with an
energy expense that is readily recoverable because the current densities and voltages of solar conversion
cells in outdoor exposure and in electroplating are very much alike. Nonelectrolytic immersion chemistries
are similarly attractive for economic manufacturing.

Examples of both chemical and electrochemical synthesis are plentiful, especially for II-VI
compounds, but there are limitations in the device quality of materials formed. Crystallinity is sometimes
achieved only with postannealing, not in the as-deposited product The epitaxy or crystalline order that
can be achieved with chemical vapor or molecular beam deposition is a problem for the solvent systems
of electrochemistry. Whether efforts to improve electrochemical morphology (by such techniques as
underpotential deposition to introduce epitaxy) will have broad impact.is a research question. These
studies can now be supported by the proliferation of surface structure and in situ techniques, such as
scanning tunneling and atomic force microscopies, which have only very recently been made available.

C. Specialized Surfaces and Sensors

Because of the need in a PEC cell to improve the kinetics of the desired charge transfer step while
inhibiting photocorrosion, much effort has gone into modifying surfaces by chemical or electrochemical
means to enhance efficiency and stability. Modification can range from using. submonolayer additions of
metal ions [5,11] or depositing thin, electron-tunnelable fIlms of surface oxides [10], all the way to
forming a buried junction of a discrete metal or polymer interphase to which the solution phase is only
a contact, not barrier-determining. The chemical lessons learned in improving these surfaces have also
been applied to solid state PV junction devices of higher efficiency and to new sensors, as examples of
interesting spin-offs.

Sensors dependent on surface interaction of liquid or gas phases with a semiconductor that alters
the potential distribution or work function of the surface have been developed for a wide range of species.
Work function devices with metallized semiconductors are used as hydrogen sensors, for example; The
field of electrolytic sensing through changing potentials in the gate region of a field effect transistor has
grown strongly during the period common to work on PEC interfaces [20]. Light addressable photo-
electrochemical sensors (LAPS) [21] have been shown to be versatile and sensitive devices for a wide
variety of species.

Insight into modulated structures such as quantum wells and possible new functions for them have
been obtained by photoelectrochemical techniques [22]. The formation of porous nanostructures with high
bandgap materials such as n-1102 was earlier mentioned as critical to improving the efficiency of dye-
sensitized cells [3]. Self-assembled monolayers may also be used to modify semiconductor substrate
surfaces. All of these areas of surface morphology manipulation are subjects of very recent interest, and
will continue to have synergistic interaction with photoelectrochemical studies.

28-6
 Further credence to the need for fundamental studies is evident from the brief mention in this
section of the inventive interface engineering already employed on PEC cell surfaces. There are also
numerous key issues in catalysis, spatial control, selectivity, kinetics, and environmental compatibility that
underlie application and need~o be pursued.

IV. SYNTHESIS, DETOXIFICATION, AND D"EGRADATION

As we have discussed, photoelectrochemical systems may facilitate not only solar to electrical
energy conversion, but may also drive electrochemical and chemical energy processes. This concept has
been productive in photoelectrochemical synthesis, production of fuels, and detoxification of pollutants
in water systems. It has also contributed to our understanding of natural solar processes occurring where
there are semiconductors in contact with reactible substrates.

The classic system exemplifying photoelectrochemical synthesis is water photoelectrolysis to

generate hydrogen. Fujishima and Honda [1] showed that n-TI02 can be used to split water at about 0.1 %
solar to chemical energy conversion efficiency. This semiconductor has a bandgap of 3.0 eV and absorbs
. about 4% of the incident insolation. Other wide bandgap materials can absorb photons energetic enough
for this reaction (Table 2), but they have similar efficiency constraints.

Materials with a bandgap of less than 2.0 eV are much more capable of excitation with a substan-
tial fraction of the incident sunlight, in which 1.4 eV for a single absorber yields an optimum solar
efficiency by balancing the overlap with the solar spectrum and photon energy. Materials with bandgaps
near 1.4 eV may be used for hydrogen generation with concurrent electrical bias (Table 2).

Photoelectrochemicalgeneration of products can result from photocatalysis when the reaction is

thermodynamically favored, but kinetically inhibited (the synthesis of ammonia from the elements).
Product formation may be driven energetically by light excitation when the reaction is uphill thermo-
dynamically, as in most fuel-generating reactions (water splitting or various carbon dioxide reduction
schemes). Goals for both types of processes include obtaining valuable products, energy savings, environ-
mental advantage, novel routes, useful fuels, remote generation on demand, and modeling of biological
pathways.

Table 2. Photoelectrolysis of Water

Year Semiconductor* Bandgap (eV) Counter Electrode Ref.

1972 n-TI02(c) 3.0 Pt 1
1976 n-TI02(c) 3.0 p-GaP (2.4 e V) 23
1979 n-F~03(f) 2.2 Pt 24
1981 p-InP(Ru)(c) 1.35 Pt 12
1986 n-Sm03 (doped) -3.0 Pt 25
1986 p-Si(c)/polypyrrole 1.1 Ru02(p) 26
1986 p-CdTe(f) 1.4 Pt 27
1986 p-InP(c) 1.35 n-GaAs 28
1988 n-CdSe(c) 1.7 29
• c =single crystal; f = film; p = powder

28-7
 A variety of photoelectrochemical synthetic processes have been studied. Carbon dioxide or
simple organics have been converted to molecules like methanol, formaldehyde, formic acid, or methane
on substrates such as Ti02 [30], GaAs and GaP [31,32], Si02 doped F~03 [33], and BaTi03 [34-37].
Hydrogen and carbon dioxide have been generated from sugar, starch, and cellulose at Ru02 and Ti02
interfaces [38]. The conversion of cr and Br- to halogens at MoS2 or MoS~ junctions has also been
reported [39]. Numerous other examples could be cited.

Photoelectrochemical systems have been suggested for decontaminating environmental pollution

or other detoxification processes. A model system has even been suggested for saline demineralization
combining photoredox and membrane processes [40]. The photoassisted oxidation of oil slicks on sea
water is being pursued and modeled on Ti02 particles [41,42]. Certain noxious inorganics can be broken
down on semiconductor particles. Practical developments in these areas could lead to large-scale applica-
tions.

Thus photoelectrochemical systems have value not only as energy conversion devices, but also
in electrosynthesis, detoxification, and understanding and preventing light-driven degradation reactions,
such as those that Iilight occur in illuminated paints containing semiconductor pigments. We stress that
the underlying kinetics and thermodynamics of particles have a close relationship to the photoelectro-
chemistry already discussed. However, there are many special circumstances to be considered, among
which are catalyzing the surfaces of small particles for both anodic and cathodic reactions, the con-
sequences of generating products in close proximity, and quantum confinement effects, in small enough
particles, that shift bandgaps, band edges, and light absorption characteristics. These generate theoretical
. problems for the underlying science above and beyond ·those of macrosized semiconductor electrodes.

v. CHARACTERIZATION

A. Introduction

The characterization of photoelectrochenllcal cells needs to serve at least the significant

functions of

• Developing standards and testing procedures for PEC devices

• Establishing the surface, interface, and bulk properties of semiconductor materials

• Developing general techniques that can be used to analyze other related systems.

Standardizing the testing of PEC devices is necessary to provide a consistent means of comparing
data on their efficiency and stability, and on other quality measures. Accelerated test procedures would
be preferable, although the complex nature of the total cell complicates such considerations. On a
fundamental level, techniques are necessary to characterize the nature of surfaces, interfaces, and bulk
materials. Both electrochemical and nonelectrochemical techniques are required. An important conse-
quence of progress in interfacial and bulk characterization is that these techniques can be applied to other
systems. Methods that can be applied in situ have received increasing attention and have obviously great
value in electrolyte systems.

B. Standardization of Testing Procedures

Although PEe engineering efficiency, which is nominally the straightforward measure of the ratio
of electrical power outllight power in, there is, nonetheless, a strong need for standardization of testing

28-8
procedures. Taking a maximum voltage-current product from a cell output is routine, but whether 2- or
3-electrode configurations are used (all or part of the resistive loss accounted for, respectively), and
whether cell engineering or counterelectrode placement' are realistic, are some of the factors that impact
on the final percent of efficiency claimed. The spectrum of the light source, as well as the absolute power
level, is also critical and has effects varying with the semiconductor bandgap, action spectrum, and solu-
tion absorbance. There are typically more variables in the measurements of a PEC device than of a PV
device. Measurement in actual sunlight or with solar simulators is desirable, but there are intensity and
spectral effects to be considered for specific conditions, and standardization is required for effective
comparisons. For the most part, stability data can be obtained with laboratory light sources as long as
there are no special wavelength-sensitive degradation mechanisms. In one such case, photon energies that
can excite the wide bandgap semiconductor in dye-sensitized cells will lead to greatly increased dye
degradation.

Accelerated testing is an important goal, especially to determine the long-term stability of PEC
cells. Reasonable means of stressing the cells for this purpose need to be evaluated. For example, an
enhanced level of light intensity may change the degradation mechanisms and, consequently, the lifetime
estimation.

C. Analysis of Surfaces, Interfaces, and Bulk Properties

Many techniques have been used in the characterization of surface, interface, and bulk properties
ofPECs. Historically, the determination of bulk parameters such as minority-carrier lifetimes and carrier
diffusion lengths have been well established from solid state physics, and certain techniques, such as Mott-
Schottky plots, were used initially for electrolyte junctions. During the last 10 years, a number of novel
techniques have been developed for the characterization of electronic, electrochemical, and chemical
processes at semiconductor/electrolyte interfaces. These can be grouped under electrOChemical, solid state,
and nonelectrochemical methods.

Table 3 contains a summary of techniques currently available for' the characterization of semi-
conductor surfaces, the interfacial region, and bulk properties of both phases. Further discussion is beyond
the scope of this chapter. Combining the methods listed in Table 3 with the many forms of in situ optical
spectroscopies and techniques such as scanning tunneling and atomic force microscopy, gives the experi-
menter powerful tools for understanding the fundamentals processes in PEC cells. The diversity of
materials introduces the question of availability to individual investigators and the encouragement of
cooperative work that compares different complementary techniques.

D. Needs

The dynamic nature of semiconductor/electrolyte interfaces requires characterization methods

sensitive to kinetic parameters. The properties of PEC cells are such that techniques should be sensitive
to bulk, interface, and surface processes arising from the potential drops in these regions. Although a wide
range of analytical tools has been identified above, there still remains a need for improved techniques to
characterize many aspects of these interfaces, particularly those sensitive to interfacial dynamics.
Processes related to passivation, surface damage, and surface stability are examples in which improved
characterization techniques would be of considerable benefit

The complications of electrode processes, however, can be reversed to advantage in many cases.
The electrochemical interface can be used as a temporary contact to characterize bulk and interfacial
properties of semiconductor materials. Such flexibility is unique to the semiconductor/electrolyte interface.

28-9
 Table 3. Characterization Techniques for PEC Cells and Components

I. Techniques at SemiconductorlElectrolyte Interfaces.

These techniques involve the use of an electrolyte as a means for voltage perturbation and current
collection. Since the electrolyte phase is removable, these techniques may also be used for the
characterization of solid state structures and devices [43].

Technique Application

Photocurrent Spectroscopy-measurement of photo- Determination of surface and bulk properties of

current as a function of wavelength, intensity, semiconducting and insulating materials (e.g.,
electrode potential, and electrolyte composition. quantum efficiency, bandgap, inter- and intra-band
transitions, structure, localized states, etc.),
characterization of processes such as recombina-
tion, trapping, photocorrosion, tunneling, etc.
Photocurrent Imaging-measurement of the spatial Identification of spatial distribution of defects,
distribution of photocurrent (or photovoltage) as a grain boundaries, secondary phases, surface
function of wavelength, intensity, electrode damage, sub-bandgap states.
potential, and electrolyte composition [44].
Resolution - 2 IJ.ID.
Capacitance!Mott-Schottky Analysis-measure- Determination of dopant concentration and flat
ment of space-charge capacitance as a function of band potential; in some cases, interband states may
band bending (voltage). Usually a single also be measUred.
frequency measurement
Carrier Depth Profiling-sequential capacitance Determination of dopant concentration as a
measurements and photootching. function of depth into the material.
Electrochemical Photocapacitance Spectroscopy Determination of density of deep-level states and
(EPS)-measurement of capacitance or futI rate of trapping.
frequency impedance response under sub-bandgap
illumination [45].
Electrochemical Impedance Spectroscopy- Analysis of kinetics of photoprocesses in space-
measurement of electrode impedance as a function charge and double layer regions; electron transfer
of frequency (typically 10 kHz-I mHz) under . to electrolyte; bulk and surface recombination;
illumination as a function of wave-length, trapping at surface states, etc.
intensity, electrode potential, and electrolyte
composition.
Photoacoustic Spectroscopy (PAS)-measurement Characterization of processes such as radiationless
of acoustic signal generated by light absorption recombination.
[46].

28-10
 Table 3. Characterization Techniques for PEC Cells and Components (Concluded)

Technique Application
Intensity Modulated Photocurrent Spectroscopy Frequency domain analysis of relaxation of
(IMPS)-measurement of the alternating current photoprocesses in terms of the frequency-
(AC) response to a modulated photon flux as a dependent quantum efficiency. Kinetic analysis of
function of direct current (DC) intensity, electron transfer, recombination, trapping, etc.
wavelength, electrode potential, and electrolyte
composition. Alternatively, the frequency
dependent quantum efficiency may be determined
from photocurrent transient data [47].
Time Domain Transient Analysis-measurement of Analysis of the kinetics of bulk and surface
the time dependent photocurrent (or photovoltage) recombination, electron transfer via surface states,
response to a short photon pulSe (1 ps - 1 ~). charging of the space-charge region, relaxation of
Measurements may be performed under open the band edges (two-electrode cell). For ultrafast
circuit conditions across a load (two-electrode cell) pulses, processes such as carrier generation may be
or with constant band bending (three-electrode investigated.
cell) [48].
Maximum Power Spectroscopy-the maximum Identification of regions of efficiency losses in
power output of a PEC or PV device is measured PEC and PV devices. Analysis of loss
from the cell response to a small amplitude AC mechanisms.
voltage perturbation as a function of light intensity
and wavelength. This technique can also be used
for the spatial distribution of the maximum power
output by scanning a focused laser beam [49].

II. Techniques at Solid State Junctions.

These techniques were developed for the characterization of solid state structures and devices.

Technique Application
Electron Beam Induced CurrentlPhoton Beam Determination of minority-carrier diffusion length
Induced Current (EBICIPBIC)-measurement of as a function of position.
current induced by focused electron or photon
beam excitation as a function of distance from a
junction. EBIC may be carried out in a scanning
electron microscope with a resolution of - 0.1 J.lIIl.
Open-Circuit Voltage Decay-measurement of the Determination of carrier lifetimes.
rate of decay of the open-circuit voltage in
response to minority-carrier injection.
Transient Capacitance Measurement-measure- Determination of carrier lifetimes.
ment of the capacitive time constant in response to
a voltage step at a reversed biased
semiconductorfmsulator interface. Spatial
resolution obtained by deposition of metal dots on
the insulating layer.

28-11
VI. FUNDAMENTAL ISSUES

The previous sections have covered a variety of applications of semiconductor/electrolyte interfaces

and their characterization. The areas considered for enhanced support are investigation of the photoelectro-
chemical conversion of light to electrical and chemical energy, investigation of electrochemical and
photoelectrochemical means for the fabrication of interfaces and structures, investigation of characterization
techniques that employ or pertain to semiconductor-electrolyte interfaces, and investigation of photoelectro-
chemically driven reactions such as chemical synthesis and detoxification of hazardous wastes. Success in
these target areas requires a parallel effort for study of the theoretical underpinnings, termed here the supporting
fundamental issues. An overall physical and chemical description for photoelectrochemical systems already
exists. Transferring this description to specific systems will require supporting further research in promising
areas defmed by these investigations.

A. Introduction

The critical components of a PEC (see, for example, Figs. 1a and 1b) are the semiconductor, the
electrolyte, and a counterelectrode. Electrical connection is made to the semiconductor through an ohmic
contact, and illumination can be provided through the electrolyte or the ohmic current collector. Developing
comprehensive models for this system requires that the physics governing the optical and electronic processes
within the semiconductor be coupled to the electrolytic processes that govern the electrolyte. A unique aspect
for the development of comprehensive models for photoelectrochemical cells is that the models must account
for the coupling of processes that take place in regions of vastly different scale. The thickness of the
electrically neutral region of a semiconductor depends on the dimensions of the electrode and may be of the
order of 100 IJlIl. The space-charge region in the semiconductor may be of the order- of 0.1 IJlIl. The
electrolytic analogy to the space-charge region is the diffuse pan of the double layer, which may extend
0.002 J.1Ill, but is typically of the order of ionic dimensions in more concentrated electrolytic solutions.
Concentrations vary in an electrically neutral region that may extend 100 J.1Ill, ~d, outside this region, current
and potential are governed by Laplace's equation.

The equations for convective and diffusive transport of species though the electrolyte are well
established, as are those that govern the solid state behavior of the semiconductor. The interface between the
semiconductor and electrolyte, however, is not as well understood. Although the semiconductor characteristics
playa significant role in determining the performance of photoelectrochemical cells, further success will require
a mechanistic understanding of the role of electrolytic species. The unresolved issues tend to center on
physical properties that determine the interaction between the electrons and holes in the semiconductor and the
ionic species of the electrolyte. Because certain aspects of this system are well understood, careful
experimental design can be used to isolate the unknown features. For example, use of a rotating ring-disk
electrode, for which the fluid mechanics and mass-transfer characteristics are well defmed, can be combined
with concomitant control of the light flux. The influence of interactive variables can be individually
distinguished through experimental designs that allow application of mathematical models for interpretation
of results.

B. Areas for Research

Fundamental research in the area of energy conversion should improve the understanding of the
semiconductor-electrolyte interface and provide a data base for electrolyte modification. Work is needed in
several coupled areas:

• Heterogeneous reaction mechanisms. The sequence of bond breaking is critical to understanding the way
facets are formed, for example, in the photoelectrochemical fabrication of small devices. Passivation
phenomena and charge transfer kinetics are important in energy conversion and chemical synthesis as well
as in fabrication. The understanding of the manner in which the surface may be stabilized against

28-12
 corrosion and the manner in which self healing can occur will also depend on knowledge of kinetic
mechanisms.

• Polycrystalline surfaces. We have mentioned that a significant difference between solid state and
photoelectrochemical solar cells lies in the relative ease of forming an interface with both crystalline and
polycrystalline materials that is accessible for characterization by external probes. Although some
empirical rules have been established to relate the photoelectrochemical performance of polycrystalline
materials to single-crystal counterparts, development of a better understanding of morphological effects is
critical. Grain boundaries are associated with increased recombination losses, reduced current densities,
and increased effective surface area. Solid state diffusion is enhanced in grain boundaries.

• Double layer structure. Many of the techniques used to characterize the electronic structure of
semiconductors rely on measurements of capacitance at the semiconductor-electrolyte interface.
Anomalous changes in the space-charge capacity with applied potential have been attributed to the
influence of deep-level electronic states, within or at the surface of the semiconductor. Surface states can
limit the photopotential obtained in photoelectrochemical cells by "Fermi-level pinning" and can reduce
the power effiCiency by providing pathways for enhanced recombination. Although. models for the
semiconductor-electrolyte interface have traditionally been based on solid-state descriptions, the influence
of ionic species, either through specific adsorption onto the surface or through adsorption in a diffuse
double layer, needs further study. Even the applicability of traditional models for the diffuse double layer
is questionable for the ionic concentrations typically used in photoelectrochemica1 processes. A better
understanding of the electrolytic contribution to the semiconductor-electrolyte interface may be needed,
for example, to explain the unexpectedly high photopotentials that have recently been reponed.

• Homogeneous reactions in electrolytic solutions. Electrolyte modification has been pursued intensively
as a means of providing high power effiCiencies with low rates of photocorrosion by matching electrolyte
and semiconductor properties. A very fundamental need exists for creating a thermodynamic data base
for ionic species in a variety of solvents. The issues include the rate and equilibrium constants for
electrochemically active species and the influence of electrochemically inen counterions (through
adsorption or homogeneous interactions). Efforts in this area can also suppon the study of the kinetics and
equilibrium constants for (heterogeneous) adsorption of ionic species, which can lead to shifts in the flat
band potential.

• Microscale processes. The application of models to photoelectrochemical fabrication of sub micron-scale

structures requires consideration of different phenomena than are treated in models of larger scale systems.
Surface roughening, tunneling, and double layer processes can playa major role on current (or reaction)
distribution and selectivity; whereas, in contrast to large-scale systems, convective transpon of electrolytic
species may be comparatively unimportant To be applicable, models must therefore account for the
interactions between potential and concentration in the electrolyte close to the semiconductor surface as
well as in solid-state processes.

The research areas listed above require that experimental studies be coupled with the parallel develop-
ment and use of comprehensive mathematical models. Funber development of photoelectrochemical energy
conversion, fabrication of interfaces and structures, synthesis and detoxification, and characterization will be
served with mathematical models that can be used to extract relevant physical properties. to guide experimental
design. and to predict the response of the system based on well-founded hypotheses. Although the fundamental
theory to be used is not new. the models must account for the complicated interactions among coupled physical
phenomena. Interpretation based on simplistic models is often inadequate and can lead to misleading or
incorrect conclusions.

28-13
Vll. RESEARCH NEEDS AND OPPORTUNITIES IN PHOTOELECTROCHEMICAL SYSTEMS

Researcb in pbotoelectrocbemical systems primarily aimed at energy conversion bas achieved notable
milestones and produced a variety of valuable spin-offs to other technologies and to the understanding of the
underlying science. We conclude that the field deserves strong consideration for support within the broader
context of pbotovoltaic systems. To accelerate this progress, a number of specific needs sbould be addressed,
given in priority order:

1. Cross-fertilization between developments in pbotocbemical and photovoltaic technologies.

2. Comprehensive studies of solution phase and surface cbemistry and modification.
3. Increased level of characterization of the bulk, interfacial, and liquid pbase properties of these systems,
with stress on techniques capable of following the dynamics of the system
4. Synergistic correlations of cbaracterization and theoretical modeling.
5. Application of novel nanostructures that can amplify energy conversion schemes and other solar
applications.
6. Development of more efficient and stable photoelectrodes to support substantive efforts for hydrogen
production from solar energy.
7. Exploration of opportunities in electrochemical deposition and processing that can lead to very low-cost
cells.
8. Integral storage schemes.
9. Fundamental understanding of etching processes and structurally sensitive control.
10. Development of pbotoelectrocbemical strategies for enhancement of the environment (detoxification and
synthesis).
11. Standardization of efficiency and stability measurements and testing procedures.

REFERENCES

1. A. Fujisbima and K. Honda, Nature, IZ., 238 (1972).

2. H. Geriscber, 1. Electroanal. Chem, 58, 263 (1915).

3. B. O'Regan and M. Griitzel, Nature, 353, 737 (1991).

4. (a) S. Licbt and D. Peramunage, Nature, 345, 330 (1990).

(b) S. Licht and D. Peramunage, Nature, 354, 440 (1991).

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28-14
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28-15
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28-16
 .. .. .
Load ..----.,;.--.... Load I+-----+.

Light Light

energy
gain
7 Red,..tOx+

.~
n-type redox counter- n-tlJpe dye redox counter-
semiconductor electrol yte electrode semiconductor electrol yte electrode

Figure 1. Carrier generation under illumination arising at (a) the semiconductor/electrolyte interface and
(b) the semiconductor/dye sensitizerlliquid interfaces

Figure 2. A PEe cell in a system combining both solar conversion and storage capabilities: (a) under
illumination and (b) in darkness or low light

28-17
 29. ORGANIZED MOLECULAR ASSEMBLIES

George M. Whitesides, Harvard University, Cochairman

Gregory S. Ferguson, Lehigh University, Cochairman
David Allara, Pennsylvania State University
Dan Scherson, Case Western Reserve University
Lois Speaker, Eastman Kodak Company
Ari Ulman, Eastman Kodak Company

SUMMARY

Organized molecular assemblies (OMAs)-self-assembled monolayers (SAMs), Langmuir-Blodgett

(LB) films, vesicles, and lipid bilayers-represent a major, important new theme in condensed-matter
science. SAMs, in particular, have properties suggesting potential wide applicability in control of
interfacial properties for systems of interest to DOE. SAMs are systems at or close to thermodynamical
minima, and are thus easy to prepare. The production of SAMs, unlike most surface technologies, is
straightforward, and they are intrinsically manufacturable: they form highly ordered ftlms by simple, low-
cost processes, and they have low defect concentrations.

A. Characteristics of SAMs

We note these characteristics of SAMs as particularly relevant to the DOE mission:

• SAMs can be formed on rough, irregular, and shaped surfaces, as well as on inner surfaces and
surfaces not accessible to line-of-sight methods.

• Damaged SAMs can be regenerated in situ. if the appropriate molecules are present in the immediate
environment (Le., as components in corrosion-, friction-, or soiling-control systems).

• The properties of SAMs can be varied with great flexibility, by control of their molecular components.

• Because the components of SAMs reliably form monolayers, small amounts of material will cover
large surface areas: typically 1-10 kg of material might provide monolayer coverage of 1 km2 of
substrate. Processing with SAMs is thus intrinsically very economical and applicable to large-scale
materials problems.

B. Recommendations for Research

1. Research in OMAs should focus on SAMs. Langmuir-Blodgett films have certain applications in
multilayer systems and in research (for example. in optics). but the Simplicity and economy of
. formation of SAMs and their applicability to rough. shaped, and interior surfaces make them much
more promiSing for large-scale, cost-sensitive applications.

2. Support should be directed toward single-investigator projects. The style of research in SAMs focuses
on small, individual research groups working alone and cooperatively. Instrumentation at the $100K
to $IM level, which is often not shared, is an important component of this research. Large national
facilities (light sources, etc.) are not crucial to the most important work in the field, although certain
problems require access to these facilities. The national laboratories have not, so far, played a

29-1
 significant role in the field, but might constitute a valuable resource at the technology-development
stage.

3. The most important areas for basic research are:

• Development of methods· for forming in-plane patterns and features in SAMs

• Use of SAMs for two-dimensional (2-D) organization of complex molecules

• Studies of SAMs as model systems for complex phenomena, including but not limited to: wetting,
adhesion, friction, wear, interactions at biosurfaces, fouling, soiling, and corrosion

• Use of SAMs to study phenomena In condensed-matter science: cooperative behaviors, phase

separations, and the influence of defects

• Use of SAMs to nucleate growth of condensed phases in three dimensions: condensation of water;
growth of crystals; attachment of polymers

• Development of new types of SAMs, especially those with enhanced stability, and new types of
surface-monolayer chemistry

• Development of computational models for SAMs and SAM-related phenomena.

4. The most important areas for generic, applied research are:

• Development of thermally and oxidatively stable SAMs formed from stable organic and inorganic
components

• Direct application of SAMs to the most important classes of substrates~teels, aluminum, copper,
semiconductors, ceramics, glass, and photolytically stable polymers.

5. Areas for applications research involving SAMs are:

• Corrosion Inhibition-Development of self-regenerating, passivating systems based on SAMs

• Tribology-Control Systems-Development of new, robust, self-regenerating systems for control of

friction

• Soiling-Control Systems-Use of SAMs to develop easily cleaned sutfaces (low surface free energy
fluorocarbons; surface-attached hydrogels) for optical components and surfaces resistant to soiling and
biofouling for membranes, and subsurface and marine structures

• Fuel Cells-controlling interfacial properties in gas/liquidlcatalystlmembrane systems to improve

performance.

SAMs are valuable in research as model systems for establishing the fundamental mechanisms of
complex phenomena like corrosion, friction, wetting, wear, adhesion, biofouling, and surface charge
dissipation. These studies will guide the design of coatings and thick films for practical applications for
which SAMs are not sufficiently strong, stable, or robust The most serious deficiency of SAMs in
practical applications is their thermal, mechanical, and oxidative instability. Known systems are limited

29-2
to tempera~es below approximately 150°C, unless they can be used in self-regenerating form. The
strategy of self-regeneration at a surface, accomplished in situ by including the molecular components of
the SAM in the surrounding fluid or vapor, constitutes a unique and valuable characteristic of self-
organizing systems.

LB fIlms and other types of organized assemblies will also be useful, especially in research
applications and in high-value uses such as optical and electrooptical devices.

I. INTRODUCTION: DEFINITIONS AND CHARAC1ERISTICS

Although the LB technique provided the first practical laboratory technique for constructing
ordered molecular assemblies in the laboratory, this report focuses on self-assembled (SA) systems [1,2].
'This focus by no means diminishes the importance of LB technology [3], but applications in the
transportation and utilities technologies require emphasis on issues such as ease of fIlm fabrication,
stability, and cost-those that favor SAMs over LB films. 'This report deals with monolayers, though
methods for fabrication of self-assembled multilayers based on molecular self-assembly have been
developed in the last decade [4].

SAMs are OMAs that form spontaneously by adsorption of amphifunctional molecules at solid-
liquid and solid-gas interfaces. These adsorbates have strong affinities-usually chemical in nature-to
the substrate surfaces. The spontaneity of monolayer formation. implies that such systems are
thermodynamically stable. They are more stable than LB films, whose molecular components are often
physisorbed to the surface of the substrate. That SAMs form in situ indicates that partially formed,
disordered moilolayers can be driven to complete, ordered systems, and that monolayers can self-regenerate
in the presence of a molecular adsorbate.

There are many types of SAMs, including carboxylic acids on A1 20 3, Ag20, and glass; phosphonic
acids on di- and trivalent metal oxides; sulfonic acids on Ag20; disulfides and thioethers on gold; thiols
on gold, silver, copper, and platinum; alkylsiloxanes on hydroxylated surfaces (Al20 3, Si02 , glass, etc.);
alcohols and amines on Pt. Common to the formation of all SAMs is an exothermic chemisorption step
(e.g., ca. 40 kcal/mol for long-chain alkanethiols on gold) that provides most of the driving force for the
process. The exothermicity of this chemisorption indicates that, unless there are interfering factors, these
systems will maximize the number of adsorbed molecules on the surface, and generate a close-'packed and
ordered assembly. The other major contributions to order and stability in SAMs are interactions between
the adsorbed chains (van der Waals, hydrogen bonding, etc.). The stabilization afforded by these
interactions can be comparable in magnitude to the energies of chemisorption; for example, the van der
Waals interactions for CIJl33S/Au(1l1) amount to approximately 26 kcaJ/mol.

The spontaneity of formation and high packing densities in these systems leads to films with few
defects. This characteristic is very important when considering issues such as wetting, tribology, and
electron transfer. The amphifunctional character of the molecules that form SAMs and the flexibility in
molecular structure offered by organic synthesis provide the capability to tailor surfaces and to control
their physical and chemical properties [5]. Incorporating functional groups into the alkyl chains of the
adsorbates will allow the synthesis of increasingly more complex systems. Such studies are vital to both
detailed understanding of self-organization and to the development of advanced materials and their
applications in technology.

To summarize, the properties of SAMs most important in technology relevant to transportation,

utilities, and conservation are:

29-3
• Spontaneity of in situ formation
• Thermodynamic stability
• Ability to apply conformal coatings on surfaces, regardless of their shape
• High packing densities and low defect concentrations
• Molecular alignment
• Capability to tailor surfaces to desired applications
• Synthetic flexibility.

II. SCIENTIFIC OPPOR11JNITIES

Unique opportunities for increasing our understanding of thin-film structures, surfaces, and
interfaces involving molecular materials are available to researchers who use SAMs. These fundamental
studies will have broad importance in the areas of materials science, condensed matter physics, chemistry,
and the biological sciences. They will have broad relevance to generic problems in surface and interface
modification, and to certain classes of problems in manufacturing and energy conservation and generation.

A. Condensed Matter Science

Recent applications of SAMs to the physics of 2-D condensed matter are particularly interesting.
SAMS provide the opportunity to study the effects of dimensionality in phase transitions and the
correlations between phase states, structural · coherence, and molecular size and shape. The highly
controlled surface structure ·in SAMs also provides opportunities for new experimental approaches to
understanding the difficult problem of nucleation and growth of molecular crystals. In this context,
biomimetic nucleation of crystal growth represents a growing area of research relating to SAMs that offers ,
exciting opportunities for fundamental study in materials science [6]. The organization of crystalline
materials on modified surfaces should not be limited to inorganic salts, but should be viewed as a more
fundamental phenomenon. Nonetheless, establishing the rules governing biomineralization may provide
inexpensive routes for the production of ceramic materials that are of interest to DOE.

B. Heteroepitaxy

One of the premier issues in materials science today is the question of how to accomplish
heteroepitaxy: that is, how to fabricate the most defect-free interface between a crystalline substrate and
a deposited, crystalline overlayer of another material with different lattice constants. A well-known, purely
inorganic example is the continuing effort to grow GaAs on silicon by molecular beam epitaxy. Creative
uses of SAMs, with appropriate chemical and thermal stability, as templates to assist such heteroepitaxy
by fme-tuning changes in lattice spacing over molecular distances, would be of great interest.

C. Nanostructures

Another area of great importance at the intersection of materials .science and physics is the
fabrication and electronic properties of surface structures patterned at the nanometer scale [7]. High-
resolution, lithographic processing demands the use of resist films with nanometer-scale thicknesses and
low defect concentrations. The combination of high chemical flexibility and other suitable properties
makes SAMs an attractive possibility [8]. The ability to create structures such as nanowires and quantum
dots has been a key factor in the development of the physics of quantum confined structures. Another
intriguing possibility in materials science is that of using SAMs for information storage applications. One
approach is suggested by the work of Fuji shima and coworkers [9]. This group used the optically induced
isomerization to modify the redox potential of surface-confmed species in an LB film. The resulting
heterogeneities in the film could be read by simple electrochemical methods.

29-4
 There are several major opportunities to use SAMs to help resolve long-standing scientific issues
in the chemical sciences. The high flexibility to -synthesize surfaces with well-defined arrays of functional
groups should continue to provide major advances in the understanding of wetting and surface chemical
phenomena. This research will provide new understanding of the complex interfacial behavior that
underlies the performance of a range of natural and synthetic structures, including environmentally
protective coatings, biocompatible surfaces, highly specific biological receptor sites, and advanced
composite materials. Studies of the organization of complex molecules, polymers, oligopeptides, and other
biomolecules are important to derive an understanding of the relation between the structure of an
individual molecule and its organization in two dimensions. Such fundamental understanding is vital for
the advancement of materials science.

III. OPPORTUNITIES FOR APPLICAnONS IN 1ECHNOLOGY

Beyond the fundamental studies, there are now a number of problems in technology to which
SAMs and other OMAs can be applied [to]. The following list is incomplete, but it provides examples
that illustrate the types of problems' for which SAMs may provide solutions.

A. Fuel Cells

A broad range of problems in the technology of phosphoric acid-organic membrane fuel cells
centers on the control of interfaces, and SAMs may be useful in solving a number of these problems.
Among the potential applications are:

• Controlling the wettability of pores in the gas distribution membranes to facilitate the transport of
gases to the cathode and anode surfaces, to control the wetting of these and surrounding surfaces, and
to control the removal of water from the cathode

• Controlling the interface between the platinum and the carbon support to limit corrosion

• Controlling the interface between the carbon and the ionomer surface layer to ensure good proton
conductivity

• Improving adhesion between the catalyst-containing surface ionomer layers and the central ionomer
membrane

• SAM-forming additives may, speculatively, be useful in controlling the kinetics of redox processes
at the interfaces. An oxygen reduction catalyst that would adsorb at the cathode surface and increase
the rate of reduction of O2 to water would lead to large improvements in cell performance. By using
a self-regenerating layer, it would be possible to compensate for material lost by corrosion or
electrochemical damage.

B. Photoelectrochemistry

Monolayer films offer interesting opportunities in electrode modification. The simplest, yet most
important application, is electrode passivation, especially for materials like amorphous silicon, that are
unstable in aqueous media. Using simple ~-alkyl derivatives as adsorbates for passivation introduces an
insulating layer at the electrode, thus decreasing electron transfer and cell performance. Using more
conductive derivatives, however, would overcome this problem. New possibilities have been reported
recently for the stabilization of semiconductor interfaces [11]. SAMs have been demonstrated to provide
useful protection of metal (Cu, Au) surfaces against chemical corrosion. Adsorption of a SAM on a

29-5
photoelectrode may also help to passivate surface states and thus reduce losses in effiCiency due to
electron-hole recombination, without inhibiting electron tunneling across the interface.

Synthetic models for photosynthesis may be important for engineering specific photoelectrodes.
Modifying these electrodes with appropriate monolayers would result in a modified potential that can carry
out a specific, clean chemical reaction. Advances in photoelectrochemical catalysis may also result from
research on SAMs, although it would likely require the use of organometallic derivatives.

C. Thin Film, Multilayer, Solar Collectors

OMAs should be useful in addressing those problems with photovoltaic (PV) panels and
concentrators, solar collectors, and electrochromic (EC) windows that require tuning of surface properties.
Current spending for research on PV modules is about $4OMJyear, with only $600K set aside for
encapsulation studies. PV efficiencies have reached more than 17%, and operation at this efficiency for
30 years would make these modules economically viable.

The lifetime of PV modules is currently limited by the photothermal degradation of the

polyethylene vinyl acetate (EV A) copolymer presently used as a protective coating. This photodegradation
causes the film to darken and leads to losses of 5% to 15% (or more in some cases) during 5 to 10 years
of operation in hot, dry climates. This process proceeds most rapidly from the interface between EVA
and the soda lime glass superstrate, as well as from around the "fingers" of metallization that protrude into
the film. Replacement of EVA is now being considered, but similar photodegradation problems will likely
be encountered with other polymeric layers, especially at the metal (oxide)/polymer interfaces. The
photochemical stability of these sensitive interfaces may be significantly enhanced by SAMs used as low-
dielectric coatings that also serve as diffusion barriers between different layers.

The efficiencies of flat-panel PV arrays, PV concentrators, and the heliostats of mirror fields are
reduced by repetitive cycling (through soiling and cleaning) that accompanies environmental exposure.
Exploratory work indicates that soil retention can be mitigated, and possibly eliminated, by treating the
outer surfaces with a single oriented layer of a fluorinated amphiphile (see Chapter 18 in this volume).
Samples treated in this way retain their original reflectances for more than a year and through 20 soiling!
cleaning cycles. Longer-term studies are required to determine specific lifetimes.

EC windows have a minimum of five layers of active materials and eight interfaces, including
poorly understood interfaces between ion-storage and ion-conducting layers as well as interfaces from a
superstrate and substrate. The barrier and dielectric properties of SAMs at these interfaces might play an
important role in maintaining layer segregation and operating efficiencies. Antisoiling SAMs at the outer
surfaces may also be beneficial.

D. PolymerlMetal (Oxide) Interfaces

SAMs offer potentially significant benefits in systems that require strong bonding between a metal
(oxide) substrate and a polymer. These systems include conformal coatings of protective films, adhesives,
primers, and paints. As mentioned in the opening section of this chapter, the formation of SAMs is driven
by strong chemical bonding of the adsorbates to the substrate. Adsorbates may be modified by organic
synthesis, before or after adsorption, to incorporate reactive end-groups that can be used to covalently
attach a polymeric coating to the surface. The high packing densities, low defect concentrations, and
molecular alignment of these films should provide efficient multisite linkages between the substrate and
polymer [12].

29-6
 This technology may also offer advantages in reducing the number and/or complexity of required
processing steps for fabricating metal (oxide)/polymer materials. As an example, a critical concern in
forming a strong adhesive bond is the cleanliness of the substrate. In a typical preparation of a SAM,
however, the desired adsorbate displaces physisorbed organic contamination, and the monolayer film is
usually less prone to contaniination than the bare metal (oxide). Hence the process is, in some
circumstances, self-cleaning and self-passivating. As the number of systems known to form SAMs grows,
the need for some processing steps (e.g., removing the native oxide from the substrate) may also become
unnecessary. Elimination of pro.cessing steps is advantageous economically and in terms of environmental
impact

IV. TECHNOLOGICAL PROBLEMS: LIMITATIONS TO THE TRANSFER OF SCIENCE INTO

TECHNOLOGY

Basic research has established a range of properties for the most useful OMAs-SAMs formed
. by spontaneous chemisorption of organic molecules onto surfaces-that make them potential solutions
to a broad range of technological problems of concern to DOE. The .most relevant of these properties
involve the ease and economy with which SAMs can be formed, and the flexibility with which their
properties can be tailored by controlling the structures of the component molecules through synthesis.
Because these systems are at thermodynamic minima, they are intrinsically defect-free and self-healing.
SAMs form with high degrees of order on exposure of the surface to the adsorbing species; the
technologist does not have to stabilize a metastable system. Oean-room conditions are not needed in
SAMs preparation; their enthalpy of formation is often enough to clean the substrate surfaces by displacing
dust and weakly adsorbed contaminants. SAMs will cover defects and can be formed on irregular and
interior surfaces.

The major limitations to the application ofSAMs in many technologies are their limited thermal,
photochemical, and oxidative stability; an incomplete base of knowledge to guide their formation on many
classes of substrates; and their low mechanical strength. Each of these limitations can be circumvented
or minimized by developments of existing science, or by extension of already demonstrated paradigms to
new classes of materials.

A. Stability

Most work with SAMs has focused on components derived from polymethylene-based organic
molecules X-(C~)D- Y, in which the X group forms a bond with the surface and the Y group provides the
function or tailors the interfacial properties. The polymethylene chain is subject to thermal damage; the
chain oxidizes relatively readily in contact with air at temperatures greater than 100°C. For many
applications, higher stability is required.

The obvious approach to this problem is to develop SAMs based on polymeric models of known
stability. For example, components for SAMs may be based on polyarylsulfones and -ethers, polyimides,
poly(diorganosiloxanes), fluorocarbons, polyphosphazines, and a range of other polymer structures that
are already used for applications that require stability under extreme conditions. These systems could be
modified for use in SAMs, either as functionalized oligomers or as functionalized polymers [13]. SAMs
prepared from these structures can be confidently predicted to show much greater thermal and oxidative
stability than those now known. It is probable that appropriate representatives of these systems will be
usable in applications requiring exposure to air at temperatures of approximately 300°-4OO°C for short
times. For higher-temperature applications, it will be necessary to make a greater step in technology. In
principle, it should be possible to build SAMs of inorganic components with very high stability
(carboranes, metal oxide clusters), but these types of systems have not yet been explored.

29-7
B. Monolayer-Substrate Interactions

Much of the research on SAMs to date has focused on well-defined, convenient model substrates:
gold and silver, alumina, silica, and mica. Other metals and metal oxides have been surveyed casually,
and there is every reason to expect that SAMs with high order can be formed on a range of substrates,
but the appropriate surface chemistry for forming SAMs on "real" materials-native oxides on steel,
aluminum alloys, copper, bronze and amorphous silicon, multi component silicate glasses, silicate minerals,
concrete and others-have not yet been developed. A program to develop the surface coordination
chemistry appropriate for these substrates will be essential. The broad principles to be followed are well-
known, but the practical details remain to be established.

C. Mechanical Stability

SAMs typically have thicknesses of the order of 1 to 5 nm. They will not be mechanically strong.
Even if they were, the underlying substrates would fail under the same mechanical stresses as they would
if unprotected. The appropriate strategy for using SAMs to protect against mechanical wear will be to
take advantage of their capability for in situ repair. . Thus, for example, for a SAM to be useful in the
control of friction or corrosion in an application in which mechanical damage or wear is probable, the
wear surface should be exposed to a solution or vapor of the molecules making up the SAM. Wear will
occur, but the SAM will regenerate itself in situ. For a solution to be used in cleaning exposed surfaces
of PV systems, the components of a surface-protective ·SAM can be included in the cleaning solution.
This capability for in situ regeneration is well-established in model systems and is the basis for the use
of fatty acids and derivatives as additives for control of corrosion, wetting, and friction. These types of
self-healing processes must, however, be studied in greater detail to provide a science and engineering base
appropriate for design in new applications.

D. Other Applications

There are many other potential applications of SAMs in the development of new technologies.
For example, SAMs could be used as "masks" to control deposition of metal oxides or metals in new types
of coating or electrodeposition processes. Existing systems are already excellent wetting and adhesion
promoters, but have not been developed for processes involving painting, or adhesion and wetting in
manufacturing applications.

E. Recommendations

The highest-priority generic opportunities for moving SAMs into technology are:

• To develop SAMs with high thermal and oxidative stability

• To develop the surface chemistry necessary to form SAMs on important classes of materials (steels,
metal oxides, semiconductors, other metals, and ceramics)

• To develop and demonstrate strategies for regenerating SAMs in situ, especially under conditions in
which wear or mechanical damage may be important.

29-8
v. NEEDS IN RESEARCH

A. Overview

Multidisciplinary approaches to research and research instrumentation are two issues that must be
properly addressed and resolved in order to ensure rapid and efficient progress in capitalizing on the
scientific opportunities and solving the technological problems mentioned above.

At this stage of development in the field of SAMs, the problems are primarily those of the
chemical sciences. In parallel with the typical structure of ~ inorganic substrate and a chemically bonded
organic overlayer, a typical research group poised for the fastest advancements in the field might be one
combining the skills of traditional disciplines of inorganic, organometallic, and organic chemistry. Such
a combination will ensure capability in broad, creative approaches to building unprecedented, mixed
inorganic/organic materials that have potential relevance to technological problems. Beyond the synthetic
aspects, however, equal efforts are needed from analytical and physical chemists to provide quantitative
analyses of the new strucrures and a detailed understanding of the formation mechanisms that lead to
desired properties. The utility of the SAM will depend on some critical property. In many cases, these
properties may be relatively complex such as an optoelectronic or biological response, or an influence on
corrosion or wear. The cooperation of other experts such as materials scientists, physicists, electrical and
mechanical engineers, or biologists would be of obvious help. Although there is no question that critical
advances in this technology can be made by individual specialists, we highly recommend that
multidisciplinary efforts be encouraged to provide novel and creative approaches.

There are clear instrumentation needs to support the tasks of quantitative chemical and structural
analysis of these organized structures. The combination of subtle but critical structural features, sensitivity
towards degradation, and the monolayer-level amounts of materials has resulted in the emergence of only
a few dependable instrumental techniques for analysis in these systems (see characterization section).
There is a need for further development of instrumentation to solve these difficult, nontraditional analytical
problems, and such efforts should be encouraged. For existing instrumentation, there are two categories
of issues: those dealing with independent investigator instrumentation and those dealing with multiuser
facilities. The majority of analytical efforts will require laboratory-centered instrumentation, such as X-ray
photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FI1RS), and secondary ion
mass spectrometry (SIMS). It is clear that the most advanced and meaningful studies of SAMs will
require the use of this type of instrumentation on a regular basis. Some of the more recent and detailed
analyses now include the use of national facilities, in particular synchrotron sources for in-plane X-ray
diffraction and near-edge X-ray fine structure spectroscopy. As the field moves to problems requiring
imaging analysis, scanning Auger and static SIMS will become more important. Scanning tunneling
microscopy (S1M), atomic force microscopy (AFM), and related techniques such as near-field imaging
are also increasingly valuable in characterizing local structure down to the atomic level. Brewster angle
microscopy and high-sensitivity scanning electron microscopy (SEM) are becoming important techniques.
Although only limited use of such facilities is needed, it is very important that these facilities continue
to be readily available to users working on the chemistry of organic films. The lack of additional facilities
of this type, however, is not limiting the progress of research at this time.

B. Payoffs

Support of fundamental and applied research into SAMs will lead to energy savings through
enhanced understanding of interfacial processes vital to almost every technology. These technologies
include:
•

29-9
1. Tribology '

. SAMs are already known to confer new friction and wear characteristics on substrates, in all cases
improving wear resistance. Because the effects of SAMs on boundary-layer lubrication can be modeled
computationally, such studies will enhance mechanistic studies and pro~ide a basis for practical
improvements.

2. Fuel Cells

SAMs can provide technology for surface modification that will improve the manufacturability
and operation of fuel cells in several areas: improved adhesion and contacts between components with
fewer defects and leaks; improved capability to control gas distribution to the electrode surfaces and water
distribution at (or removal from) these surfaces; possibly improved overall performance of the cells as
redox catalysts for the cathode, thus dramatically affecting energy costs.

3. PV Cells and EC Windows

SAMs may find applications as protective coatings or adhesion-promoting layers for both active
and passive components of PV cells and EC windows. Chemisorbed monolayers having close-packed
alkyl chains should decrease diffusion rates of water to, and their condensation at, interfaces containing
polycrystalline active layers (e.g., CdTe), processes that are probably associated with failure of almost all
devices. These monolayer fIlms might also increase device lifetimes by stabilizing heterojunctions (e.g.,
CdTe [p]/CdS [n]) or "fingers" of metallization. One of the most immediate benefits in this area may be
in relating modes of failure at critical device interfaces to their molecular and atomic compositions. The
potential applications of SAMs for the encapsulation of passive components, such as mirrors and solar
collectors, are discussed in the following section.

4. Surface Contamination: Soiling and Fouling

Interfacial contaminants can interfere with virtually every industrial unit process, thereby
increasing energy consumption, even if their concentration in the bulk is very low. Systematic
modification of surface properties-critical surface tension, hydrogen-bonding capacity, polarity,
dispersion-force energies, and extent of fluorination-using SAMs will clarify the mechanisms by which
industrial streams contaminate equipment, thereby facilitating prevention. Heat-transfer pipes are
notoriously subject to fouling and clogging, and should be given top priority for antisoiling treatment with
SAMs designed for high-temperature stability.

5. Fouling in Membrane Separations

Distillation, an enormously energy-consumptive technology, still accounts for 95% of U.S. indus-
trial separations. Almost all of these separations could be carried out more efficiently, near ambient
temperature and with much less waste of products, using membrane technology (microfIltration, ultra-
fIltration, reverse osmosis, electrodialysis, etc.) or hybrids of membrane separations with other methods.
Membrane fouling, which reduces efficiency and raises costs, has strongly inhibited substitution of
membrane separations for distillation. Fluorinated LB monolayers can, in certain circumstances, virtually
eliminate membrane fouling, and fluorinated SA monolayers should confer the same benefit. Further
research and development and lifetime-testing are essential.

29-10
 The National Research Council reported in 1983 that a critical need for improved detection by
sensors is improved membranes for selective transport between source and sensor. A nonfouling
membrane is also necessary for this application in any real environment

6. Selectivity in Membrane Separations

The polymeric and ceramic membranes now commercially available each have wide ranges of both
pore size and selectivity. Selectivity in these systems depends on the pore diameters and the physico-
chemical interactions between the memorane and feed stream. The only exceptions to the problem of non-
unifonn pore size are "drilled" polycarbonate membranes, which have regular pores with nearly zero taper,
. but these membranes are inapplicable for many separations because of their large pore diameters. SAMs
provide the means for healing the surface defects that account for much nonselective flux through standard
membranes, adjusting pore sizes by deposition of films within pores, modifying the surface wettability of
membranes to optimize separations, and adjusting the surface chemistry of membranes to optimize
interactions with given feed streams.

Membranes with optimized selectivity are needed to provide chemically selective sensors and
detectors. A related application of membranes anisotropically treated with SAMs is done in protective
suits that do not allow diffusion of pesticides, pollutants, and chemical-warfare agents, while allowing the
diffusion of moisture and CO2, and the conduction of heat. This type of selectivity has been demonstrated,
in fact, using LB films.

7. Biosurfaces

Natural cell membranes are OMAs with a minimal tendency to agglomerate proteins or cause other
deleterious physiological reactions. Synthetic OMAs (e.g., those comprising organized phospholipids or
derivatives thereot) have the potential for mimicking the characteristics of natural cells for in vivo
applications without introducing materials that would be recognized as foreign. SAMs composed of these
materials, therefore, offer great potential for coating prosthetic devices and implants, as well as for
optimizing the biocompatability of hemodialysis membranes and the surfac.es in devices such as heart-lung
machines [14,15l

Biofouling is an important problem in a very broad range of technologies-marine corrosion due

to anaerobic archaebacteria, corrosion of buried power cables, contamination of heat-transfer surfaces in
cooling towers causing a decrease in thermal efficiency, and decreased efficiency in ship transportation
due to marine growth on hulls. SA organic structures will certainly be the best systems with which to
determine the fundamental molecular processes underlying these types of fouling, and the results will aid
in the design of improved systems (for example, engineered polymer coatings) for their control. In certain
circumstances, SAMs themselves may be solutions to the problems. For examples, appropriate additives
in cooling towers or heat exchangers may provide optimal strategies for controlling biofouling in these
systems. 'Inclusion of SAM-forming components in polymers, in a way that would permit them to
"bloom" to the surface, might be effective in preventing microbial adhesion and formation of slime layers.

8. Sensors

SAMs, by virtue of the flexibility with which they can be modified, provide the basis for
technology that will introduce sensor molecules into appropriate systems [16]. For example, SAMs have ·
already been built into small-area (ca. 1 ,.un?) sensors for pH and ion-concentration measurement [17,18].
SAMs involving immobilized antibodies are the basis of a highly promising new technology using surface
plasmon spectroscopy to carry out biospecific detection [19,20]. The recently developed method for

29-11
attaching SAMs directly to the bare surface of GaAs suggests possibilities for developing new Classes of
chemical-sensing, semiconductor devices [11]. For a range of sophisticated environmental sensors of .
interest to DOE, SAMs will probably provide the best technology for introducing molecular recognition
capability in optical and electrochemical systems.

9. Corrosion

Corrosion inhibition is an area in which SAMs have traditionally played an important role,
although it has not always been recognized as such. Long alkyl chains, for example, form excellent
barriers to H20, O2 , and various other. corrosive agents. A better understanding of the principles
underlying this phenomenon should lead to the rational design of SAMs for applications in corrosion
inhibition involving a wide variety of both metals and semicondUctors. SAMs could also be useful in
coupling chemically labile substrates (e.g., copper) and chemically resistant layers (e.g., a micron layer
of polymer), a strategy that would increase the mechanical durability of the interface.

REFERENCES

1. For reviews of SAMs, see: Wet Chemical Approaches to the Characterization of Organic Surfaces:
Self-Assembled Monolayers, Wetting, and the Physical Organic Chemistry of the Solid-Liquid
Interface, G. M. Whitesides and P. E. Laibinis, Langmuir, Q, 87 (1990); A. mman, An Introduction
to mtrathin Organic Films: From Langmuir Blodgett to Self-Assembly, Academic, New York, NY,
1991.

2. For a general review and discussion of research needs, see: Molecular Monolayers and Films,
1. D. Swalen, D. L. AHara, 1. D. Andrade, E. A. Chandross, S. Garoff, 1. Israelachvili,
T. J. McCarthy, R. Murray, R. F. Pease, 1. F. Rabolt, and K. J. Wynne, Langmuir, J., 932 (1987).

3. Review: Optical Properties of Langmuir-Blodgett Films, J. D. Swalen, J. Molec. Electronics, b 155

(1986).

4. Formation of Multilayers by Self-Assembly, N. TIllman, A. mman, and T. L. Penner, Langmuir, i-

101 (1989); Inorganic Analogues of Langmuir-Blodgett Films: Adsorption of Ordered Zirconium
1,100Decanebisphosphonate Multilayers on Silicon Surfaces, H. Lee, L. J. Kepley, H.-G. Hong, and
T. E. Mallouk, J. Am. Chem. Soc., 110,618 (1989); Self-Assembled Multilayers of Mercaptoalkanoic
Acids: Selective Ionic Interactions, S. D. Evans, A. Ulman, K. E. Gopert-Berrarducci, and
L. 1. Gerenser, 1. Am. Chem. Soc., 113. 5866 (1991).

5. Surface Potential Studies of Alkanethiol Monolayers on Gold, S. D. Evans and A. mman, Chem.
Phys. Lett., 170.462 (1990); Mixed Alkanethiol Monolayers on Gold Surfaces: Wetting and Stability
Studies, A. mman, S. D. Evans, Y. Shnidman, R. Sharma, and J. E. Eilers, Adv. Conoid Interface
ScL, ~ 175 (1992).

6. Control and Design Principles in Biological Mineralization, L. Addadi and S. Weiner, Angew. Chern.
Int. Ed. Eng., 11 153 (1992).

7. Deep UV Photochemistry of Chemisorbed Monolayers: Patterned Coplanar Molecular Assemblies,

C. S. Dulcey, 1. H. Georger, Jr., V. Krauthaner, D. A. Stenger, T. L. Fare, and J. M. Calvert, Science,
252. 551 (1991).

29-12
· 8. Patterned Functionalization of Gold and Single Crystal Silicon via Photochemical Reaction of
Surface-Confined Derivatives of (l1s-CsHs)Mn(CO), D. Kang and M. S. Wrighton, Langmuir, L 2169
(1991); X-ray Damage to CF3C02--Terminated Organic Monolayers on SilAu Supports is Due
Primarily to X-ray Induced Electrons, P. E. Laibinis, R. L. Graham, H. A. Biebuyck, and
G. M. Whitesides, Science, 254. 981 (1991).

9. Photoelectrochemical Infonnation Storage Using an Azobenzene Derivative, Z. F. Liu, K. Hashimoto,

and A. Fujishima, Nature, 347, 658 (1990).

10. For reviews of OMAs, see: Molecular Architecture and Function of Polymeric Oriented Systems:
Models for the Study of ·Organization, Surface Recognition, and Dynamics of Biomembranes,
H. Ringsdorf, B. Schlarb, and J. Venzmer, Angew. Chern. Int. Ed. Engl., lL 113 (1988); Molecular
Self-Assembly and Nanochemistry: A Chemical Strategy for the Synthesis of Nanostructures,
G. M. Whitesides, 1. P. Mathias, and C. T. Seto, Science, 254, 1321 (1991).

11. A New Oass of Organized Self-Assembled Monolayers: Alkane lhiols on GaAs (100),
C. W. Sheen, J.-X. Shi, J. M:1rt:ensson, A. N. Parikh, and D. L. Allara, J. Am. Chern. Soc., 114. 1514
(1992).

12. Improved Adhesion of lhin Confonnal Organic Films to Metal Surfaces, K. R. Stewart,
G. M. Whitesides, H. P. Godfried, and I. F. Silvera, Rev. Sci. Instrum., 57, 1381 (1986).

13. Polymer Monolayers Prepared by the Spontaneous Adsorption of Sulfur-Functionalized Polystyrene

on Gold Surfaces, 1. M. Stouffer and T. J. McCarthy, Macromolecules, 111204 (1988).

14. Spontaneous Assembly of Phosphatidylcholine Monolayers via Chemisorption onto Gold,

W. Fabianowski, L. C. Coyle, B. A. Weber, R. D. Granata, D. G. Castner; A. Sadownik, and
S. L. Regen, Langmuir, ~ 35 (1989).

15. Fonnation of Self-Assembled Monolayers by Chemisorption of Derivatives of Oligo(ethylene glycol)

of Structure HS(C~)11(OCH2CH2)mOH on Gold, C. Pale-Grosdemange, E. S. Simon, K. L. Prime,
and G. M. Whitesides, J. Am. Chern. Soc., 113, 12 (1991); Self-Assembled Organic Monolayers:
Model Systems for Studying Adsorption of Proteins at Surfaces, K. L. Prime, and G. M. Whitesides,
Science, 252. 1164 (1991).

16. Ionic Recognition and Selective Response in Self-Assembling Monolayer Membranes on Electrodes,
I. Rubinstein, S. Steinberg, Y. Tor, A. Shanzer, and J. Sagiv, Nature, 332,426 (1988); Organized
Self-Assembling Monolayers on Electrodes Part I. Octadecyl Derivatives on Gold, E. Sabatani,
I. Rubinstein, R. Maoz, and 1. Sagiv, 1. Electroanal. Chern., 219. 365 (1987).

17. Molecular Self-Assembly of Two-Terminal, Voltametric Microsensor with Interna References,

J. J. Hickman, D. Ofer, P. E. Laibinis, G. M. Whitesides, and M. S. Wrighton, Science, 252. 688
(1991).

18. Selective Functionalization of Gold Microstructures with Ferrocenyl Derivatives via Reaction with
lhiols or Disulfides: Characterization by Electrochemistry and Auger Electron Spectroscopy,
J. J. Hickman, D. Ofer, C. Zou, M. S. Wrighton, P. E. Laibinis, and G. M. Whitesides, 1. Am. Chern.
Soc., 113. 1128 (1991).

29-13
19. Biotin-Functionalized Self-Assembled Monolayers on Gold: Surface Plasmon Optical Studies of
Specific Recognition Reactions, L. Haussling, H. Ringsdorf, F.-J. Schmitt, and W. Knoll, Langmuir,
L 1837 (1991).
20. Electron Transfer Reaction of Cytochrome c Adsorbed on Carboxylic Acid Terminated AlkanethioI
Monolayer Electrodes, M. J. Tarlov and E. F. Bowden, J. Am. Chern. Soc., 113, 1847(1991); Redox
Reaction Mechanism of Cytochrome c at Modified Gold Electrodes, T. Sagara, K. Niwa, A. Sone,
C. Hinnen, and K. Niki, Langmuir, .Q., 254 (1990).

29-14
 AI. OFFICE OF BASIC ENERGY SCIENCES (OBES) .

The OBES supports basic research under the following divisions:

Materials Sciences
Chemical Sciences .
Energy Biosciences
Engineering Geosciences
Advanced Energy Projects

DIVISION OF MAlERIALS SCIENCES (OMS)

The DMS supports basic research on materials properties and phenomena important to all energy
systems. This research is performed primarily at the DOE national laboratories and universities. The
research covers a spectrum of scientific and engineering areas of interest to DOE. The aim is to provide
the necessary base of materials knowledge required to advance the nation's energy programs. For more
information about the research sponsored by the DMS, the publication entitled "Materials Sciences
Programs" is available in limited quantities by calling the DMS at (301) 903-3426 [1].

The DMS also supports a number of National User Facilities that are mainly used for the
characterization of materials and research involving the interaction of photons, neutrons, or ions with
materials. For .more information, the publication entitled "Scientific User Facilities, a National Resource"
is available in limited quantities by calling the DMS at (301) 903-3426.

The total operating budget of the DMS in FY 1989 of $180M was divided by discipline as
follows:

Metallurgy, Materials Science, Ceramics 30.6%

Physics, Solid State Sciences, Solid State Physics 28.1%
Materials Chemistry 10.3%
Facility Operations 31.0%

The DMS supports a variety of research topics that provide the basis for "surface processing."

The following summary (for FY 1989) gives the number of projects supported by the DMS that
use the listed techniques and may be used for characterization of surfaces:

Auger Electron Spectroscopy 46

Electron Diffraction Technique Development 28
Electron Energy Loss Spectroscopy 30
Electron Spectroscopy for Chemical Analysis 15
Ion Channeling of Scattering 18
Infrared Spectroscopy 23
Laser Spectroscopy 31
Raman Spectroscopy 23

At-l
 The following summary (for FY 1989) gives the number of projects supported by the DMS that
use the listed method and may be used for surface modification:

Chemical Vapor Deposition 22

Surface Treatment and Modification 47
Ion implantation
Laser processing
Electron beam processing
Sputtering
Coatings 20

The following summary (for FY 1989) gives the number of projects supported by the DMS that
specifically study surfaces:

Chemisorption 39
PhySisorption 21
Structure 47
Thin Films 61

Abstracts of program summaries that are most relevant to surface processing and compiled in
Reference 1 are:

1,31,33,40,42,48,49,58,69,70,84,92,99,101,102, 105, 112, 113, '118,120,132, 134, 149,

155,163,168,171,180,187,190, 192,200,206,209,220,221,222,226,231,250,267,271,
286, 333, 346, 349, 351, 366, 397,404,417, and 425.

The DMS supports the following user facilities that are likely to be useful in the study of surfaces:

National Synchrotron Light Source

Brookhaven National Laboratory

Stanford Synchrotron Radiation Laboratory

Stanford University

Electron Microscopy Center for Materials Research

Argonne National Laboratory

Shared Research Equipment Program (SHaRE)

Oak Ridge National Laboratory

Center for Microanalysis of Materials

University of lllinois

Surface Modification and Characterization Collaborative Research Center

Oak Ridge National Laboratory

Combustion Research Facility-Materials Program

Sandia National Laboratories

National Center for Electron Microscopy

Lawrence Berkeley Laboratory

Al-2
 ."

The DMS has supported the following workshops that may contain information useful for "surface
processing" :

"Research Opportunities on Cluster and Cluster-Assembled Materials-A Department of Energy, Council

on Materials Science Panel Report," R.W. Siegal, L.E. Burns, et al., J. Mater. Res., ~(3), 704 (1989).

"Fundamental Issues in Heteroepitaxy-A Department of Energy, Council on Materials Science Panel '
Report," P.S. Peercy, et al., 1. Mater. Res., .2.(4), 852 (1990).

"Molecular Monolayers and Films," Panel Report, Langmuir, .1 932 (1987) J.D. Swalen, et al.

"Bonding and Adhesions at Interfaces," J.R. Smith et aI., Mat. Sci. Eng., ll. 175 (1986).

"Coatings and Surface Modificaitons," R.L. Schwoebel et al., Mat. Sci. Eng., 1Q., 5 (1985).

"Basic Research Needs and Opportunities on Interfaces in Solar Energy Materials," A.W. Czanderna,
R.J. Gottschall, et al., Mat Sci. Eng.,.ll. 1 (1982).

REFERENCE

1. Materials Sciences PrOImUIlS: Fiscal Year 1990. DOElER0483P, January 1991. U.S. Department
of Energy, Office of Energy Research, Basic Energy Sciences, Division of Materials Sciences,
Washington, DC; also Fiscal Year 1991, DOElER0537P, Febrp~ 1992, is available, but the program
summary chapters cited are for the January 1991 document.

Al-3
 A2. NATIONAL SCIENCE FOUNDATION (NSF)

The summary of surface processing relevant research supported by the National Science
Foundation has been prepared by Peter Sherwood, Department of Chemistry, Kansas State University,
Manhattan, KS' 66506, who served as Program Officer for Analytical and Surface Chemistry from
September 1990 until September 1991. The summary thus represents his personal reflections of the
situation at that time.

SUMMARY

Surface Science is funded by a number of divisions of the National Science Foundation (NSF).
The main support is provided by the Chemistry Division, the Division of Materials Research, and
Chemical and Thermal Systems. In the Chemistry Division, the support comes largely from the Analytical
and Surface Chemistry Program. In the Division of Materials Research, the support comes largely from
the Solid State Chemistry Program and the Electronic Materials Program.

The charts that follow refer to the Chemistry Division Program.

A2-1
Support for Academic Chemistry
Federal Support - FY 1982 Chemistry Division Budget
FY 1982: Total $201.1M Current and Constant Dollars

100 I

90
($77) 80
70
~ 60
en
c 50
Federal Support - FY 1990 ~ 40
~
FY 1990: Total $461.7M 30
20
10
($98) 0
76 77 78 79 80 81 82 83 84 85 86 87 88 89 90
Fiscal Year

'--N~;F·OtIn..r ($88)
1_ Current Dollars _ Constant Dollars

Chart 1: The changes in support for academic chemistry from FY 1982 to FY 1990.

Chart 2: Changes in the Chemistry Division budget over the years. Note that the budget is
approximately the same in constant dollars, but the number of research active university faculty
has increased considerably.

CHEMISTRY DMSION - KEY STATISTICS

o 900 Research Grants in 1990

o 81% of CHE funds go to individual investigators

o 33% success rate for research grants

. (higher for renewals, lower Jor first applications)

o 17% of budget spent on instrumentation

- $7.6 million - departmental
- $9.7 million - individual

o Presidential Young Investigator Awards - up to 20 per year

($100,000 5-year grants with industrial matching funds)

o Postdoctoral Fellowships - 15-20 per year

($26,000 stipend, 2-year tenure, starter grant option)

Chart 3: The activities of the Chemistry Division in FY 1990.

A2-2
 Instrumentation Funding
25
I!

-
1U
{2
c
0
20

15
~
I

V V --'" ~V ~ ~

'in
:~

-
0
0
E
10
I ...... ~I
.......
/ V-- ~
~
.....
'"'-,
Q)
~
Q)
0- I
I
i---j
5
.
0
80 81 82 83 84 85 86 87 88 89 90
Fiscal Year

1- Chem.lnst.Prog. - Chern. Equip.Total

Chart 4: Distribution of funding for equipment between the Chemical Instrumentation Program (CIP)
and normal research grants. The CIP requires matching monies and multiinvestigator
proposals.

DiYlaIon DI_
KennMh G. Bancock
Deputy Dlvlaioft DI....tor
JabnB.Hunt

I
CHEMICAL
I I
INORGANIC CHEMISTRY ANALYTICAL AND
\ 1
SPECIAL PROJECTS
INSTRUMENTATION SURFACE CHEMISTRY
Richard C. ThomplOn A. F. Findei.l. Head
JoeephIl-t,Jr. Unw.Al~rl.QXumb~ Peter M.A. Sherwood
l4araaret A. CavanauJh- Kan.u Slot. Ullit/. Seymour J . LappartAl-
SI. Alory·. eouc,. Alexander Sch••Une l4araaret A. Cavanausb-
Seymour J . LappartAl- Unill. lUinou. Urbono
Cltellron R.uorch Corp.

ORGANIC DYNAMICS ORGANIC SYNTHESIS THEORETICAL EXPERIMENTAL

PHYSICAL CHEMISTRY PHYSICAL CHEMISTRY
William H. Richardlon JohnS. Showell
Son Diego St. Ullill. Richard 1.. Hilderbrandt· FrankJ. Woclarczyk
Alan P. Marchand 1-1- GaorpM.Rubottom I-
Unill. North T ....... Jules W. MOlkowltz Cynthia J. Jameson
R. Bl')'an Miller N.w York Unill. Until. lUwL., Chic4go
Ullill. Col., DoIiL.

Chart 5: The programs comprising the Chemistry Division in FY 1991.

A2-3
 Distribution of Funds by Program
Chemistry Division - FY 1990
(Dollar Amounts are in Millions)

Division Total: $99.72 Special Projects

MCCP
$0.70

Physical REU
$29.06 $2.00 C&C
$0.50
SPO
$8.84
Oth Projects
$1.32
Inorganic Prog Support
$16.25 $0.30

CIP·Chemloll Inauum.ntatlon P,ogram CoLP·Chlmll"Y of LUI P'oo •••••

SPO-Splelel PrOJ.CI1 O"lc.
C&C·Cour •• and Currlaulurn
STe-Sellnc' and T.chnoiOGY Clnt.,
REU.A •••• 'ch Exp.,llnc •• to, Undlrondul" •. Sit ••

Chart 6: The distribution of funds among the Chemistry Division programs in FY 1990.

Funding Patterns In Chemistry

1985 1990

INTRA
SRPS SRPS 4.11
75 .; 80.3
(811.:) ~~Ic"c 0.5
(87:") MCCP
CoLP
4.;

$87.2M $99.7M

Chart 7: The change in distribution of funds to normal research grants (SRPS) and special research
programs between FY 1985 and FY 1990, in which STC denotes the science and technology
centers, INST denotes the chemical instrumentation program, INFRA denotes the infrastructure
support, MCCP denotes materials chemistry and chemical processing, and COLP denotes the
chemistry of life processes.

. A2-4
 Chart 8: Activities of the Office of Special Projects.

lni tia tives

Collaborative Interdisciplinary -- Balanced -- Synergistic

MCCP

Materials Research COLP

(DMR)
MCCP

~
Bulk Properties
CHEMISTRY COLP BIOLOGY
1~ MCCP
(CRE)
I----------i ~
Molecular Structure
~
(BNS. DCB. DMB)
1---------:-1
Neural and ce1lular interaction.

Chemical Engineerin,
(CTS)

Process Details • Protein Foldin,

• Catalytic Antibodies
• Photosynthesis
• Superconductors • Neurochemistry
• Composites
• Molecular Electronics
• Ceramics

Chart 9: lbe MCCP and COLP Initiatives in FY 1990. (please note that MCCP has been replaced by
the Materials Synthesis and Processing Initiative involving nine NSF divisions in FY 1992.)

A2-5
 Average Chemistry Research Grant
1990

-Pe,rson''1e1 ($34)

Support
Benefits ($5)

Averace Irani budeet in thousands or dollars

Indirect Costs
-Pe'rson"el (534)

Benefits ($5)

Salaries, waees, and (rinlt benefits ($38.8 thouuad) for the annie lrant

Averact grant size is $15,500 per year: Range is $30,000 10 S3OO,OO per yur

Chart 10: The Average Chemistry Research Grant in FY 1990.

Analytical and Surface Chemistry

Topical Breakdown

20 25

Chart 11: The topical breakdown of grants in FY 1990 in the Analytical and Surface Chemistry Program.
Note that some grants have more than one topic.

A2-6
 Analytical and Surface Chemistry
Funding Levels according to Grant Type

14--------~--~--~----~--~------~

12~------+---~--~--~~---+~

1_ ESC _ ASC _ Total

Chart 12: The distribution of funds between grant type and program element for FY 1990 in the
Analytical and Surface Chemistry Program, in which ESC denotes electrochemistry and surface
chemistry and contains all the surface chemistry grants (ASC denotes the rest of the program);
CGA denotes the continuing grant award, the second and third year ()f funding of a normal
three year grant; Supp denotes supplements to existing grants; and Prior denotes proposals
from a principal investigator (PI) who was previously funded by NSF but had a renewal
proposal declined.

Analytical and Surface Chemistry

Award Size vs Ph.D. Year

~~----~r--'---'---'---r---r-----.100

Iii'
c:
~ g
~ 1 ~-II-----I-+---+---I--+

0.5-11----11 ..~.. f--t

18-4748-54 55-61 62-68 69-7576-82 83-90

1_ Total $ _ Average $ 1
Chart 13: The relationship between the size of grant and the Ph.D. year of the principal investigator.

A2-7
 A3. TIlE AIR FORCE OFFICE OF SCIENTIFIC RESEARCH

The Directorate of Chemistry and Materials Science of the Air Force Office of Scientific Research
. (AFOSR) has the mission to encourage and support fundamental research designed to increase knowledge
and understanding, to stimulate the recognition of new concepts, and to provide for early exploitation by
defense technology. The Directorate, led by Dr. Donald Ball, is the single manager for basic research in
chemistry and structural materials for the Air Force.

The Directorate obtains and maintains for the Air Force a diversified program of research at Air
Force laboratories as well as extramurally at university and industry laboratories. Sponsored research
programs totaled approximately $16.6 million in FY 1991. The Directorate also functions as a dynamic
interface between the Air Force and the scientific community, ensuring the free, full, and constant
interchange of ideas from each to the other through publications, personal contacts, meetings, and
sponsored symposia. The agents for this work are the Program Managers. The Directorate Program
Managers, who are all located at AFOSR, Bolling AFB, Washington, DC, 20332-6448, and the program
titles are as follows:

Chemical Reactivity and Synthesis: Dr. Fred Hedberg

Polymer Chemistry: Dr. Charles Lee
Inorganic Materials Chemistry: Capt Thomas Erstfeld
Electrochemistry: Dr. John Wilkes
...
Theoretical Chemistry: Lt. Col. Larry Burggraf and Dr. Mark Gordon
Molecular Dynamics: Dr. Michael Berman
Metallic Structural Materials: Dr. Alan Rosenstein
Ceramics and Nonmetallic Structural Materials: Lt. Col. Larry Burggraf

For more than two decades, the Directorate has featured a strong program in Surface Chemistry.
Within the past year, we have reorganized the Directorate to accommodate a strengthened materials
emphasis. As part of that reorganization, we have combined the Surface Chemistry Program and the
inorganic materials portion of the ultrastructure materials program created by the late Dr. Donald Ulrich
into a single Inorganic Materials Chemistry Program.

I. INORGANIC MA1ERIALS CHEMISTRY, Capt Thomas Erstfeld

The inorganic materials chemistry program supports basic research for synthesis and processing
of structural materials and thin fIlms.

Structural materials research encompasses multifunctional ceramics, solution ceramics, glasses,

ultrastructure processing of ceramics 'and electroniclelectrooptic materials, and oxidation-resistant
carbon/carbon composites. The goal of this research is to produce structural, optical, and electronic
materials that perform better at lower cost than do currently available materials. These improved materials
can be used in systems for both the space and aerospace environments.

Thin-filin research deals with control of chemical reactions at surfaces and interfaces. This
research includes (1) the processing and characterization of electronic and electrooptic materials that are
essential to future information, communication, and command and control systems; (2) the chemical
control of friction on surfaces, which is necessary for the production of solid lubricants and bearings
essential to future aerospace systems that will be subjected to high temperatures; (3) the study. of
hyperthermal surface reactions, common in the space environment and responsible for "shuttle glow,"

A3-1
erosion, and charge exchange·that limit systems performance and the operational life of spacecraft, with
the goal of designing inert skins for space vehicles; and (4) the chemistry of catalysts for endothermic
fuels to determine selectivity. efficiency, and rapid energy transfer to design a catalystlsupercritical fuel
system for the high-temperature engines proposed for 21st-century aircraft.

The core surface chemistry portion of the Inorganic Materials Chemistry Program totals
$1.54 million plus an additional $821 "thousand through University Research Initiative (URI) Programs.
The following chart outlines the FY 1992 investment in this program.

Surface Chemistry (FY 1992)

Topic # PIs * $K
Molecular Electronics/Optics 3 254
Novel Surface Techniques 1 130
Space Environment Effects 3 246
Carbon/Carbon Composite Oxidation 3 285
Endothermic Fuels Catalysis 1 202
Tribochemistry 4 421
... URIs 5 821
TOTAL 20 2359
Excluding URIs (15) 1538
*# PIs is the number of principal investigators.

However, other programs in the Directorate and in other AFOSR directorates also contribute
research in interface phenomena. Examples of such efforts are given in the following program descrip-
tions.

II. CERAMICS AND NONMETALLIC STRUCTURAL MATERIALS. Lt Col. Larry W. Burggraf

Interest in nonmetallic structural materials is driven by a broad range of technological needs.

Systems such as stoichiometric gas turbine engines and hypervelocity transatmospheric space planes are
limited by the inability of current structural materials to function at high temperatures without degradation.
Nonmetallic materials including ceramics such as borides, oxides, nitrides, carbides. and carbon/carbon
composites. which have ionic and covalent bonding, have high binding energies and therefore high melting
points. However, these materials are brittle and/or susceptible to oxidation.

We seek a fundamental understanding of how the physical and chemical properties of a material
result in the macroscopic properties of interest, such as toughness, strength. fatigue resistance, and
oxidation resistance. An understanding of the high-temperature mechanical properties and methods of
imparting toughness to brittle materials at high temperatures is of great interest. The issues of interface
phenomena ·and control in heterogeneous systems are also of interest. We seek better understanding of
the role that oxidation protection debonding coatings play in the mechanics of composites. We want to
understand the processing-microstructure-properties relationships in these materials. Of specific interest

A3-2
are . novel precursors for ceramic matrix compositeS and carbon/carbon that allow control· of the
microstructure and provide an atomic-level distribution of dopants in the composite. A better
understanding of the relationship between the electronic structure (e.g., atomic positions and band
structure) and the physical properties, especially the mechanical properties, is of great interest. We seek
proposals to perform innovative research to further our understanding of these issues.

III. ELECTRONIC DEVICES, Dr. Gerald L. Witt, Device Issues; Maj. Gernot S. Pomrenke, Materials
Issues

The research program encompasses a wide variety of advanced electronic structures and devices,
primarily fabricated from compound semiconducting materials. A range of materials systems (e.g., GaAs,
InP, Si-Ge alloys on Si, the antimonides, and heteroepitaxial materials) and devices (such as
pseudomorphic high electron mobility field effect transistors, heterojunction bipolar transistors, and
resonant tunneling structures) are of interest~specially those structures exploiting quantum mechanical
effects. The use of Si-Ge alloys for device applications is of particular interest. Special focus is placed
on the understanding and applications of so-called "low temperature" GaAs and related layers. Research
efforts are sought in approaches to wafer-level integration such as selected area heteroepitaxy, the use of
patterned substrates, and the lift-off layer technique.

IV. SEMICONDUCTOR MA1ERIALS, Maj. Gernot S. Pomrenke and Dr. Gerald L. Witt

Air Force electronic and photonic signal processing, communications, surveillance, and electronic
warfare systems require continual improvements in performance. This research program is directed toward
developing advanced electronic and photonic materials to provide the required improvements in future Air
Force electronic and photonic systems. In particular, we seek to generate the fundamental knowledge and
the materials data base required for the growth and use of novel, as well as existing, electronic and
photonic materials and structures. No single electronic material has the combination of properties required
for all applications, so several classes of semiconductor materials, including heterostructural combinations,
are currently under investigation. Similarly, several Classes of photonic materials, including semiconductor
heterostructures and nonlinear optical magnetooptical materials, are also under investigation. .There is a
growing interest in pushing toward a higher level of material integration with emphasis on selective-area
epitaxy and growth on patterned or nonplanar substrates.

Compound semiconductors such as GaAs and InP, the ternary alloy GaAlAs, and heterostructural
combinations of such materials are the foundation of a whole new generation of ultrahigh-speed, high-
frequency digital and microwave devices and are being investigated in this effort. These materials provide
the electronic and optpelectronic properties necessary for advanced information and signal processing
applications and for optoelectronic communications. We are investigating these materials for potential use
in detectors for the ultraviolet to infrared region, solid state laser, display, and emitter sources, and in
infrared-active optoelectronic countermeasures.

An effort aimed at developing a Si and Si-Ge heterostructure technology for next generation digital
computer, microwave, and optical sensor systems has recently begun and will continue. Efforts to develop
combinations of Group n to VI and III to V materials and Group IV and Group In to V materials hetero-
structure technology for future device applications are also continuing. Novel concepts are being explored
in quantum transport and structures. Interface issues and understanding of equilibrium and nonequilibrium
growth processes through modeling are also important in heterostructure technology. Our overall emphasis .
in sponsored research is to combine materials science with solid state physics to investigate the
fundamental aspects of ~owth, defects, and properties of multilayer semiconductor structures.

A3-3
 The program also .addresses optical thin-film investigations. The aim is to gain a fundamental
understanding of optical film properties using solid state physics and material science. Specific interests
are in anti- and high-reflection coatings as they concern high-power laser applications and electrooptic
sensors, nonlinear optical films, microscopy, and optoelectronic devices.

V. LIST OF PRINCIPAL INVESTIGATORS AND PROJECTS RELEVANT TO SURFACE

PROCESSING

A. Kummel, The Effects of Molecular Orientation Geometry and Surface Antisotropy Upon Etching
S. J. Sibener, Dynamics of Gas-Surface Interactions
C. M. Ueber, Scanning Tunneling Microscopy Investigations of Metal Dichalcogenide Materials
E. Matijevic, Colloid and Interface Chemistry Aspects of Ceramics
B. H. Cooper, Resonant Charge Transfer in Hyperthermal Atomic and Molecular Ion-Surface Collisions
W. Ho, High Translational Energy Induced Reactions on Silicon
G. B. Hoflund, Development of an O-Atom Gun
L. L. Hench, Multifunctional Gel-Silica Optics
A. J. Gellman, Surface Species in Tribology
G. M. McClelland, Fundamental Studies of Friction, Lubrication and Wear by Atomic Force Microscopy
...
M. Trenary, The Structure and Reactivity of Boron Surfaces
J. Jonas, Fluids, Gels and Glasses Under Extreme Conditions of Pressure and Temperature
P. C. Stair, Experimental and Theoretical Investigation of Photodissociation on MgO(OOl)
J. T. Yates, Jr., The Synthesis and Characterization of Tribophysical Layers on Diamond and Silicon
Carbide Surfaces
P. C. Stair, Experimental Investigations and Molecular Dynamics Simulations of Radiation Induced
Surface Damage
T. Engel, Fundamental Aspect of Plasma Processing
B. E. Koel, Surface Science and Modeling Studies of Endothermic Fuels Catalysis

A3-4
 A4. GLOSSARY OF ACRONYMS AND ABBREVIATIONS

AEM analytical electron microscopy

AES Auger electron spectroscopy
AFM atomic force microscopy
ALT accelerated life testing
APFIM atom probe field ion microscopy
ARUPS 'angle resolved ultraviolet photoelectron spectroscopy
ATR attenuated total reflection
BET' Brunauer, Emmett, and Teller
BLE bom~ardment induced light emission
CDP compositional depth profiling
CVD chemical vapor deposition
DIET desorption induced by electronic transitions
DLC diamond-like coating
EDX energy dispersive X-ray analysis
EELS electron energy loss spectroscopy
EIID electron impact ion desorption
ELEED elastic low energy electron diffraction
EM electron microscopy
EMP electron microprobe (analyzer)
EPMA electron probe microanalysis (analyzer)
ER electromagnetic radiation
ESCA electron spectroscopy for chemical analysis (see also XPS)
ESD electron stimulated desorption
ESDIAD electron stimulated desorption ion angular distribution
EVA ethylene vinyl acetate (copolymer)
EXAFS extended X-ray fine structure spectroscopy
FAB-SIMS fast atom bombardment-secondary ion mass spectrometry
FEM field emission microscopy
FIM field ion microscopy
FIMS field ion mass spectrometry
FTIR Fourier transform infrared (spectroscopy)
FWHM full width at half maximum
GDMS glow discharge mass spectrometry
GDOS glow discharge optical spectrometry
GIS gas/solid interface
HEED high energy electron diffraction
HFS hydrogen forward scattering spectrometry
HREELS high resolution electron energy loss spectroscopy
HR1EM high resolution transmission electron microscopy
HV high vacuum
HVEM high voltage electron microscopy
lAD ion assisted deposition
IBAD ion beam assisted deposition
IBED ion beam enhanced deposition
, IIR ion induced radiation
ILEED inelastic low energy electron diffraction
IMFP inelastic mean free path
IMMA ion microprobe mass analyzer

A4-1
 INS ion neutralization spectroscopy
IR(S) infrared (spectroscopy)
I,SS ion scattering spectroscopy
LAMMA laser microprobe mass analysis
LB Langmuir-Blodgett
LEED low energy electron diffraction
LEEM low energy electron microscopy
UG liquid/gas interface
LIMS laser ionization mass spectrometry
UL liquidlliquid interface
LMP laser microprobe
LPE liquid phase epitaxy
LRS laser Raman spectroscopy
US liquid/solid interface
MBE molecular beam epitaxy
ML monolayer
MRIS multiple reflectance infrared spectroscopy
MSSN mass spectrometry of sputtered neutrals
NRA nuclear reaction analysis ·
NREL National Renewable Energy Laboratory
NSS neutral scattering spectrometry
OMA organized molecular assembly
PAl post ablation ionization ...
PIXE particle induced X-ray emission
PMMA polymethylmethacrylate
PV photovoltaic
PVD physical vapor deposition
QCM quartz crystal microbalance
QMS quadrupole mass spectrometer
(RA)IR (reflection absorption) infrared
RBS Ruthe"rford backscattering spectroscopy
RGA residual gas analysis
RHEED reflection high energy electron diffraction
SA self assembly
SALI surface analysis by laser ionization (of sputtered neutrals)
SAM scanning Auger microscopy or self assembled monolayer
SARISA surface analysis by resonance ionization of sputtered atoms
SBEC single binary elastic collision
SCANIIR surface compositional analysis by neutral and ion impact radiation
SE spectroscopic ellipsometry
SECS solar energy conversion systems
SEM scanning electron microscopy
SERS surface enhanced Raman spectroscopy
SEXAFS surface extended X-ray fine structure
SFE surface free energy
SFG sum frequency generation
S/G solid/gas interface
SHEED scanning high energy electron diffraction
SHG second harmonic generation
SIMA secondary ion mass analyzer

A4-2
 SIMS secondary ion mass spectrometry
SIL solidlliquid interface
SIN signal-to-noise ratio
SNMS secondary neutral mass spectrometry
SIS solid/solid interface
STEM scanning transmission electron microscopy
STM scanning tunneling microscopy
STS scaniting tunneling spectroscopy
SN solid/vacuum interface
1D(MS) thermal desorption (mass spectrometry)
TED transmission electron diffraction
TEM transmission electron microscopy
TOF-AP time-of-flight atom probe
TOF-MS time-of-flight mass spectrometry
TOF-SIMS time-of-flight secondary ion mass spectrometry
'!PD temperature programmed desorption
UHV ultrahigh vacuum
UPS ultraviolet photoelectron spectroscopy
UV ultraviolet
VHV very high vacuum
XANES X-ray absorption near edge structure
XPS X-ray photoelectron spectroscopy (see also ESCA)
XRD X-ray diffraction
XRF X-ray fluorescence

A4-3
 AS. PARTICIPANTS AT THE WORKSHOP ON SURFACE PROCESSING
December 10-12, 1991
Dearborn, Michigan

A C

Aldissi, Mahmoud Chaffee, Kevin

Champlain Cable Corporation U.S. Air Force
12 Hercules Drive OLAC PURKCP
Colchester, VT 05446 Edwards AFB, CA 93523
802/655-2121 FAX 802/655-2025 805/275-5740 FAX 805/275-5144

Allara, David Cheng, Yang

Pennsylvania State University General Motors Research Laboratories
Polymer Science Dept 30500 Mound Road
309 Steidle Building . Warren, MI 48090
UI1iversity Park, PA 16802 313/986-0939 FAX 313/986-8697

Anderson, Richard Coduti, Phillip

Sandia National Laboratories Inland Steel Research Laboratories
Division 8342; P.O. Box 969 3001 E. Columbus Drive
Livermore, CA 94551-0969 E. Chicago, IN 46312
510/294-3258 FAX 510/294-3231 219/299-6111 FAX 219/399-6562

B Czanderna, Alvin
National Renewable Energy Laboratory
Baird, Ronald 1617 Cole Boulevard
Ford Motor Company Golden, CO 80401
Room S-3061, SRL 3031231-1240 FAX 3031231-1381
Dearborn, MI 48121-2053
313/337-1303 FAX 3131323-7397 D

Barber, Gary Davis, Guy

Detroit Diesel Corporation Martin Marietta Laboratories
Oakland University 1450 S. Rolling Road
Detroit, MI 48239-4001 Baltimore, MD 21227
313/592-5145 FAX 313/592-7888 4101247-0700 FAX 410/247-4939

Baughman, Ray deVries, James

Allied-Signal Ford Motor Company
Road T, P.O. Box 1021R 20000 Rotunda, P.O. Box 2053
Morristown, NJ 07962 Canton, MI 48188
201/455-2375 FAX 201/455-5991 3131322-2494

Boerio, F. James Duke, Charles

University of Cincinnati Xerox Webster Research Center
Dept of Materials Science 800 Phillips Road 0114-38D
Cincinnati, OH 45221 . Webster, NY 14580
513/556-3111 FAX 513/556-2569 716/422-2106 FAX 716/265-5080

AS-I
 '". '
, .': ~
.:--. . ~ .' - -: :
~. ~ .'
. . ' . -
. .' .; '. .: ......... .

E Graham, Michael
BIRlJNorthwestern University
Eberhardt, James 1801 Maple Ave.
U.S. Department of Energy, CE-34 Evanston, IL 60201
1000 Independence Ave., S.W. 708/491-5436 FAX 708/467-1022
Washington, DC 20585
202/586-9837 FAX 202/586-8134 H

Erck, Robert Halley, J. Woods

Argonne National Laboratory University of Minnesota
MCT-212 Corrosion Research Center
Argonne, IL 60439 .and Physics Department
7081252-4972 FAX 708/252-4798 School of Physics and Astronomy
Minneapolis, MN 55455
F 6121624-0395 FAX 612/624-4578

Fenske, George Hubler, Graham

Argonne National Laboratory Naval Research Laboratory
MCT-212 Code 4671
Argonne, IL 60439 Washington, DC 20375
708/252-5190 FAX 708/252-4798 202/767-4800 FAX 202/767-5301

Ferguson, Gregory Hurd, Alan

Lehigh University Sandia National Laboratories
Department of Chemistry Division 1841
S. G. MUDD Bldg. 6 Albuquerque, NM 87185
Allentown, PA 18015 505/845-8629 FAX 505/844-2974
215/758-3462 FAX 215/758-3461
J
Fischer, Richard
3M Weathering Resource Center Jorgensen, Gary
3M Center 209-2W-05 National Renewable Energy Laboratory
St Paul, MN 55144 1617 Cole Boulevard
612/736-1769 FAX 612/733-4457 Golden, CO 80401
303/231-7273 FAX 303/231-1199
G

Gaarenstroom, Stephen
General Motors Research Laboratories Kassner, Michael
30500 Mound Road OBESILLNL
Box 9055 U.S. Department of Energy
Warren, MI 48090-9055 M.S. G236 G1N-ER13
313/986-0835 FAX 313/986-0817 Washington, DC 20585
301/903-4271
Ginder, John
Ford Motor Company Kelley, Frank
Scientific Research Laboratories Caterpillar Inc.
Dearborn, MI 48121 P.O. Box 1875
Peoria, IL 61656
309/578-6181 FAX 309/578-2953

AS-2
' ;' :
, '.
Ketola, Warren " " ": ,', '. . , .. , '
Macdonald, Digby' , '~', .. " '!. ~.

3M The Pennsylvania State University

Bldg. ' 553-A, 3M Center Center for Advanced Materials
St Paul, MN 55144 517B Deike Building
6121733-1845 FAX 6121733-2227 University Park, PA 16802
814/863-7772 FAX 814/863-4718
Kuhn, Hans
Milliken Res. Corp. Martin, Jonathan
P.O. Box 1927 M-405 NIST
Spartanburg, SC 29301 Building 226, Room B348
803/573-2320 FAX 803/573-2417 GaitherSburg, MD 20899
3011975-6717 FAX 301/975-4032
L
Mayanovic, Robert A.
Landgrebe, Albert Department of Physics and Astronomy
U.S. Department of Energy, CE-34 Southwest Missouri State University
1000 Independence Ave., S.W. Springfield, MO 65804
Washington, DC 20585 417/836-5606 FAX 417/836-6934
2021586-1483 FAX 202/586-1600
McConnell, Robert
Lemons, Ross National Renewable Energy Laboratory
Los Alamos National Laboratory 1617 Cole Boulevard
P.O. Box 1663, MS D429 Golden, CO 80401
Los Alamos, NM 87545
505/667-6832 FAX 5051665-4292 McCune, Robert
Ford Motor Company-Research
Licht, Stuart MIS S-2023
Clark University Dearborn, MI 48121
Department of Chemistry " 313/845-0610 FAX 313/594-4929
950 Main Street
Worcester, MA 01610 Means, Ken
West Virginia University
Liehr, Michael Mechanical and Aerospace Engineering
IBM T. 1. Watson Research Center Morgantown, WV 26506
P.O. Box 218 304/293-3111 FAX 3041293-6689
Yorktown Heights, NY 10598
914/945-3718 FAX 914/945-4015 Mertzel, Elaine
B F Goodrich
M Moore and Walker Road
Avon Lake, OH 44012
MacArthur, Donald 2161933-1801 FAX 216/933-0132
CHEMAC International
200 East Big Beaver Miller, Barry
Troy, MI 48083 AT&T Bell Laboratories, 10-305
313/879-0587 600 Mountain Ave.
Murray mn, NJ 07974
908/582-6610 FAX 908/582-3609

AS-3
Miller, Carl o
General Motors Corporation
1300 North Dort Olsen, Royal
Flint, MI 48556 General Motors Corporation
3131257-7402 FAX 313/257-2001 33500 Mound Rd.
Sterling Heights, MI 48310
Mittal, Kastuniri 313/947-0547 FAX 313/947:"1584
IBM U.S. Technical Education
500 Columbus Ave. Opila, Robert
Thornwood, NY 10594 AT&T Bell Laboratories
9141748-5747 FAX 9141748-5594 Room lC-260
Murray Hill, NJ 07076
N 908/582-3390 FAX 908/582-2226

Naylor, Malcolm Orazem, Mark

Cummins Engine Co. University of Florida
P.O. Box 3005 Department of Chemical Engineering
MC50183 Gainesville, FL 32611
Columbus, IN 47201 904/392-6207 FAX 904/392-9513
812/377-7713 FAX 812/377-7808
P
Neidlinger, Hermann
SBH .. Pernisz, Udo
810 Kifer Road Dow Corning Corporation
Sunnyvale, CA 94086 Mail #C041Al
408/991-6300 FAX 4081773-5282 Midland, MI 48686-0994
517/496-6087 FAX 517/496-5121
Nelson, Gerald
Sandia National Laboratories Pitts, Roland
P.O. Box 1800 National Renewable Energy Laboratory
Albuquerque, NM 87185 1617 Cole Boulevard
505/844-5200 FAX 505/846-4168 Golden, CO 80401
303/231-1929 FAX 3031231-1381
Nichols, Fred
Argonne National Laboratory Powell, Cedric
9700 South Cass NIST
Argonne,IL 60439-4838 Chemistry, B-248
708/252-8292 Gaithersburg, MD 20899
301/975-2534 FAX 301/975-3845
Nuzzo, Ralph
University of Illinois at Urbana-Champaign S
168 Materials Research Laboratory
Urbana, IL 61801 Savinell, Robert
2171244-0809 FAX 217/244-2278 Case Western Reserve University
Department of Chemical Engineering
A. W. Smith Building
Cleveland, OH 44106
216/358-2728 FAX 216/368-3016

AS-4
 Scherson, Dan Speaker, Lois
Case Western Reserve University Eastman Kodak Company
Department of Chemistry Bldg. 82A, Floor 7RL
Cleveland,OH 44106 Rochester, NY 14650-2104
. 216/368-5186 FAX 216/368-3006 716/588-7057

Schuetzle, Dennis Swathirajan, S.

Ford Motor Company General Motors Research Laboratories
Scientific Research Laboratory-53086 Physical Chemistry Department, RCEL
Dearborn, MI 48121 Warren, MI 48090-9055
313/323-1734 FAX 313/323-7397 313/986-0702 FAX 313/986-2244

Searson, Peter U
The Johns Hopkins University
Department of Materials Science Ulman, Abraham
102 Maryland Hall, JHU Eastman Kodak Company
Baltimore, MD 21218 Rochester, NY 14650-2109
301/338-8774 FAX 301/338-5293 716/477-6815 FAX 716/477-6498

Sherwood, Peter v
Kansas State University
Department of Chemistry Ventura, Susanna
Willard Hall SRI International
Manhattan, KS 66506 333 Ravenswood Ave.
913/532-6689 FAX 913/532-6666 Menlo Park, CA 94025
415/859-4467 FAX 415/859-2316
Shobet, 1. Leon
University of Wisconsin Vojnovich, T.
Engineering Research Center U.S. Department of Energy
for Plasma-Aided Mfg. Office of Transportation Technologies
1410 Johnson Drive, Room 101 1000 Independence Ave., S.W.
Madison, WI 53706 Washington, DC 20585
6081262-2181 FAX 608/262-3632
W
Smyrl, William
University of Minnesota Whitesides, George
Corrosion Research Center Harvard University
Minneapolis, MN 55455 Chemistry Department
612/625-0717 FAX 612/626-7246 12 Oxford St.
Cambridge, MA 02138
Snyder, Dexter 617/495-9430 FAX 617/495-9857
General Motors Research Laboratories
Physical Chemistry Willermet, Pierre
31500 Mound Road Ford Motor Company
Warren, MI 48090-9055 3179 SRL, PO Box 2053
313/986-0750 FAX 313/986-2244 Dearborn, MI 48121
313/337-3939 FAX 313/337-5581

AS-5
 -
Williams, James . y
Oak Ridge National Laboratory
Solid State Division Yasuda, Hirotsugu
Bldg. 3137, MS 6057 University of Missouri-Columbia
Oak Ridge, TN 37831 Center for Surface Science
615/574-6265 FAX 615/574-4143 and Plasma Technology
Columbia, MO 65211
Wilson, Dane 314/882-9602 FAX 314/882-1831
Oak Ridge National Laboratory
P.O. Box 2008 Z
Oak Ridge, TN 37831-6156
615/576-4810 FAX 615/574-5118 Zaluzec, Matt
Ford Motor Company
Wilson, Mahlon 15000 N. Commerce Drive
Los Alamos National Laboratory Dearborn, MI 48120
MS 0429 313/323-2734 FAX 313/337-1046
Los Alamos, NM 87545
505/667-6832 FAX 505/665-4292 Zerlaut, Gene
SC-Intemational Inc.
346 W. Pine Valley Drive
Phoenix, AZ 85023
6021993-7877 FAX 6021789-6616

AS-6
 I. INDEX

Accelerated life testing, ES-4, ES-S, ES-7 to 9, 20-17, 23-14, 24-6, 2S-1 to 9, 26-1
Acronyms and abbreviations, A4-1, 17-9,26-4
Adhesion or adhesives, ES-4, 6-1, 9-1, 16-6, 17-14, 18-3 to 6, 20-3, 20-7, 21-6, 22-4, 23-1, 23~7, 23-10,
23-11,23-12, 23-13, 24-S, 26-1, 27-1,27-10, 29-1, AI-3
Adsorption, 2-7, 3-1, 4-1, 12-S, AI-2
AES, 1-1, 11-4, 11-6, 17-9, 18-7,20-13,26-4, Al-l
advantages and limitations, 1-10
compared with other techniques, 1-4 to 7
emission, 7-22
Alloys (see metal of interest)
Alodine conversion coatings, 20-14
Alumina, 10-7
Aluminum, 12-7, IS-9, IS-IS, 16-22, 19-8,20-3,20-18
adsorbates, 0 (7-7)
alloys, 2-1, 7-1S, 20-3
nitride, 16-9
oxide, 12-6, IS-9, IS-14, 16-9, 17-13,20-11,29-3
Amoriphization, IS-6, IS-8 .
Angular resolved AES, SIMS, and XPS, 26-4
Argon bombardment, 1-4,2-3,26-1
Arsenic oxides, 10-4
Artificial diamond, IS-1
ASTM
Atom probe FIM, 1-14,26-4
Atomic force microscopy (AFM), 6-1, 17-9, 18-7,20-14,26-4,29-9
Atomic geometries, 2-S .
Atomic oxygen, 9-1, 12-7
Auger electron spectroscopy (see AES)
Auger yield, 7-4, 7-6
Automotive technologies, interfaces, 26-3

Backscattering, 1-3
Batteries, solid, ES-4, ES-6, 20-S, 21-1 to 14, 27-1, 27-3
Beam damage, 1-6
Bearings and bushings, 22-6
Binary scattering, 1-6
Biological membranes, 4-1
Bismuth, 2-8
Bonding, chemical (see Chemical bonding)
Boron nitride, 16-9, 16-13, 16-16,20-11
Bragg peaks, 7-4
Buried.interfaces, ES-S, ES-7 to 9, 7-1S, IS-I, 24-4, 26-2, 26-S
Button pull in adhesion testing, 23-13

1-1
Cadmium
selenide, to-3, 28-7
sulfide, 10-3, 29-tO
telluride, to-3, 15-9,20-6,28-7, 29-tO
Calcium fluoride, 8-1
Cams and cam-roller followers, 22-6
Carbon contamination
Catalysts
automotive
fuel cell, ES-4, 21-5, 21-9
general, ES-4, 4-1, to-I, 15-1, 16-11, A3-2
~eramic membranes, 14-7
Chalcogenides, to-3
Charge neutralization, 1-7, 16-3
Chemical bonding, 26-6
EELS, HREELS, 1-14, 8-1, 17-9,26-4, Al-l
ESDIAD
IR-RA and IR spectroscopies, 3-1 to 17, 11-2, 11-4, 17-6, 20-16,23-8,26-4,29-9, Al-l
ISS. 1-1,2-7, 17-9,26-4
Kissing, 23-15
Raman spectroscopy, 1-14, 17-9, 26-4, Al-l
SEXAFS (EXAFS), 2-4, 7-1,20-14,23-8,26-4 .
STM, 1-14,2-4, 6-1, to-6; 17-9, 18-7,20-14,26-4, 29-9, A3-4
UPS, 17-9
Weak,23-15
XPS, 1-1,26-4
Chemisorption, 18-4, AI-2
Chromium, 15-9, 15-15, 16-9
Chromium compounds, 20-11
Clean surfaces, 2-1, 2-4, 5-4, 8-1, 18-3,23-15
Climatic stresses and ALT, 25-8
Climbing drum in adhesion testing, 23-13
Coating technologies, ES-3, 11-2, 18-6, 23-1
Coefficients of thermal expansion, 23-1
Composites, 23-1
Compositional depth profiling, CDP (see Depth profiling)
Condensed matter science, 29-4 (OMAs)
Conducting polymers, ES-4, ES-I0, to-5, 27-1 to 13
applications areas, 27-1
composites, 27-10
composition. 27-12
electroluminescent, 27-5. 27-6
fllms and coatings. 27-8
ionically conductive, 27-4
overview, 27-2
photonic, 27-5
properties, 27-11
research needs, 27-13
stability, 27-2, 27-11
types of, 27-3, 27-7

1-2
Cones from sputtering, 15-11, 16-12
Conservation and renewable technologies, ES-l, ES-4, ES-7 to 13,21-1,23-1,24-1,26-1,27-2,28-1,29-1
Contact angles, 18-9
Cooperation by industry, government, and academic laboratories, 26-3, 26-9
Copper, 7-9, 10-6, 16-23, 24-3
adsorbates,l (7-9), 0 (7-10), S (7-11), a (7-11), Te (7-11), Xe (7-11), HOCO (7-12)
alloys, 7-15
multilayers, 10-5, 10-12
oxides, 10-4, 16-9
Corrosion, ES-4, 20-1
basic research, 20-19
coatings techniques, 20-9, 23-1
conversion layers, 20-4, 20-14
fundmentals related to applications, 20-19, 23-6
inhibition, 29-10
in road transportation systems, 20-3
modeling of systems, 20-17
organic coatings, 20-7
protection, ES-5, 11-1, 16-11, 20-1, 20-7
resi&tance, 9-1, 15-1,21-4,29-2,29-10
Covalent bonding, 2-2
Cross-linked polymers, 11-4
CVD, 8-1, 14-2, IS-I, 16-12, 19-9, 19-12, 20-9, 20-12, AI-2

Damage to surfaces, 1-3

Data
bases for ALT, 2S-8
collection, 7-3 (EXAFS), analysis (mAD), 16-8
comparisons of surface techniques, 1-4
Debye-Waller factor, 7-2
Defects at interfaces, 26-S
Degradation mechanisms, 20-1, 21-2, 23-5 to 7, 23-11, 24-2, 25-1, 2S-7, 26-2, 26-5, 27-12
Deposition processes (see CVD, mAD, PVD, ERC)
Deposition, selective, 24-3
Depth profiling, 1-5 to 10,3-3, 14-13, 15-11
Design of interphase systems, 23-2
Desorption, 2-7, 7-7
Detection limits in surface analysis, 1-6
Diamond like coatings, DLC (see also Artificial diamond), ES-4, 12-8, 16-9, 16-11, 20-11
Dielectrics, 16-10, 23-9
Die materials, wear, 22-7 to 9
Diesel engine component R&D needs, 22-5
Diffusion studies, 21-4, 21-8
Diffusion, surface, 11-2,21-4,24-2,26-2,27-12
Doctor blading, 14-5
Durability (see Lifetime)

EBIC, 28-11
Eddy current NDE analysis, 23-14
EELS (see Chemical bonding)

1-3
Electric vehicles, 20-5, 20-13
Electrochemical techniques, ES-3, 10-1
automobile industry, 10-2
conducting polymers, 27-10
electronics industry, 10-1
for PECS, 28-6
impedance analysis, 20-15, 23-8, 28-10
interfaces, 21-7
metals, 10-1,20-12
semiconductors, 10-3
superconductors, 104
Electrochromic materials (windows), 20-6, 20-18, 24-2, 24-3, 24-8, 24-11, 24-12, 27-1, 27-6, 29-6, 29-10
Electrode impedance spectroscopy, 23-8, 23-9, 23-10
Electrode modified surfaces, 17-13
Electroless (processes), ES-3, 20-6
alloys, 10-2
cobalt, 10-2
copper, 10-1
electronic materials, 10-2
gold, 10-1
nickel, 10-1
palladium, 10-1
Electronic materials, 19-11
Electrophoresis, 144
ELEED (see LEED)
Ellipsometry, 18-7, 20-16
Engine wear, 22-2, 26-1
ERC, 11-3
Escape depths, electron, 1-12, 7-5
ESDIAD (see Chemical bonding)
Ethylene vinyl acetate, EV A, 29-6
EXAFS (see Chemical bonding)

FEM,26-4
Fermi level, 7-22
FIM,264
Fluorescence spectroscopies, 23-8
Fluorescence yield, 74, 7-22
Friction and wear, 22-1
Fuel cells, ES4, ES-6, 21-1 to 14,27-1,29-2,29-5,29-10

Gallium arsenide, 2-1, 2-6, 7-15, 10-3, 104, 15-9, 16-9, 17-15, 19-10,24-4, A3-3
Gallium nitride, 7-15
Gears and bearings, 22-2
Germanium, 2-6, 54, 7-12, 10-3, 16-9, 16-18, A3-3
Gold, 2-5, 54, 10-1, 10-6, 12-7, 17-13,29-3
Graded index coatings, 16-9
Grain boundaries, 24-2

14
Heteroepitaxy, 29-4
HEED, 2-3
Hostile environments, 24-2, 25-1, A3-1, A3-4
HREELS (see Chemical bonding)
HR1EM, 2-3, 26-4
HVEM, 1-14,26-4
Hydrocarbon(s)
contamination
detection
in OMAs, 17-1, 18-1
fluorizated, 18-10
Hydrogen detection, 1-6, 26-6
Hydrogen oxidation, 21-5, 21-7

IBAD (see also Ion beams for)

materials deposited, 16-9
modeling, 16-4
ILEED (see LEBO)
Imaging, lateral, 1-5 to 10, 3-3
Implant profiles, 15-1
Indium phosphide, 28-7, A3-3
Infrared absorption (see also Chemical bonding) .
advantages and limitations, 3-2, 3-14
applications, 3-13, 17-6, 17-9, 20-16, 26-4 to 6
information from, 3-2
measurement time, 3-14
theory, 3-2, 3-4
types of experiments, 3-7 to 12
Infrastructure issues, 26-9
In situ diagnostics, 24-4, 26-1, 27-12
Interdiffusion, 24-2, 26-5
Interdisciplinary research needs, ES-12, 11-6, 26-9
Interfacial microchemical characterization needs, ES-9, 26-1 to 12
Interference microscopy, 20-16
Interphases, 23-1 to 16
characterization, 23-7
degradation in systems, 23-5
formation mechanisms, 23-3
modification, 23-10
process variables, 23-15
Ion beams for
assisted deposition, 11-1, 11-5, 12-3, 15-1, 16-1, 16-6,20-9
depth profiling (see Depth profiling)
enhanced deposition, 11-5, 12-3, 16-1, 16-6, 20-9
surface analysis (see ISS, RBS, SIMS, SNMS)
Ion bombardment effects, 13-1, 16-3
Ion desorption, 7-7
Ion implantation, 15-1, 20-9, AI-2
automotive industry, 15-1
corrosion resistance, 15-1, 20-7

1-5
 cost, IS-3, IS-1O
depth of layers, IS-3
electronics industry, IS-1
equipment, IS-4, IS-7, IS-12
fundamentals, IS-2
in polymers, IS-8
Ion plating, 12-3, 12-9, 20-9
Ion trapping, 24-2
Ionic bonding, 2-2
Ionization in plasma processes, 11-1
Iridium, 2-S, 10-3 (oxides)
Iron oxide, 28-7
Isotopes, 1-8 to 10
ISS, 1-1,2-7, 17-9, 18-7,20-14,26-4, Al-1
advantages and limitations, 1-10
comparisons with other surface analysis, 1-4 to 8

Knock-in effects (see Depth profiling, SIMS, SNMS, ISS)

LAMMA,26-4
Lap shear in adhesive bonds, 23-13
Laser(s), Al-1
induced fluorescence, 11-2
Raman spectroscopy, 17-9, Al-l
Lateral resolution, comparisons, 1-4 to 6
LB, Langmuir-Blodgett, S-S, 9-2, 14-2, 17-S, 17-6, 17-11, 18-1, 18-8 to 11,20-16,23-10,29-1, AI-3
applications, 17-11
compared with self-assembly of OMAs, S-6, 17-11 to 13
Lead-acid batteries, 20-S, 20-13, 26-3
Lead compounds, 10-3
LEED, 2-3, 7-8, 17-9, 26-4
LEEM, 2-4, 26-4
LEPD,2-3
Lifetime (of devices or components), ES-l, ES-S, ES-12, 20-2, 22-2, 22-7, 23-1, 23-S, 23-14, 2S-1, 2S-4,
26-1, 27-10, 29-10
Linear model for ALT, 2S-2
Liquid/solid interfaces, ES-4, 28-1
Lithium solid polymer electrolyte batteries, 20-S, 21-1, 21-10 to 14
Lo E glass, 24-12
Low energy surfaces, ES-4, ES-11, 17-Iff, 18-1, 20-7
Lubricating and wear surfaces, ES-4, ES-6, 1-1, 10-6, 11-S, 14-7, IS-I, IS-10, 16-12,20-4,20-11,
20-18,22-1 to 9, A3-1, A3-4

Magnesium alloys, 20-3, 20-18

Manufacturing monitoring, 23-1, 24-1, 26-1
Mechanical stresses in films, 16-6, 24-S
Membranes, 21-6 to 10
Metal-semiconductor interfaces, 7-14
Methanol oxidation, 21-1, 21-9, 22-2
Microbalance applications, 20-16

1-6
 Micros~cture, 16-8
Mirrors, 24-3
automotive, 14-2
cleaning, 18-2
dielectric, 16-6
optical properties, 18-3
reflectance losses, lS-2, lS-lO
silvered polymers, lS-lO, 20-6, 20-1S, 24-1, 24-10
solar applications, 14-7, IS-I, lS-lO, 20-2, 20-5
Moisture in manufacturing processes, 23-6, 23-14, 23-15
Molecular orientation, 3-2,4-1
Molybdenum oxides, 10-3
Molybdenum sulfide, 16-9
Monolayers
inorganic, 2-7, 7-9, 7-13, 12-S
organic - see OMAs, 7-13
single crystals, 2-7, 7-9
self-assembled, 17-1 ff, 29-1 ff
Mossbauer spectroscopy, 23-S, 23-9
Multiple reflectance infrared spectroscopy, MRIR, 26-4

Nanostructures, 29-4
. Neutral desorption,
Neutron reflectometry, 20-15
Nickel, 5-4, 7-15, 19-5, 24-3
PTFE co'mposites, 10-6
with ~, 5-4, 5-9
with I, 7-9
with 0, 7-9
with S, 7-10
Nickel compounds, 10-6
Niobium, 16-1S
Nondestructive analysis needs, 23-S, 23-10, 23-14, 26-7
Nonlinear optical properties, 17-13
Nuclear reaction analysis, NRA, 26-4
Nucleation and growth, 11-2, 12-5

Optical ftlms, 16-9, 17-13

Optically stimulated electron emission, 23-S
Organic materials, 1-10
adsorbates, 5-5, 7-12
corrosion protection, 20-7
molecular assemblies, 17-1
Organized molecular assemblies, ES-4, 17-1,29-1
applications, ES-4, 17-1, 17-7, 17-13,29-5 to 12
characterization, 17-6, 17-9
coatings, 17-3
critical issues, 17-2,29-1 to 3
defects, 17-2,27-10
devices, 17-3,27-10, 29-5

1-7
 multi functionality , 17-13
multilayers, 17-4, 17-12, 17-17
optimum materials, 17-7, 27-lO
pinholes, 17-2, 17-12
polymeric, 17-12, 27-lO
preparation variables, 17-4, 17-5, 19-1O
processing, 17-8, 17-12
research needs and opportunities, ES-ll, 29-1 to 3, 29-8 to 12
review of properties, 17-1, 17-2, 17-12,29-1
soiling protection, 18-1
stability, 17-2, 17-12,29-7
Oxidation, 16-11
Oxygen electrocatalysis, 21-7
Oxygen reduction, 21-7
Ozone cleaning, 8-1, 18-7

Particle bombardment effects, 13-1

Parylene polymerization, 23-12
Peel and T-peel in adhesion testing, 23-13
Performance ranking from ALT, 25-3
Perovskites, lO-4
Phosphate conversion layers, 20-4, 26-3
Photoacoustic spectroscopy, 28-10
Photodegradation, 9-1, 23-6
Photoelectrochemical systems, ES-4, ES-I0, 28-1 to 17
applications, 28-1
background, 28-1 to 4
characterization, 28-8 to 11
fabrication of structures, 28-4, 29-5
fundamentals, 28-2, 28-12,28-13
preparation, 28-7
research needs, ES-lO, 28-14
stability, 28-7
surface modification, 29-5
Photoemission, 7-22, 7-21
Photovoltaic devices (PV), ES-2, 20-2, 20-5, 20-18, 24-1, 24-3, 24-8 to 10,29-6,29-10
Physical adsorption, 18-4
Piston ring/bore wear, 22-1
PIXE,26-4
Plasma
detection and control; 11-2
polymerization, 11-3, 23-5, 23-11, 23-12, 24-4
processes, 11-1, 12-6
spraying, 11-5
thermal CVD, 11-5
types of, 11-7
Platinum, 2-5, 5-4, 10-6, 16-11,20-11, 21-7, 21-9, 26-3, 29-3
Polyaniline, 10-6,27-3,27-7
Polycarbonate, 10-6

1-8
Polymers, 20-3
applications, 23-2
characterization in interphase systems, 23-4
electrolyte membrane, 21-1
ion implanted, 15-8
plasma polymerization, 23-5, 23-11
Polymer/polymer and polymer/meta1(oxide) interfaces, ES-4, ES-7, 23-1 to 16,26-3,29-6
Polymethylmethacrylate, PMMA, 11-3, 19-7,20-6,20-18,24-4
Polypyrrole, 10-6, 27-9, 28-7
Processibility in interphase systems, 23-2
Process monitors, 23-9 23-10, 26-1
Processing variables/properties relationships, 23-13, 23-15
Properties-preparation relationships, 12-9, 19-8, 23-13, 23-15
PVD, 12-1, 16-1, 16-2, 16-6, 19-9,20-6, 20-12

Quadrupole mass spectrometer or analyzer, 15-6

Quantitative analysis in
compositional analysis, 1-13
surface structural analysis, 2-1

Radiography, 23-14-
RBS, 1-1, 11-6, 17-9,20-14,26-4, Al-1
advantages and limitations, 1-10
Recombination centers, 24-2
Reconstruction, 2-2
Recyclability of materials in composite systems, 23-2
Real time and accelerated testing, 25-5
Real time monitoring, 26-7
Reference data in surface analysis, 1-14,26-8
Refractory compounds, 10-5
Relaxation, 2-2
RGA,15-1O
RHEED,26-4
Rugate filters, 16-10, 16-20
Ruthenium, 21-9

SALI (see SNMS)

SAM, scanning Auger microscopy, 11-6
Sample preparation for
compositional analysis, 1-4
infrared measurements, 3-8
structural determination, 2-4
SAMs, self-assembled monolayers, ES-11, 5-6, 17-1,23-11,29-1 to 14
Scanning probe microscopies (see also S1M), 6-1
Self-assembly (see also SAMs), 17-6, 17-12, 18-1,23-11,29-1
SEM, 11-6, 16-23, 17-9,23-8,29-9
Semiconductors (general), 11-7, 15-9, A3-3
Sensors, 4-1, 17-6, 20-4,26-3,28-6,29-11
SERS, 23-8
SEXAFS (see Chemical bonding)

1-9
SFE, ES-4
SFG, 5-1, 5-5, 17-9,23-8, 26-4
SHG, 4-1, 5-1, 5-3, 20-16, 23-8, 26-4
Silane, 12-8
Silicides, 2-8, 5-4, 16-9, 19-7
Silicon, 2-6, 5-4, 8-1, 10-3, 11-7, 16-9, 16-17, 19-7,20-6,20-11, 20-18, 24-3, 28-7, A3-3
adsorbates on, 3-3,5-4, 7-12, 7-14, 8-1, 19-7 .
carbide ftlms, ES-4, 15-9, 16-9, 19-7
impurities in, 24-4
nitride films, 16-1, 16-4, 16-9, 16-13, 20-11
oxide, 8-1, 12-7, 14-7, 16-9, 17-13,20-11,29-3
PV cells (see Photovoltaic)
semiconductors, 5-4, A3-3
Silver (see also Mirrors), 10-6, 17-14,24-1, 24-3, 29-3
structure, 2-5
with iodine, 7-8
with oxygen, 7-10, 29-3
SIMS, 1-1 to 4, 17-6, 17-9, 18-7,20-14, 26-4, 29-9
advantages and limitations, 1-10
SNMS, 1-1 to 4, 20-14, 26-4
advantages and limitations, 1-10
Soda-lime glass, 14-6
...
Sodium-sulfur batteries, 20-5
Soiled surfaces, 18-3,29-2, 29-10
Solid/gas or solid/vacuum interfaces, ES-4, 1-1,2-1, 3-1,4-1,5-1,26-3
Solidlliquid interfaces, 3-14,4-1,5-1, 7-13, 29-1
Solid/solid interface (see also Buried interface), 7-13, 26-3
Solar energy (conversion or devices), ES-l, 4-1, 10-3, 10-4, 14-1, 18-1, 19-1,20-1,20-5,24-1,26-1,28-1
Solar flux, 19-6
Solar furnaces, 19-2 to 5
Solar insolation, 19-3, 19-18
Sol-gel films, 14-1 to 8
Spectroscopic ellipsometry, 17-9,20-15, 23-8
Spin coating, 14-4
Sputter deposition, 12-2, 20-6, 20-9, AI-2
Sputtering, 15-2, 15-11, 16-12
Standards, 26-10
Steels, hardening of, 19-5
SlEM, 1-14,26-4
STM (see Chemical bonding)
Stresses in ALT, 25-7
Stresses in films, 12-5, 16-6,24-5
Superconducting oxides, 10-4, 14-7, 16-9, 19-10
Substrate cleanliness, 23-15
Surface analysis (see also AES, ISS, RBS, SIMS, SNMS, XPS)
analytical features, 1-5 to 9
applications in R&D, ES-2, 23-8, 26-2
characterization, ES-2, ES-9, 1-1, 3-1, 3-3, 20-2,20-13,20-18,23-5,23-8
comparisons of methods, 1-3, 1-9, 3-3
limitations, 26-2

1-10
 major uses, 1-10 to 13
overview, 1-1
research needs, 26-2
sampling depth, 1-2
spatial resolution, 1-3, 1-8, 1-13
Surface composition (see also Surface analysis), ES-1, 1-1, 3-2,26-1 to 12
Surface modification (see also methods listed), ES-3, 20-2, 20-6, 21-6, 23-10, 24-2, Al-3
coatings (see also PVD, CVD), ES-3, 9-1, 17-9, 18-6
electrodeposition (and electroless), ES-3, 54, 9-3
ion beam assisted deposition (see IBAD), ES-3, 9-3
ion implantation, ES-l, 9-3, 15-1, 16-2,20-7
overview, 9-2
plasma processes, 9-3, 11-1, 11-5, 19-8,23-5,23-11
polymer surfaces, 9-1
solar furnace, 19-1, 19-5, 19-17
sol-gel processes, 9-3, 14-1,20-12
submonolayer, 5-6
vacuum deposition, 12-1
Surface nonlinear optical spectroscopy (see SFG and SHG)
Surface processing overview, ES-l, ES-2, ES-12
Surface reflectivity, 23-8
Surface science, basic support, ES-1, AI-I, A2-1, A3-1
Surface soiling, 18-1 to 25
Surface structure, ES-2, 2-1, Al-2
adsorbate overlayers, 2-7, 2-9,4-1, 7-1
compilations, 2-3
materials themselves, 2-5 to 9
reconstruction and relaxation, 2-2, 2-5
theory, 2-1
Surface tension (see also SFE), 14-4, 18-5
Surface thermodynamics (see SFE)
Surface topography, 26-2, 26-5
Surface treatments, 23-10 (see also Surface modification)

Tantalum oXide, 16-9

Tellurium, 7-12
TEM, 11-6, 12-8, 17-9
Thallium oxide, 10-3
Thermography in NnE, 23-14
Thin films, A34
densification, 14-1, 16-8
multilayers (see also Solar devices), 10-5,24-1, 29-6
solar devices, ES-4, ES-5
stresses in, 12-5, 14-6
TIme-of-flight (see ISS, SIMS, SNMS)
TItanium, 15-9
TItanium carbide, 12-5, 20-11
TItanium dioxide, 14-1, 14-6, 16-9, 28-7
TItanium nitride, 12-6, 164, 16-9, 16-17,20-11
Topography of surfaces, 15-11,26-5

1-11
Total electron yield, 7-6
Transmission wear, 22-4
Transportation technologies, ES-4 to 7,20-1,21-1,22-1, 26-3, 27-2
Tribology, 4-1; 9-1, 10-2, 16-12,22-3,29-2,29-10
Tungsten oxides, 10-3 .

rntrasound in NDE analysis, 23-14

rntraviolet-ozone cleaning, 8-1, 18-7
UPS (see Chemical bonding)
UV degradation of polymers, 23-6

Vacuum requirements, 1-1, 12-1

Valve guide/stem wear, 22-1
VUV emission, 11-2,23-8

Weak and kissing bonding at interphases, 23-15

Wear (see Lubrication)
Wettability, 18-6, 18-7
Weathering environments, 25-1, 25-6
Work function 7-22
Wurtzite, 2-1

XANES, 7-1, 23-8, 23-9, 29-9 ..

XPS, 1-1, 11-4, 11-6, 12-8, 17-6, 17-9, 18-7,20-13,26-4,29-9, Al-1 .
advantages and limitations, 1-13
compared with other techniques, 1-4 to 7
X-ray diffraCtion, grazing, 20-14, 26-4
XRF, 1-14,23-8,26-4

Young-LaPlace equation, 14-6

Zeolites, 14-8
Zincblende, 2-1, 16-9
Zinc-coated steel, 20-3, 20-6, 20-12,20-18,26-3
Zinc compounds, 16-9
Zirconium nitride, 16-9
Zirconium oxide, 16-9, 16-10, 16-19

1-12