Outline

What is XPS?
Background
Principle
Instrumentation
Analysis of XPS Data
Applications
Facility at Ohio University
Summary

Center for Electrochemical Engineering Research, Ohio University 2

 What is XPS?

X-ray photoelectron spectroscopy (XPS) is also

XPS is a surface analytical technique

Widely used to determine the chemical information
in addition to elemental information of the samples
Related techniques are Auger electron
spectroscopy (AES) and Ultra-violet photoelectron
spectroscopy (UPS)

Center for Electrochemical Engineering Research, Ohio University 3

 Background

In 1887, Heinrich Hertz observed the photoelectric effect

In 1905, Albert Einstein explained the photoelectric effect with a simple

mathematical description, which lead to Nobel Prize in Physics

E k = h - Eb
Ek and Eb is the kinetic energy and binding energy of the photoelectron,
respectively, and h is the energy of the incident beam

Center for Electrochemical Engineering Research, Ohio University 4

 Background

Prof. Kai Siegbahn from the University of

Uppsala, Sweden, utilized the photoelectric
effect to develop an analytical technique
During the mid-
and his co-workers developed the analytical
technique known as X-ray photoelectron
spectroscopy (XPS)
He coined the term Electron spectroscopy
for chemical analysis (ESCA)
In 1981, Prof. Kai Siegbahn was awarded
the Nobel Prize in Physics for the
development of the XPS technique

Center for Electrochemical Engineering Research, Ohio University 5

 Principle
Conducting Sample

Ek = h Eb sample

is the work
sample
function of the sample

Work function is the

energy difference
between Fermi level
and Vacuum level

University of Illinois at Urbana-Champaign [groups.mrl.illinois.edu/nuzzo/0-ppt/XPS Class 99.pps]

Center for Electrochemical Engineering Research, Ohio University 6

 Principle
Analysis of sample with the XPS instrument
e-

Sample Spectrometer
Free Electron Energy
Ek (1s) Ek (1s)
Vacuum Level, Ev
hv sample spec

Fermi Level, Ef

Eb (1s)
E1s

Ek = h Eb spec

University of Illinois at Urbana-Champaign [groups.mrl.illinois.edu/nuzzo/0-ppt/XPS Class 99.pps]

Center for Electrochemical Engineering Research, Ohio University 7

 Instrumentation
Photo of a XPS Instrument

Kratos Axis Ultra model in Surface Science Western Laboratory

at The University of Western Ontario
Center for Electrochemical Engineering Research, Ohio University 8
 Instrumentation
Schematic for a XPS instrument
Computer
System
Hemispherical Energy Analyzer

Outer Sphere Magnetic Shield

Inner Sphere Analyzer Control

Electron Multi-Channel Plate

Lenses for Energy
Optics Electron Multiplier
Adjustment
(Retardation) Resistive Anode
X-ray Encoder
Source Position Computer
Lenses for Analysis Position Address
Area Definition Converter
Position Sensitive
Detector (PSD)
Sample
5 4 .7
University of Illinois at Urbana-Champaign [groups.mrl.illinois.edu/nuzzo/0-ppt/XPS Class 99.pps]

Center for Electrochemical Engineering Research, Ohio University 9

 Instrumentation
Ultra high vacuum (UHV) chamber

Typical pressure: 10-9 10-11 torr

Reason to have UHV condition
Maintain sample surface integrity
Minimize scattering of the photoelectrons
Maximize mean free path of the photoelectrons
Helpful to use tungsten filament or other
electron source in the X-ray source cathode

Center for Electrochemical Engineering Research, Ohio University 10

 Instrumentation
Ultra high vacuum (UHV) chamber

XPS instrument with facility to perform electrochemical experiments

C. J. Corcoran, H. Tavassol, M. A. Rigsby, P. S. Bagus, and A. Wieckowski, Journal of Power Sources 195 (2010) 7856-7879.

Center for Electrochemical Engineering Research, Ohio University 11

 Instrumentation
X-ray source
Energy of the x-ray beam
depends on the anode material
in the x-ray source
High intensity x-ray beam with a
narrow line width gives best
spectroscopic result
Commonly Mg K (1253.6 eV)
and Al K (1486.6 eV) are used
Dual-anode x-ray source
(Al/Mg, Mg/Zr, and Al/Zr) are
also used
X-ray beam lines from
synchrotron facility can be used
for XPS analysis
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 Instrumentation
X-ray source

Diameter of X-ray beam ranges

from 5 mm to 1-5 µm
X-ray penetration depth ~ 1 µm
Sampling depth depends on
wavelength of the x-ray beam
and sample material
For Al K , sampling depth is
generally 10 nm and 10 atomic
layers for heavier elements

D. R. Vij, Handbook of Applied Solid State Spectroscopy, Springer, New York, 2006.

Center for Electrochemical Engineering Research, Ohio University 13

 Instrumentation
Electron energy analyzer

Cylindrical mirror analyzer (CMA)

Concentric
hemispherical
analyzer (CHA) Used in XPS and AES instruments

University of Western Ontario [mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]

Center for Electrochemical Engineering Research, Ohio University 14

 Instrumentation
Samples for the XPS analysis
Sample size depends on the instrument

Any solid sample (conducting and non-conducting) can be

analyzed
Sample has to be compatible in the ultra high vacuum (10-9
torr) condition
Sample preparation
Degrease before loading in the holder
Use conductive tape for attachment
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 Analysis of XPS Data
Example of XP spectrum

XPS Spectra, CasaXPS www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf

Center for Electrochemical Engineering Research, Ohio University 16

 Analysis of XPS Data
Identify Auger peaks in XP spectrum

Cu XP spectra illustrating the shift in auger peak positions with the change from Mg
to Al anodes in the X-ray source

D. R. Vij, Handbook of Applied Solid State Spectroscopy, Springer, New York, 2006.

Center for Electrochemical Engineering Research, Ohio University 17

 Analysis of XPS Data
Peak quantification in XP spectrum

XPS Spectra, CasaXPS www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf

Center for Electrochemical Engineering Research, Ohio University 18

 Chemical Effects in XPS

Chemical shift:
change in binding energy of a core electron of an element
due to a change in the chemical bonding of that element

increase in
Withdrawal of valence electron charge
Binding energy

decrease in
Addition of valence electron charge
Binding energy

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 Chemical Effects in XPS

Charges are withdrawn from Ti to

form Ti4+, which results in higher
Binding energy for the Ti 2p orbitals

Chemical shift information very

powerful tool for functional group,
chemical environment, and
oxidation state
University of Western Ontario [mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]

Center for Electrochemical Engineering Research, Ohio University 20

 Chemical Effects in XPS
Chemical shift for Gold (Au) 4f7/2 peak

University of Western Ontario [mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]

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 Chemical Effects in XPS
Curve fitting for Carbon 1s peak

C 1s region XP spectrum for polymethylmethacrylate (PMMA)

D. R. Vij, Handbook of Applied Solid State Spectroscopy, Springer, New York, 2006.

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 Depth Profile
Examples of XPS spectrum
Ar+ sputtering of the sample results in layer-by-layer
removal of the sample using Ion gun

XP spectrum of the sample surface was collected after

each step of Ar+ sputtering
XPS Spectra, CasaXPS www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf

Center for Electrochemical Engineering Research, Ohio University 23

 Depth Profile
Multi layer SiO / TiO2 sample

The set of O 1s spectra measured during a depth profiling experiment

XPS Spectra, CasaXPS www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf

Center for Electrochemical Engineering Research, Ohio University 24

 Depth Profile
Architectural Glass Coating sample

Atomic concentration for the elements found in the Architectural Glass

Coating sample from depth profiling experiment
University of Western Ontario [mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]

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 Strengths of X-ray Photoelectron Spectroscopy

Surface sensitive technique (top 10 nm)

Chemical state identification on surfaces
Identification of all elements except for H and He
Quantitative analysis, including chemical state
differences
Applicable for a wide variety of materials, including non
conducting samples (paper, plastics, and glass)
Depth profiling with matrix-level concentrations
Oxide thickness measurements

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Limitations for X-ray Photoelectron Spectroscopy

Detection limits typically ~ 0.1% atomic

Smallest analytical area ~ 10 µm diameter
Limited organic information (short-range bonding only)
Samples must be ultra high vacuum compatible
Samples that decompose under X-ray irradiation
cannot be studied

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 Applications

Analyzing the composition of powders and debris

Determining contaminant sources
Examining polymer functionality before and after processing
Bonding and adhesion issues
Obtaining depth profiles of thin film stacks (both conducting and
non-conducting) for matrix level constituents
Identifying stains and discolorations
Characterizing cleaning processes
Assessing the differences in oxide thickness between samples

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 Applications
Industries using XPS technique

Aerospace Pharmaceutical
Automotive Photonics
Biomedical / Polymer
Biotechnology
Semiconductor
Data Storage
Solar Photovoltaics
Defense
Telecommunications
Displays
Electronics
Lighting

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 Applications
Analysis of Pigment from Mummy Artwork
Pb3O4
Egyptian Mummy
2nd Century AD
World Heritage Museum
University of Illinois

PbO2

C
O
150 145 140 135 130
Binding Energy (eV)

P Pb
b
N XPS analysis showed
Ca that the pigment used
Na
Cl Pb
on the mummy
wrapping was Pb3O4
rather than Fe2O3
500 400 300 200 100 0
Binding Energy (eV)
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