Ministry of High Education and Scientific Research

University of Technology
Department of Materials Engineering

STRUCTURE DETERMINATION BY
DIFFRACTION AND SCATTERING

Presented by:

Noor Dawood Salman

Outlines:

1) X-Ray Diffraction, XRD

2) Extended X-Ray Absorption Fine Structure, EXAFS
3) Surface Extended X-Ray Absorption Fine Structure and
Near Edge X-Ray Absorption Fine Structure, SEXAFS/NEXAFS
4) X-Ray Photoelectron and Auger Electron Diffraction, XPD and AED
5) Low-Energy Electron Diffraction, LEED
6) Reflection High-Energy Electron Diffraction, RHEED
 X-Ray Diffraction, XRD

• X-ray diffraction is a powerful nondestructive technique for characterizing crystalline

materials. It provides information on structures, phases, preferred crystal orientations
(texture), and other structural parameters, such as average grain size , crystallinity, strain,
and crystal defects.
• X-Ray Diffraction is a rapid analytical technique primarily used for phase
identification of crystalline materials. It can provide information on unit cell
dimensions.
• XRD peaks are produced by constructive interference of a monochromatic beam of X-
rays scattered at specific angles from each set of lattice planes in a sample. The peak
intensities are determined by the atomic positions within the lattice planes. Consequently,
the XRD pattern is the fingerprint of periodic atomic arrangements in a given material.
 Principle

• Based on the constructive interference of monochromatic x-rays and a crystalline sample in

which the crystalline structure causes a beam of incident x-rays to diffract into many specific
directions.
• The X-rays are produced when the electrons are suddenly decelerated upon collision with the
metal target, and these x-rays are commonly called "Bremsstrahlung or Breaking Radiation".
• If the bombarding electrons have sufficient energy, they can knock an electron out of an inner
shell of the target metal atoms.
• Then the electrons from the higher states drop down to fill the vacancy, emitting x-ray photons
with precise energies determined by the electron energy levels.
These rays are called characteristic x-rays.
 Bragg's Law

It explains the relationship between an

x-ray light shooting into, and it is
reflected off from the crystal surface.
The law states that when an x-ray is an
incident onto a crystal surface, with an
angle of incidence θ, it will reflect with
the same angle of scattering θ.
When the path difference (d) is a whole Where,
number (n), of wavelength (λ), λ = wavelength of the x-ray.
d = spacing of the crystal layers(path difference).
constructive interference will occur. θ = incident angle.
n = integer.
 X-Ray Diffraction pattern

This is a typical x-ray diffraction pattern.

The pattern consists of a series of peaks
with various intensities.
The spectrum shows peak intensity vs .measured
diffraction angle
Each peak or reflection in the diffraction pattern
corresponds to the x-rays diffracted from a
specific set of planes in the specimen.
 Applications of XRD

• Distinguishing between crystalline and amorphous materials

• Determination of the structure of crystalline materials
• Determination of electron distribution within the atoms and
throughout the unit cell
• Determination of the orientation of single crystals
• Determination of texture of poly grained materials
• Measurement of strain and small grain size…..etc
Advantages & Disadvantages of XRD
Compared to Other Methods
Advantages
• X-Rays are the least expensive, the most convenient & the most
widely used method to determine crystal structures.
• X-Rays are not absorbed very much by air, so the sample need not be
in an evacuated chamber.
Disadvantages
• X-Rays do not interact very strongly with lighter elements.
 Extended X-Ray Absorption Fine Structure, EXAFS
• EXAFS is a nondestructive, element-specific spectroscopic technique with
application to all elements from lithium to uranium. It is employed as a direct
probe of the atomic environment of an X-ray absorbing element and provides
chemical bonding information. Although EXAFS is primarily used to determine
the local structure of bulk solids (e.g., crystalline and amorphous materials), solid
surface, and interfaces.
• The EXAFS spectrum results from the constructive and destructive interference
between the outgoing and incoming photoelectron waves at the absorbing atom.
The interference gives rise to the modulatory structure (i.e., peaks and valleys) of
the X-ray absorption versus incident X-ray energy
• An EXAFS experiment involves the measurement of the X-ray photo absorption
of a selected element as a function of energy above its core-shell electron binding
energy.
 Basic Principles

• Both inner-shell (K and L) and outer-shell

(M, N, etc.) electrons can be excited by the
absorption of X rays and by the inelastic
scattering of electrons. In either instance, at
an electron binding energy characteristic of
an element in a sample absorption occurs and
a steeply rising absorption edge is observed.
For example , molybdenum exhibits an X-ray
absorption edge at 20,000 eV, which is the 1s
electron binding energy (K edge)
 Surface Extended X-Ray Absorption Fine Structure and Near
Edge X-Ray Absorption Fine Structure, SEXAFS/NEXAFS

• SEXAFS is a research technique providing the most precise values obtainable for
adsorbate -substrate bond lengths, plus some information on the number of nearest
neighbors (coordination numbers).
• NEXAFS has become a powerful technique for probing the structure of molecules
on surfaces. Observation of intense resonances near the X-ray absorption edge can
indicate the type of bonding. The energies of resonances to estimate the
intermolecular bond length.
• The principles and analysis of EXAFS and SEXAFS are the same
 X-Ray Photoelectron and Auger Electron Diffraction, XPD and AED

• X-ray Photoelectron Diffraction (XPD) and Auger Electron Diffraction (AED) are
well-established techniques for obtaining structural information on chemically
specific species in the surface regions of solids.
• Auger Electron Spectroscopy (AES), is a widely used technique to investigate
the composition of surfaces.

Ultrahigh-vacuum conditions are

necessary to maintain surface
cleanliness
XPD given some of the advantages it has over AED, such as reduced sample degradation for
ionic and organic materials, quantification of chemical states and, for conditions usually
encountered at synchrotron radiation facilities, its dependence on the polarization of the X rays.
 XRD XPD

Range of element All, but not specific , Low z element may difficult to detect All, except H and He
Sample requirement Any material , greater than 0.5cm although Smaller with micro Primary single crystal , but also textured
focus Samples
main information give information about phase, defects & 'structure Give elemental information , chemical
state & structure
Depth & width depth probed is 10 Mm & width probed in mm Depth propped is 3nm & width propped is
probed 150 Mm
Types of solid sample Crystalline Single crystal

Vacuum needed? not need vacuum Need vacuum

Depth profiling Normally no, but this Can be achieved Yes , to 30 A beneath the surface

Technique & used In XRD a collimated beam of x-ray with wave length 0.5 -2A is In XPD a single crystal or textured
beam incident on a specimen and is diffracted by the Crystalline polycrystalline sample is struck by photon
phases in a specimen according to braggs Low 2d sin. or electrons to produce outgoing
;where d= distance Between at pl.) electrons that contain surface chemical
and structural information
main use identification of Crystalline phases, determination of strain, To determine adsorption sites and thin
and Crystalline orientation and size, accurate determination of film growth modes in chemically specific
atomic arrangement ; special use: film manner
thickness
Low-Energy Electron Diffraction, LEED

• Low-energy electron diffraction (LEED) is a technique for the

determination of the surface structure of single-crystalline materials by
bombardment with a collimated beam of low energy electrons (20–200
eV)

High surface sensitivity

Easy information on symmetry
and shape of surface unit-cell
Atomic structure can be retrieved
with high accuracy
 Basic Principles

• LEED is one of the most informative technique for determining the

arrangement of atom close to the surface. Beam of electrons of a well-
defined low energy (typically in the range 20 - 200 eV) corresponding to
wave lengths in the range 100 to 400 pm is incident normally on the
sample.
• The diffracted electrons can be observed by a fluorescent screen after
energy-filtering grids, which selects only the electrons with the same
kinetic energy as the primary electrons.
 diffraction patterns:
• If an ED is made of an amorphous structure (i.e. no crystalline formation)
then one simply gets a central bright spot.
• If an ED is made of field of many crystals, some of which are oriented at
the Bragg’s angle while others are not, a pattern with well-defined
concentric rings, but not spots, will result.
 Reflection High-Energy Electron Diffraction, RHEED
• Reflection High-Energy Electron Diffraction (REED) is a technique for probing
the surface structures of solids in ultrahigh vacuum (UHV). Since it is a
diffraction based technique, it is sensitive to order in solids and is ideally suited
for the study of clean, well-ordered single-crystal surfaces.
•Reflected the high energy of the electrons would result In high
penetration depth . However , because of the glancing angle of
incidence ,a few atomic layers are only probed . This is the reason
of the high surface sensitivity of RHEED.

• Upon reflection ,electrons diffract ,forming a

diffraction pattern that depends on the structure and the
morphology of the probed surface.
•Can be used during film growth
 Principles
• The spots form a characteristic RHEED pattern depend on the morphology and
roughness of the sample surface. Therefore, RHEED is a powerful tool for in-situ
analysis of thin film deposition. As the RHEED intensity depends on the film
roughness, the growth process leads to characteristic intensity oscillations of the
RHEED spots during the growth process with a single oscillation usually
corresponding to the completion of a single monolayer.
 LEED RHEED

Range of element all, but not element specific All, but not chemical specific

Depth propped Depth propped 4-20 A Depth propped 2-100 A

Energy of beam Beam of electrons in the energy range Beam of high energy electrons in the energy range
5-50 Kev

Lateral resolution Typical beam size , 0.1 mm 200Mm * 4mm

Best system ~ 10 Mm In special cases 0.3 nm * 6nm

Sample requirements Single crystal of conductors and semi conductors, Usually single crystal conductor or semiconductor
insulators and poly crystalline sample under surfaces
special circumstance
Main uses Analysis of surface crystallography and Monitoring surface structures , especially during
microstructure , surface clean lines thin film epitaxial growth , can distinguish 2 and 3
dimensional defect
Destructive No, expect in special cases of e- beam damage No, except for electron – sensitive materials
RHEED pattern taking during film growth
 choice of X-ray target
Copper has the shortest wave length. Good resolution of peaks (Resolution is
dependent on the radiation used) Cu, are true, having a wavelength approximating
inter-bond distances is best for structure determination/Brage Scatter. The
preference for copper is simply due to the fact that, out of the candidate metals, it
has the shortest wavelength above 1 Angstrom. If one considers the fact that the
anode needs to be metallic (to conduct electrons) and have a high enough melting
point (as >kW is generated), the choice narrows down. If the wavelength is below 1
Angstrom as is the case for molybdenum, there will be loss in resolution as the
diffraction will tend to lower angles. However, copper is not necessarily the best
choice for every type of analysis. With copper you get Fe, Mn, etc. fluorescence.
The use of cobalt is the best way to get round this problem. Chromium tends to be
good for XRD of complex organic compounds and for stress measurements on
steels.
THANK YOU