X-ray Diffraction (XRD)

What is Diffraction?
X-ray Diffraction (XRD)
X-ray Diffraction (XRD): Generation of X-ray
Characteristics X-ray
Bragg’s law

2d sin  = n 
Bragg’s law
A diffracted beam may be defined as a beam
composed of a large number of scattered rays
mutually reinforcing each other

Scattering
Interaction with a single particle

Diffraction
Interaction with a crystal
Bragg’s law
❑ Diffraction occurs when light is scattered by a periodic array with long-range order,
producing constructive interference at specific angles

❑ The electrons in an atom coherently scatter light.

– We can regard each atom as a coherent point scatterer
– The strength with which an atom scatters light is proportional to the
number of electrons around the atom.

❑ The atoms in a crystal are arranged in a periodic array and thus can diffract light.
❑ The wavelength of X rays are similar to the distance between atoms.
❑ The scattering of X-rays from atoms produces a diffraction pattern, which contains
information about the atomic arrangement within the crystal
❑ Amorphous materials like glass do not have a periodic array with long-range order,
so they do not produce a diffraction pattern
 The powder diffractometers geometry

Detector
X-ray
tube

w  2

• The incident angle, w, is defined between the X-ray source and the sample.
• The diffracted angle, 2, is defined between the incident beam and the detector angle.
• The incident angle w is always ½ of the detector angle 2 .
• In a :2 instrument (e.g. Rigaku RU300), the tube is fixed, the sample rotates at  °/min
and the detector rotates at 2 °/min.
• In a : instrument (e.g. PANalytical X’Pert Pro), the sample is fixed and the tube rotates at
a rate - °/min and the detector rotates at a rate of  °/min.
 XRD of a single crystal
❑ Produce only one family of peaks in the diffraction pattern.

2

At 20.6 °2, Bragg’s law
fulfilled for the (100) planes,
producing a diffraction peak.
The (110) planes would diffract at 29.3
°2; however, they are not properly
aligned to produce a diffraction peak
(the perpendicular to those planes does
not bisect the incident and diffracted
beams). Only background is observed.
The (200) planes are parallel to the (100)
planes. Therefore, they also diffract for this
crystal. Since d200 is ½ d100, they appear at
42 °2.
 XRD of a polycrystalline material
❑ all possible diffraction peaks should be observed.

2 2 2

➢ For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).

➢ Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of
crystallites, not just one or two.
Example: Analysis of X-ray diffraction pattern
of single phase

2(˚) d (Å) (I/I1)*100

27.42 3.25 10
31.70 2.82 100
45.54 1.99 60
53.55 1.71 5
56.40 1.63 30
Intensity (a.u.)

65.70 1.42 20
76.08 1.25 30
84.11 1.15 30
89.94 1.09 5

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Example: Analysis of X-ray diffraction pattern of single phase

Procedure

• Note first three strongest peaks at d1, d2, and d3

• In the present case: d1: 2.82; d2: 1.99 and d3: 1.63 Å
• Search JCPDS manual to find the d group belonging
to the strongest line: between 2.84-2.80 Å
• There are 17 substances with approximately similar
d2 but only 4 have d1: 2.82 Å
• Out of these, only NaCl has d3: 1.63 Å
• It is NaCl

Caution: It could be much more tricky if the sample is oriented or textured or your goniometer is not
calibrated
 Intensity of the diffraction peaks
Structure Factor

N
Fhkl =  f n e 2 i ( hun + kvn + lwn ) Intensity of the diffracted beam  |F|2

1
− h,k,l : indices of the diffraction plane under consideration
− u,v,w : co-ordinates of the atoms in the lattice
− N : number of atoms
− fn : scattering factor of a particular type of atom

Bravais Lattice Reflections possibly present Reflections necessarily absent

Simple All None

Body Centered (h+k+l): Even (h+k+l): Odd

Face Centered h, k, and l unmixed i.e. all h, k, and l: mixed

odd or all even
 Systematic Absences
Permitted Reflections

Simple Cubic (100), (110), (111), (200), (210), (211),

(220), (300), (221) ………
BCC (110), (200), (211), (220), (310), (222)….
FCC (111), (200), (220), (311)…..
 Structure
➢ Subatomic level Electronic structure of
individual atoms that defines interaction
among atoms (interatomic bonding).

➢ Atomic level Arrangement of atoms in

materials (for the same atoms can have
different properties, e.g. two forms of carbon:
graphite and diamond).

➢ Microscopic structure Arrangement of small

grains of material that can be identified by
optical microscopy.

➢ Macroscopic structure Structural elements

that may be viewed with the naked eye
Structure. Disclaimer: The above material is purely for teaching purpose
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 Interfaces in Thin films
❑Different techniques have been developed to prepare high-quality
metal oxide films, such as molecular beam epitaxy (MBE).

❑In most cases both the grown film and the metal substrate
experience strain due to the lattice mismatch

Thin Film

Substrate

The sources of internal film stress include both the mismatch in

thermal expansion coefficient and mismatch in lattice parameter
between film and substrate.

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 Interface Lattice Strains
❑ For many applications nearly matched
lattices are desired to minimize defects and
increase electron mobility.

❑ As the mismatch gets larger, the film

material may strain to accommodate the
lattice structure of the substrate. This is the
case during the early stages of film
formation and with materials of the same
lattice structure. The Si-Ge system is an
example.

❑ If strain accommodation is not possible

then dislocation defects at the interface
may form leading to relaxed epitaxy and
the film returns to its original lattice
structure above the interface.

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 Epitaxial Layer
❖A single crystal layer that has been deposited or grown on a
crystalline substrate having the same structural arrangement.

❖A crystalline layer of a particular orientation on top of another

crystal, where the orientation is determined by the underlying
crystal.

❖Homoepitaxial layer
The layer and substrate are the same material and possess the
same lattice parameters.

❖Heteroepitaxial layer
The layer material is different than the substrate and usually
has different lattice parameters.

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 Coherent Interface-without strain
Schematics of strain free coherent interfaces

Matching spacing but with different

Same crystal structure (& lattice
crystal structure.
spacing) but different composition
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 Coherent Interface-strained

Region with Tensile Stresses

Interface

Compressively stressed region

Coherent interface with a small lattice mismatch

Coherency stresses develop in the adjoining crystals

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 Semi-Coherent Interface
❖ Semi-coherent interfaces have an array of dislocations which partially relax the misfit
strains arising from the lattice mismatch across the interface between the two materials

Schematic showing a semi-coherent interface: A series of edge dislocations at a spacing of

D partially relax the misfit strain at the interface (this can be thought of as the interface
breaking up into regions with registry and those with dislocations)
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Incoherent Interface-strained

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 Lattice Mismatch

A useful measure of strain (ε) at the interface between a film

and substrate is the lattice mismatch strain or simply misfit, f,
defined as;

f = [ao(S) - ao(f)]/ao(f);

where ao is the lattice parameter and f and s refer to the film

and substrate, respectively.

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References

1. home.iitk.ac.in/~anandh/E-book/
2. Solid State Physics- Charles Kittel
3. B. D. Cullity- Elements Of X-Ray Diffraction
4. Fundamentals of Materials Science and Engineering- William D.
Callister

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