Method of Experimental Physics

Course No: PH -404

Chapter-5
X-ray diffraction
XRD

©Prof. Dr. M. Mizanur Rahman

 X-rays
➢ X-rays are short wavelength electromagnetic radiations produced by
the deceleration of high energy electrons or by electronic transitions of
electrons in the inner orbital of atoms. X-ray wavelength range: 0.1 to
100 Å.
➢ X-rays were discovered by Wilhelm Roentgen who called them X-rays
because the nature at first was unknown so, x-rays are also called
Roentgen rays. X-ray diffraction in crystal was discovered by Max von
Laue. The wavelength range is 0.01 to about 10 nm.
➢ The penetrating power of X-rays depends on energy also, there are
two types of X-rays.
i) Hard X-rays: which have high frequency and have more energy
ii) Soft X-rays: which have less penetrating and have low energy.
 History of X-ray Diffraction
1895 X-rays discovered by Roentgen

1914 First diffraction pattern of a crystal made by Knipping and von

Laue

1915 Theory to determine crystal structure from

diffraction pattern developed by Bragg.

1953 DNA structure solved by Watson and Crick

Now diffraction improved by computer technology;

methods used to determine atomic structures
and in medical applications
 Production of X-rays
❑ A cathode, heated by a filament through which an electric current is passed,
supplies electrons by thermionic emission.
❑ The high potential difference V maintained between the cathode and a
metallic target accelerates the electrons toward the latter.
❑ The face of the target is at an angle relative to the electron beam, and the x-
rays that leave the target pass through the side of the tube.
❑ The tube is evacuated to permit the electrons to get to the target
unimpeded.
 Characteristic X-ray vs Bremsstrahlung
Characteristic X-rays and Bremsstrahlung are two types of X-ray
radiation generated in different ways.
Characteristic X-rays:
➢ Produced when inner-shell electrons are ejected from an atom
and outer-shell electrons fall into the lower energy level to fill
the vacancy.
➢ Characteristic X-rays have specific energies determined by
the energy difference between the involved electron shells.
➢ Produces sharp, well-defined peaks in the X-ray spectrum.
➢ Commonly used in X-ray crystallography.
Bremsstrahlung:
➢ The term "Bremsstrahlung" is German for "braking
radiation." It occurs when a high-energy electron is
deflected or decelerated by the nucleus of an atom.
➢ A high-speed electron is influenced by the electric field of a
nucleus, causing the electron to lose energy in the form of
an X-ray photon.
➢ Bremsstrahlung X-rays have a continuous spectrum,
covering a range of energies, as a result also known as white
radiation.
➢ Produces a continuous spectrum without well-defined peaks.
➢ Commonly used in medical imaging like X-ray radiography.
 Components of X-ray Diffractometer

1. X-ray source
2. Collimator
3. Monochromator
4. Sample holder
5. Sample
6. Detector
7. Imaging system
 Working principle of X-ray Diffractometer
1. X-ray Source: Typically, a cathode-ray tube (X-ray tube) generates X-rays. These
X-rays have sufficient energy to interact with the crystal lattice of the sample.
2. Collimator: In X-ray diffraction (XRD), a collimator helps to limit the divergence of
the X-ray beam. Its primary purpose is to ensure that only a parallel beam of X-
rays reaches the sample being analyzed. This parallel beam is essential for
obtaining accurate and high-quality diffraction patterns.
3. Monochromator: A monochromator is an optical device that transmits a narrow
band of wavelengths of light or other radiation chosen from a wider range of
wavelengths available at the input. The name is from the Greek roots mono –
‘single’ and chroma-’color’ and the Latin suffix –ator denoting an agent.
4. Sample Holder or Goniometer: The sample holder holds the specimen at a
fixed orientation, and the goniometer allows for precise rotation of the sample,
enabling the collection of diffraction data at different angles.
5. Sample: The material being analyzed, usually a crystalline substance. The X-rays
interact with the crystal lattice, leading to constructive interference patterns that
can be analyzed to determine the crystal structure.
6. Detector: Positioned opposite the sample, the detector captures the diffracted X-
rays. Detectors can be divided into two major categories: Imaging detectors, such
as photographic plates or Xray film and digital detectors like GM or Scintillator
counter.
7. Data Processing System: This system processes the signals from the detector
and converts them into a diffraction pattern. The diffraction pattern is then
analyzed to extract information about the crystal structure.
 How Diffraction work: Bragg’s Law
X-rays diffraction is based on constructive interference of monochromatic x-rays
and a crystalline sample. These x-rays are generated by a cathode ray tube, filtered
to produce monochromatic radiation, collimated to concentrate and directed
towards the sample. The interaction of incident rays with the sample produces
constructive interference when conditions satisfy Bragg’s law.

Bragg’ law states that constructive interference of

the reflected beams emerging from two diffracted
planes will take place if the path lengths of two rays
is equal to whole number of wavelengths.
The path difference between ray 1 and ray 2 is
2dSinθ. For constructive interference,
2dsinθ = nλ
 Derivation of Bragg’s law

Optical path difference between ray 1 & 2 is,

AB + BC = dSinθ + dSinθ
= 2dSinθ

Now, for constructive interference the optical path difference must be equal
to integer multiple of wavelength λ.

Hence, 2dSinθ = nλ

Which is known as Bragg’s law of X-ray diffraction.

 Basic Crystallography

The atoms are arranged in a regular

pattern, and there is as smallest volume
element that by repetition in three
dimensions describes the crystal. The
smallest volume element is called a unit
cell.
Crystals consist of planes of atoms that are
spaced a distance d apart, but can be
resolved into many atomic planes, each
with a different d spacing. The dimensions
of the unit cell is described by three axis; a,
b, c and the angles between them α, β, and γ
are lattice constants which can be
determined by XRD.
Basic Crystallography: Miller Indices (hkl)

❑ Miller indices: the reciprocals

of the fractional intercepts
which the plane makes with
crystallographic axes.

➢ Axial length = 4Å 8Å 3Å
➢ Intercept lengths = 1Å 4Å 3Å
➢ Fractional intercepts = ¼ ½ 1
➢ Miller indices = 4 2 1 (h kl)
Relation between interplanar spacing and Miller indices
Relation between interplanar spacing and Miller indices
 X-ray Diffraction Method
There are generally three X-ray diffraction method for investigating the internal
structures and crystal structures of various solid compounds.
a) Laue Method: A stationary single crystal is irradiated by a range of X-ray
wavelengths. It is again two types.
1)Transmission method & 2) Back reflection method
b) Rotating crystal Method: A single crystal specimen is rotated in a beam of
monochromatic X-rays.
c) Powder Method: A polycrystalline powder specimen is kept stationary in a
beam of monochromatic radiation.
Of these techniques, Laue method is used only for known crystal orientation
measurement.
 Transmission Laue Methods
❖ In the transmission Laue method, the film is placed behind the
crystal to record beams which are transmitted through the crystal.
❖ One side of the cone of Laue reflections is defined by the
transmitted beam. The film intersects the cone, with the diffraction
spots generally lying on an ellipse.
❖ It can be for the study of thin specimens.
❖ Also used in determination of symmetry of single crystals

Laue pattern of an LiF

(100) crystal.
Mo-X-ray tube: Ua = 35
kV; IA = 1 mA Distance
between sample and film:
D = 19 mm Exposure time:
t = 120 min
 Back Reflection Laue method
❖ In the back-reflection method, the film is placed between the x-ray
source and the crystal. The beams which are diffracted in a
backward direction are recorded.
❖ One side of the cone of Laue reflections is defined by the
transmitted beam. The film intersects the cone, with the diffraction
spots generally lying on an hyperbola.
❖ This method is similar to transmission method however, back-
reflection is the only method for the study of large and thick
specimens.
❖ Disadvantage: big crystals are required.
 Von Laue X-ray Diffraction Formulation
Incident x-ray: along direction n ̂
wavelength λ
wave vector k = (2π/λ)nˆ
A scattered wave: direction nˆ′
wavelength λ
wave vector k′ = (2π/λ)nˆ′
Optical path difference between two rays,
d cos + d cos ′ = d ⋅(nˆ − nˆ′)
Now, Condition for constructive interference d ⋅(nˆ − nˆ′) = mλ, for integer m.
Or, d ⋅(k − k ′) = 2πm
The condition d ⋅(k − k ′) = 2πm holds for all possible d.
If d is the real lattice vector R. then,
R ⋅(k − k ′) = 2πm
Equivalently, e^i(k ′− k ).R = 1.
Therefore, (k ′− k ) must be reciprocal lattice vector G for constructive
interference. This is known as Laue condition.
Equivalence of the Bragg and von Laue formulations
The Laue condition can be rewritten as,
G = k ′− k
Or, k = k ′− G
Or, |k|^2= |k ′− G|^2
Or, |k|^2= |k ′ |^2 − 2k ′.G + |G|^2
For elastic scattering (in other word, incoming and
diffracted wave at same frequency for constructive
interference), |k ′|= |k|
Hence,
|k ′ |^2= |k ′ |^2 − 2k ′.G + |G|^2
2k ′ .G = |G|^2
2k ′ *G*Cos(90-θ) = |G|^2
2k ′ *G*Sinθ=|G|^2
2kSinθ=G
2kSinθ = 2πm/d
[d ⋅G= 2πm & d,G same directed]
kdSinθ= πm
(2π/λ)dSinθ= πm
2dSinθ=mλ
Which is the Bragg’s law of diffraction.
Crystal Structure Determination (Cubic Crystal)

From Bragg’s law:

2dSinθ = nλ
 Crystal Structure Determination (Cubic Crystal)
Allowed hkl values for different cubic crystals:
Based on atomic scattering factor (f) and structure factor (F), the allowed values for
different cubic crystal system can be determine.
According to atomic structure factor,

S(hkl)=∑f*exp(-2πi(xh+yk+zl)
Simple Cubic:
one atom per unit cell at (0,0,0).
Hence,
S(hkl)=f*exp(0)=f
Since S is non zero for all values of hkl, hence Bragg’s reflection are allowed for all values
of hkl.
Body Centered Cubic:
Two atoms per unit cell at (0,0,0) & (1/2,1/2,1/2).
Hence, S(hkl)=f(1+exp(-πi(h+k+l))
Here, S(hkl) is non zero, when h+k+l=even
Face Centered Cubic:
Four atoms per unit cell at (0,0,0), (1/2,1/2,0), (1/2,0.1/2) &(0,1/2,1/2).
Hence, S(hkl)=f(1+exp(-πi(h+k)+exp(-πi(k+l)+ exp(-πi(l+h))
Here, S(hkl) is non zero, when hkl all even or all odd.
Crystallite size, Dislocation density & Microstrain
 Crystallite size, Dislocation density & Microstrain

K= Scherrer constant. Typically 0.94 for spherical crystallite with

cubic symmetry 0.89 for spherical crystal without cubic symmetry.
β= FWHM in radian.
 Problems

i. What crystal structure it is?

ii. What is lattice constant of this?

Example 02:
An element show diffraction peak at 2θ: 40, 58,73, 86.8, 100,4, 114.7
i. Determine its crystal structure?
ii. Determine its lattice constant?
 Problems
Example 03
The wavelength of the X-rays is 0.071 nm which is diffracted by a plane of salt
with 0.28 nm as the lattice constant. Determine the glancing angle for the third-
order diffraction. Assume the value of the salt plane intercept is (11∞), and the
given salt is rock salt.

Example 04
Determine the wavelength of the diffraction beam, when a beam of X-ray
having wavelengths in the range 0.2Å to 1Å incident at an angle of 9° with the
cube face of a rock salt crystal (d = 2.814Å).

Example 05
Determine the crystalline size, dislocation density and microstrain for a
nanoparticle whose most intense peak occurred at 44.9588° and corresponding
FWHM value is 0.2378.