Chhatrapati Shahu Ji Maharaj University

(Formerly Kanpur University)

Pre -Ph.D. Course Work 2021

Department of Physics
Topic: Experimental Tools and Techniques

Lecture 1: Principle and Applications of Powder X-Ray Diffractometer

Lecture by: Dr.Anju Dixit

 Outlines

1. Introduction to X-Rays
2. Principle of X-Ray Diffraction
3. Bragg’s Law
4. X-ray Diffractometer
5. Types of X-Ray radiation
6. X-Ray Diffraction Methods
7. Applications of Powder X-Ray Diffraction
 Experimental tools and Techniques

S.No. Title of the Lecture Lecture No.

1 Principle and Application of Powder X-Ray Lecture 1
Diffractometer
2 SEM and Energy Dispersive X-Ray Analysis Lecture 2

3 TEM Lecture 3

4 AFM and STM Lecture 4

5 Spectrometer ( IR and UV Visible) Lecture 5

FT-IR Spectrometer
 Introduction

1.X-rays were discovered in 1895 by the German physicist

Wilhelm Conrad Röntgen.

2.Electromagnetic radiation described as having packets of

energy, or photons. The energy of the photon is related to its
frequency by the following formula: E = hν (E = hc/ λ )

3.Electromagnetic radiation can be expressed in terms of energy,

wavelength, or frequency.
The entire range (electromagnetic spectrum) is given by radio waves,
microwaves, infrared radiation, visible light, ultra-violet radiation, X-rays,
gamma rays in the increasing order of frequency and decreasing order of
wavelength. The type of radiation and their frequency and wavelength ranges
are as follows:
Type of Radiation Frequency Range (Hz) Wavelength Range

gamma-rays 1020 – 1024 < 10-12 m

x-rays 1017 – 1020 1 nm – 1 pm

ultraviolet 1015 – 1017 400 nm – 1 nm

visible 4 – 7.5*1014 750 nm – 400 nm

near-infrared 1*1014 – 4*1014 2.5 μm – 750 nm

infrared 1013 – 1014 25 μm – 2.5 μm

microwaves 3*1011 – 1013 1 mm – 25 μm

radio waves < 3*1011 > 1 mm

 X-Ray Diffraction
X-rays are electromagnetic radiation with wavelengths between 1
pm to 1 nm. The wavelength of X-rays is on an atomic level and is
much smaller than that of visible light (400 nm to 750 nm).

Since X-rays have a smaller wavelength than visible light, they

have higher energy and are more penetrative. Its ability to
penetrate matter, however, is dependent on density of the matter.
Therefore, X-rays are useful in exploring structures of atoms.
X-Ray Crystallography is a technique used for identifying the
atomic and molecular structure of a crystal, in which the
crystalline atoms cause a beam of incident X-rays to diffract into
many specific directions. This forms a pattern, this type of pattern
is called the X-ray diffraction pattern
 Interference
X-ray diffraction, a phenomenon in which the atoms of a crystal, by virtue of
their uniform spacing, cause an interference pattern of the waves present in an
incident beam of X rays. The atomic planes of the crystal act on the X rays in
exactly the same manner as does a uniformly ruled grating on a beam of light.

Because X-rays are bundles of separate waves, each wave can interact with on
another either constructively or destructively. The interaction between waves is
called interference. If waves are in phase meaning that each of their crests and
troughs occur exactly at the same time, then the waves will stack together to
produce a resultant wave that has a higher amplitude and results in the
constructive interference.

If they waves are out of phase, then destructive interference occurs and the
amplitude of the resultant wave will be reduced. If waves are exactly out of
phase by a multiple of n/(2*lambda) then there will be complete destructive
interference and the resultant wave has no amplitude, meaning that it is
completed destroyed.
 Principle of X-Ray Diffraction
The atomic planes of a crystal cause an incident beam of X-rays
to interfere with one another as they leave the crystal. The
phenomenon is called X-ray diffraction. And scattering of X-
rays by the atoms of a crystal that produces an interference
effect so that the diffraction pattern gives information on the
structure of the crystal or the identity of a crystalline substance.

So X-ray diffraction is based on constructive interference of

monochromatic x-rays and a crystalline sample. Or X-rays
are relatively short-wavelength EM radiation and can exhibit
wave characteristics such as interference when interacting
with correspondingly small objects.
 Bragg’s Law

Bragg's law is a special case of diffraction, which determines

the angles of coherent and incoherent scattering from a crystal
lattice. When X-rays are incident on a particular atom, they
make an electronic cloud move like an electromagnetic wave.
When the X-ray is incident onto a crystal surface, its angle of
incidence, θ, will reflect with the same angle of scattering, θ.
And, when the path difference, d is equal to a whole number,
n, of wavelength, constructive interference will occur.
Bragg's Law can easily be derived by considering the conditions
necessary to make the phases of the beams coincide when the
incident angle equals to reflecting angle.

The rays of the incident beam are always in phase and parallel up to
the point at which the top beam strikes the top layer at atom z.

The second beam continues to the next layer where it is scattered

by atom B. The second beam must travel the extra distance
AB + BC if the two beams are to continue traveling adjacent and
parallel.

This extra distance must be an integral (n) multiple of the

wavelength ( ) for the phases of the two beams to be the same:

nλ = AB +BC----------------------------------------------(1)
 Recognizing d as the hypotenuse of the
right triangle ABZ, we can use
trigonometry to relate d and to the
distance (AB + BC).

The distance AB is opposite θ So,

AB = d sin θ----------------------------( 2)

Because AB = BC eq. (1) becomes,

nλ = 2AB ----------------------------( 3 )

Substituting eq. (2) in eq. (3) we have,

nλ = 2 d sin θ ------------------------( 4 )

So the principle is that when a beam of X-rays of wavelength λ enters a crystal, the
maximum intensity of the reflected ray occurs when sin θ = nλ/2d, where θ is the
complement of the angle of incidence, n is a whole number, and d is the distance between
layers of atoms.
X-ray Diffractometer
 Working of X-ray Diffractometer
X-ray diffractometers consist of three basic elements: an X-ray tube, a
sample holder, and an X-ray detector. X-Rays are generated in a cathode
ray tube by heating a filament to produce electrons, accelerating the
electrons toward a target (tungsten) by applying a voltage, and
bombarding the target material with electrons.

When electrons have sufficient energy to dislodge inner shell electrons

of the target material, characteristic X-ray spectra are produced.

These spectra consist of several components, the most common being

Kα and Kβ. Kα consists, in part, of Kα1 and Kα2. Kα1 has a slightly shorter
wavelength and twice the intensity as Kα2. The specific wavelengths are
characteristic of the target material (Cu, Fe, Mo, Cr).
Filtering, by foils or crystal monochrometers, is required to produce monochromatic X-
rays needed for diffraction. Kα1and Kα2 are sufficiently close in wavelength such that a
weighted average of the two is used.

Copper is the most common target material for single-crystal diffraction, with CuKα
radiation = 1.5418Å. These X-rays are collimated and directed onto the sample. As the
sample and detector are rotated, the intensity of the reflected X-rays is recorded.

When the geometry of the incident X-rays impinging the sample satisfies the Bragg
Equation, constructive interference occurs and a peak in intensity occurs. A detector
records and processes this X-ray signal and converts the signal to a count rate which is
then output to a device such as a printer or computer monitor.

The dominant effect that occurs when an incident beam of monochromatic X-rays
interacts with a target material is scattering of those X-rays from atoms within the
target material.

In materials with regular structure (i.e. crystalline), the scattered X-rays undergo
constructive and destructive interference. This is the process of diffraction. The
diffraction of X-rays by crystals is described by Bragg’s Law,
nλ = 2 d sin θ.
The directions of possible diffractions depend on the size and shape of the
unit cell of the material. The intensities of the diffracted waves depend on
the kind and arrangement of atoms in the crystal structure.

However, most materials are not single crystals, but are composed of many
tiny crystallites in all possible orientations called a polycrystalline
aggregate or powder.

When a powder with randomly oriented crystallites is placed in an X-ray

beam, the beam will see all possible interatomic planes. If the experimental
angle is systematically changed, all possible diffraction peaks from the
powder will be detected.

X-rays are generated via interactions of the accelerated electrons with

electrons of tungsten nuclei within the tube anode. There are two types of
X-ray generated: characteristic radiation and bremsstrahlung radiation.
Electrons traveling from the filament (cathode) to the target (anode)
convert a small percentage (1%) of their kinetic energy into x-ray photons
by the formation of bremsstrahlung and characteristic radiation.
 BREMSSTRAHLUNG RADIATION

Bremsstrahlung interactions, the primary source of x-ray photons from an x-ray

tube, are produced by the sudden stopping, breaking or slowing of high-speed
electrons at the target. When the electrons from the filament strike the tungsten
target, x-ray photons are created if they either hit a target nucleus directly (rare)
or their path takes them close to the nucleus.

If a high speed electron hits the nucleus of a target atom, all its kinetic energy is
transformed into a single x-ray photon. (Total absorption has occurred). Thus,
the energy of the resultant photon (keV) is numerically equal to the energy of
the electron. This in turn is equal to the kilovoltage applied across the x-ray
tube at the instant of its passage.
 CHARACTERISTIC RADIATION

Characteristic radiation occurs when an electron from the filament displaces

an electron from an inner-shell of the tungsten target atom, thereby ionizing
the atom.

When this happens, another electron in an outer-shell of the tungsten atom is

quickly attracted into the void in the deficient inner-shell.

When the displaced electron is replaced by the outer-shell electron, a photon

is emitted with an energy equivalent to the difference in the two orbital
binding energies.
 X-Ray Diffraction Methods

There are three diffraction methods by which we can obtain the

information about crystal structures:

 Laue Diffraction method

 Rotating crystal Diffraction method

 Powder Diffraction method

 Laue Diffraction method
The Laue method is a single crystal diffraction method. The
discovery of the phenomenon of crystal diffraction was obtained
for the first time by the Laue method.

The method requires a polychromatic beam, i.e. the full spectrum

of x-ray wavelengths. The single crystal placed in the
polychromatic beam diffracts in many different directions.

The resulting Laue diffraction pattern depends on the orientation

of the crystal. Thus the Laue method is ideal to detect the
orientation of a single crystal, i.e. to find the directions of the
translation vectors of the unit cell.
Laue Diffraction method
 Laue Diffraction method
A single crystal is mounted on a rotating table which enables the crystal to be
rotated through certain known angles and maintained stationary with respect
to a beam of X-rays of different wavelengths.

The crystal selects out and diffracts those discrete values of λ, for which
crystal planes exist, of spacing d and glancing angle θ satisfying Bragg’s
equation:
nλ=2dsin(θ)

A narrow, parallel beam is collimated on the crystal. Photographic films are

placed either to receive the transmitted or reflected beams.

The resultant pattern consists of a series of sharp well defined spots. These are
indicative of a perfect crystal structure, whereas broken, extended spots
indicate lattice distortion and imperfections in the crystal.
 Laue Diffraction method
Single crystal placed on a three-axis goniometer in front of
narrow beam of x-rays

X-rays are not monochromatic

2θ and d remain fixed for each set of planes (only λ is varied)

 Each set diffracts that particular λ which satisfies the Bragg

equation for it

 Each diffracted beam has a different λ

 Incident beam passes through photographic film, hits the

crystal, and is back-reflected towards the film
 Rotating crystal Diffraction method
In the rotating crystal method, a single crystal is mounted with an axis
normal to a monochromatic x-ray beam.

A cylindrical film is placed around it and the crystal is rotated about the
chosen axis. As the crystal rotates, sets of lattice planes will at some point
make the correct Bragg angle for the monochromatic incident beam, and at
that point a diffracted beam will be formed.
Lattice constant of the crystal can be determined by means of this method;
for a given wavelength if the angle θ at which a reflection occurs d hkl
known, is can be determined.

The reflected beams are located on the surface of imaginary cones. By

recording the diffraction patterns (both angles and intensities) for various
crystal orientations; one can determine the shape and size of unit cell as well
as arrangement of atoms inside the cell.
 Powder Diffraction method
It is a scientific technique using X-Ray , neutron, or electron diffraction on
powder or microcrystalline samples for structural characterization of materials. An
instrument dedicated to performing such powder measurements is called a powder
diffractometer.

Powder diffraction stands in contrast to single crystal diffraction techniques, which work
best with a single, well-ordered crystal. If a powdered specimen is used, instead of a single
crystal, then there is no need to rotate the specimen, because there will always be some
crystals at an orientation for which diffraction is permitted. Here a monochromatic X-ray
beam is incident on a powdered or polycrystalline sample. This method is useful for samples
that are difficult to obtain in single crystal.

The powder method is used to determine the value of the lattice parameters accurately.
Lattice parameters are the magnitudes of the unit vectors a, b and c which define the unit cell
for the crystal. For every set of crystal planes, by chance, one or more crystals will be in the
correct orientation to give the correct Bragg angle to satisfy Bragg's equation. Every crystal
plane is thus capable of diffraction. Each diffraction line is made up of a large number of
small spots, each from a separate crystal
 Powder Diffraction method

A diffractometer produces waves at a known frequency, which is

determined by their source. The source is often x-rays, because they are
the only kind of energy with the correct frequency for inter-atomic-
scale diffraction. However, electrons and neutrons are also common
sources, with their frequency determined by their de Broglie
wavelength.

When these waves reach the sample, the atoms of the sample act just
like a diffraction grating, producing bright spots at particular angles.
By measuring the angle where these bright spots occur, the spacing of
the diffraction grating can be determined by Bragg's law Because the
sample itself is the diffraction grating, this spacing is the atomic
spacing .
 Powder Diffraction method
The distinction between powder and single crystal diffraction is the
degree of texturing in the sample. Single crystals have maximal
texturing, and are said to be anisotropic

In contrast, in powder diffraction, every possible crystalline orientation

is represented equally in a powdered sample, the isotropic case. PXRD
operates under the assumption that the sample is randomly arranged.

Therefore, a statistically significant number of each plane of the crystal

structure will be in the proper orientation to diffract the X-rays.
Therefore, each plane will be represented in the signal. In practice, it is
sometimes necessary to rotate the sample orientation to eliminate the
effects of texturing and achieve true randomness.
Laue method Rotating crystal method Powder method

Orientation Lattice constant Lattice parameter

Single crystal Single crystal Polycrystal

Polychromatic beam Monochromatic beam Monochromatic

beam
Fixed angle Variable angle Variable angle
 Applications of PXRD

Diffraction occurs when light is scattered by a periodic array with long-

range order, producing constructive interference at specific angles.

The atoms in a crystal are periodically arranged thus diffract light. The
wavelength of X-ray are similar to the distance between atoms, Powder X-
ray Diffraction (PXRD) techniques uses this principle to elucidate the
crystalline nature of materials.

The scattering of X-rays from atoms produce a diffraction pattern that

contains information about the atomic arrangement in crystal.

Amorphous materials like glass do not have periodic array with long-range
order so; they do not produce any significant peak in diffraction pattern
Crystal structure and Lattice parameters
using PXRD
X-ray diffraction provides ample information about the lattice
parameters. The position of a diffraction peak is determined by the size
and shape of unit cell of the crystalline phase. Peak represents a lattice
plane and therefore can be characterized by Miller index.

If the symmetry is high as in case of cubic or hexagonal, it is not

difficult to identify the peak index for an unknown phase. This is very
useful in solid-state chemistry to identifying new materials. Once a
pattern gets indexed, it serves as reference for new entitie
XRD Graph
 Polymorph study

PXRD is helpful in identification and characterization of polymorph

( Polymorphism describes the existence of a solid material in more than one
form or crystal structure). , monitoring the stability, method development and
validation for identification and quantification of drugs in Pharmaceutical
Industries.

The part of the X-ray that is not scattered simply passes through the next
layer of atoms, where again part of the X-ray is scattered and part of it
passes through to the next layer. This causes an overall diffraction pattern,
similar to how a grating diffracts a beam of light. In order for an X-ray to
diffract, the sample must be crystalline and the spacing between atom
layers must be close to the radiation wavelength.
 Polymorph study

If beams diffracted by two different layers are in phase,

constructive interference occurs and the diffraction pattern
shows a peak. However, if they are out of phase, destructive
interference occurs appear and no peak is observed. Diffraction
peaks only occur if it follows Bragg’s Law.

Since, a highly regular structure is needed for diffraction to

occur, only crystalline solids diffract, the PXRD of amorphous
materials do not depict any significant peak in diffraction
pattern
 Crystallinity study by PXRD

The XRD analysis of crystalline compounds gives a diffraction

pattern consisting of a well-defined, narrow, sharp and
significant peak while amorphous materials do not give clear
peaks rather the pattern has noise signals, smeared peak or it can
have some short order bumps.

Many polymers depict semi-crystalline behavior and produce

halo pattern. Powder XRD can be used to determine
the crystallinityy by comparing the integrated intensity of the
background pattern to that of the sharp peaks.
 Particle Size and Crystallite Size

The term particle size and crystallite size refer to two distinct
properties in a material. Particles comprise of several
small crystallite.

Crystallite size is the fundamental property of materials.

Properties of nanomaterials depend on crystals size and not
particle size.

PXRD can measure millions of crystals and accurately

determine the size distribution of nanomaterials.
 Phase Transition
Some crystals exhibits several phase transitions such as BaTiO3.
With temperature variation these different phases occurs. At this
point new diffraction peaks will appear or old ones disappear
according to the symmetry of the new phase.

These phases have different symmetry. So diiferent phases with

correspond to different crystal structure can be identified. In such
cases the symmetry may change because the existing structure is
distorted rather than replaced by a completely different one.
 Summary
X-Ray Diffraction is a technique used for identifying the atomic and
molecular structure of a crystal, in which the crystalline atoms cause
a beam of incident X-rays to diffract into many specific directions. This
forms a pattern, this type of pattern is called the X-ray diffraction pattern

When the X-ray is incident onto a crystal surface, its angle of incidence, θ,
will reflect with the same angle of scattering, θ. And, when the path
difference, d is equal to a whole number, n, of wavelength, constructive
interference will occur.

X-Ray diffraction methods along with Several Applications of Powder X-

Ray Diffraction were explored.
 References
1. Review Article: Powder XRD Technique and its Applications in
Science and Technology, Ashish Chauhan and Priyanka
Chauhan , Journal of Analytical & Bioanalytical Techniques, 5,
2014. DOI: 10.4172/2155-9872.1000212

2. Elements of X-Ray Diffraction , Second Edition by B.D.

Cullity.