XRD

Contents

• Origin of X-rays
• Basic aspects of crystals and Principle involved
• X-ray crystallography and Bragg’s Law
• XRD Techniques: Rotating crystal technique, single
crystal diffraction, powder diffraction,
• Instrumentation
• Structural elucidation
• Applications
 DIFFRACTION

• Where have we heard about this word Diffraction?

Diffraction Grating
 What is X-ray diffraction?

• Diffraction of X rays from a crystal surface

• Crystalline substances consist of parallel rows of
atoms separated by a ‘unique’ distance
• Diffraction occurs when radiation enters a crystalline
substance and is scattered
• Direction and intensity of diffraction depends on
orientation of crystal lattice with radiation
• Identification and quantification is achieved by
comparing the X-ray diffraction pattern
 How Diffraction Works?
• Waves interact with a single particle
• Incident beams are scattered uniformly in all
directions
• Scattered beams interfere constructively in some
directions, producing diffracted beams
• Random arrangements cause beams to randomly
interfere and no distinctive pattern is produced
• Regular pattern of crystalline atoms produces regular
diffraction pattern.
• Diffraction pattern gives information on crystal
structure
 X-ray diffraction Application

• Non-destructive analytical technique for

identification and quantitative determination of the
various crystalline forms, known as ‘phases’.
 X-ray diffraction Application

X-ray Crystallography is a scientific method used to

determine the arrangement of atoms of a crystalline
solid in three dimensional space.
This technique takes advantage of the interatomic
spacing of most crystalline solids by employing them as a
diffraction gradient for x-ray light, which has wavelengths
on the order of 1 angstrom (10-8 cm).

7
X-ray diffraction Application

8
 Fundamental Principle of X-ray Powder
Diffraction (XRD)
• X ray diffraction methods are based on generation of X-
rays in an X-ray tube.
• These X-rays are directed at the sample, and the
diffracted rays are collected.
• Diffraction could be from the crystal or from the
powder
• A key component of all diffraction is the angle between
the incident and diffracted rays.
• The interaction of the incident rays with the sample
produces constructive interference (and a diffracted ray)
when conditions satisfy Braggs Law (nλ=2d sin θ)
Originof X rays
XRD: Bragg’s Law
 Derivation of Bragg’s Law
• Constructive interference is possible
if nλ= AB + BC
• AB=BC
• nλ= 2AB
P • But in triangle ABP,
• AB= d sin θ, where d is the distance
between two crystal planes
• So now
P
• nλ = 2d sin θ [ Bragg’s Law ]
 n is the positive integer, the order,
 λ [m] is the wavelength of the X-ray,
 d [m] is the interplanar distance, the
distance between consecutive layers
of atoms,
 θ [rad] is the angle of the incident X-
ray.
 Bragg’s Law
• This law relates the wavelength of electromagnetic
radiation to the diffraction angle and the lattice spacing
in a crystalline sample.
• These diffracted X-rays are then detected, processed and
counted.
• By scanning the sample through a range of 2θangles, all
possible diffraction directions of the crystal lattice/
powder should be attained.
• Conversion of the diffraction peaks to d-spacings allows
identification of the sample because each mineral has
a set of unique d-spacings.
• Typically, this is achieved by comparison of d-spacings
with standard reference patterns.
 Instrumentation

X Ray Diffraction spectrophotometer

 Essential Parts of the Diffractometer
• X-ray Tube: the source of X Rays
• Incident-beam optics: condition the X-ray beam
before it hits the sample
• The goniometer: the platform that holds and moves
the sample, optics, detector, and/or tube
• The sample & sample holder
• Receiving-side optics: condition the X-ray beam after
it has encountered the sample
• Detector: count the number of X Rays scattered by
the sample
XRD Instrumentation
XRD Instrumentation : Schematic
 X Ray tube

https://images.app.goo.gl/gKQMN6MbzSViJQr66
 X Ray tube
• X Ray tube generate X rays by striking the anode target
with an electron beam in a glass envelope (vacuum) from
a tungsten filament.
• The target must be water cooled.
• The wavelength of X rays is determined by the anode of
the X-ray source.
• Electrons from the filament strike the target anode,
producing characteristic radiation via the photoelectric
effect.
• The anode material determines the wavelengths
of characteristic radiation.
 Collimator

https://images.app.goo.gl/gFD53gNGLoiXUwFk8
 Device for restricting wavelength of X
rays
While we would prefer a monochromatic X Ray source,
the X-ray beam actually consists of several characteristic
wavelengths of X rays. K L M

Filters Monochromators

Absorb Produce the X

unwante ray of a
d single
radiations wavelength
 Device for restricting wavelength of X
rays
Filters
• Target element
Molybdenum emits Kα
and Kβ lines
• Kα line is used for
analytical purpose
• Kβ line is absorbed by
Zirconium filter
 Device for restricting wavelength of X
rays
Monochromaters
• Two collimators serve
purpose of entrance and
exit slits.
• A single crystal works as
a dispersing element and
disperses incident light
into component
wavelength
• Selected wavelength
then passes through the
second collimator and
falls on the sample
crystal.
Crystal Monochromator
 Sample holder and Goniometer

https://images.app.goo.gl/tZnYgJUuQLwCsfDa8
https://images.app.goo.gl/WuhALCoYAagKVBrM9
Detectors : Gas filled Transducers

https://images.app.goo.gl/dHgny79LB4rignoPA
 Detectors : Geiger Tubes

https://images.app.goo.gl/iyd1HEzLFo4cEem89
Detectors :Scintillation Detector
 Applications of XRD

• To identify crystalline phases and orientation

• To determine structural properties
• Lattice parameters (10-4Å), strain, grain size, phase
composition, preferred orientation (Laue) order-
disorder transformation, thermal expansion
• To measure thickness of thin films and multi-layers
• To determine atomic arrangement
 Applications of XRD
• X-ray powder diffraction is most widely used for the
identification of unknown crystalline materials (e.g.
minerals, inorganic compounds).
• Determination of unknown solids is critical to studies in
geology, environmental science, material science,
engineering and biology.
• Characterization of crystalline materials
• Identification of fine-grained minerals such as clays and
mixed layer clays that are difficult to determine optically
• Determination of unit cell dimensions measurement of
sample purity
 Applications of XRD
• With specialized techniques, XRD can be used
• To determine crystal structures using Rietveld refinement
• To determine of modal amounts of minerals (quantitative analysis)
• To make textural measurements, such as the orientation of grains, in
a polycrystalline sample
• To characterize thin films samples by:
 determining lattice mismatch between film and substrate and to
inferring stress and strain
 determining dislocation density and quality of the film by rocking
curve measurements
 measuring super lattices in multilayered epitaxial structures
 determining the thickness, roughness and density of the film using
glancing incidence X-ray reflectivity measurements
 Advantages of X ray Diffraction

• Powerful and rapid (< 20 min) technique for

identification of anunknown mineral
• In most cases, it provides an unambiguous mineral
determination
• Minimal sample preparation is required
• XRD units are widely available
• Data interpretation is relatively straight forward
 Limitations of X ray Diffraction
• Homogeneous and single phase material is best for
identification of an unknown
• Must have access to a standard reference file of in
organic compounds (d-spacings, hkls)
• Requires tenths of a gram of material which must be
ground into a powder
• For mixed materials, detection limit is ~ 2% of
sample
• For unit cell determinations, indexing of patterns for non-
isometric crystal systems is complicated
• Peak overlay may occur and worsens for high angle
reflections
XRD
 Crystal Related terms

• Miller indices
• Bravais lattice
 Bravais lattice
• Unlimited number of possible lattices because there
is no restriction on the size of and angle between the
lattice vectors a, b and c.
• Lattices can, however, be categorized into groups
which are invariant under certain combinations of
the rotational symmetry operations identified above
and under mirror reflection.
• There are 5 such lattice types in 2 dimensions and 14
types in 3 dimensions.
• These distinct types of lattice are called ‘Bravais
lattices’ after Auguste Bravais, who demonstrated
that there are 14 types in 1848.
Miller Indices
 Crystalline materials are characterized by the
orderly periodic arrangements of atoms.

• The unit cell is the basic repeating unit that defines a crystal.
• Parallel planes of atoms intersecting the unit cell are used to define
directions and distances in the crystal.
– These crystallographic planes are identified by Miller indices.
 Miller Indices

• Used to specify directions and planes of lattices and

crystals
• Used to study direction of crystals
• Helps to understand how to give direction to the
crystallographic plane.
• Crystallographic plane is the plane which passes
through lattice points
 How to determine miller indices?

• The value looks like this (1,0,0)

• Identify the plane intercepts on the X, Y and Z axes
• a ,b and c are the related vectors for X, Y and Z axes
respectively
• (h, k, l) represent a point in the crystal
• Specify intercepts in fractional coordinates
• Take the reciprocals of the fractional intercepts
Observe the pink plane
• X intercept=1
• Y intercept= infinity
• Z intercept= Infinity
• Fractions =( 1, ∞, ∞)
• Reciprocals=(1,0,0)
• Miller indices =(1,0,0)
Observe the yellow plane

• X intercept= ∞
• Y intercept= 1
• Z intercept= ∞
• Fractions =(∞,1, ∞)
• Reciprocals=(0,1,0)
• Miller indices =(0,1,0)
Find out the miller indices for green
plane
• X intercept=
• Y intercept=
???? • Z intercept=
• Fractions =( ,)
,
• Reciprocals=( , )
,
• Miller indices =( , ,
)
Find out the miller indices for green
plane
• X intercept= ∞
• Y intercept= ∞
???? • Z intercept=1
• Fractions =(∞ ,∞ ,1)
• Reciprocals=(0,0,1)
• Miller indices =(0,0,1)
Miller Indices for planes
Miller Indices for planes
Miller Indices for planes
 X-Ray Powder Diffraction (XRPD) uses information about the position,
intensity, width, and shape of diffraction peaks in a pattern from a
polycrystalline sample.

The x-axis, 2theta, corresponds to the angular position of the detector that
rotates around the sample.
A single crystal specimen in a Bragg-Brentano diffractometer would
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 The (200) planes are parallel to the (100) planes.
°2; however, they are not properly Therefore, they also diffract for this crystal. Since
aligned to produce a diffraction peak (the d200 is ½ d100, they appear at 42 °2.
perpendicular to those planes does not
bisect the incident and diffracted beams).
Only background is observed.
 A polycrystalline sample should contain thousands of crystallites.
Therefore, 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.
 Diffraction data consists of a record of photon
intensity versus detector angle 2.

Raw Data Reduced dI list

Position Intensity hkl dhkl (Å) Relative
[°2] [cts]
25.2000 372.0000 Intensity
25.2400 460.0000 (%)
25.2800 576.0000
{012} 3.4935 49.8
25.3200 752.0000
25.3600 1088.0000 {104} 2.5583 85.8
25.4000 1488.0000
{110} 2.3852 36.1
25.4400 1892.0000
25.4800 2104.0000 {006} 2.1701 1.9
25.5200 1720.0000
{113} 2.0903 100.0
25.5600 1216.0000
25.6000 732.0000 {202} 1.9680 1.4
25.6400 456.0000
25.6800 380.0000
25.7200 328.0000
 XRD Application

• Identification of crystalline phases and orientation

• Structure and structural properties of crystal
• Lattice parameters
• Qualitative and quantitative analysis about
compounds present in the same.
• Characterization of polymers
• Thickness of thin films and multilayers
• State of annealing in metals
• Particle size determination
THANK YOU!