X-Ray Diffraction

How Crystals follow symmetry?

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 Crystal Structure

Crystal structure: the manner in which atoms, ions, or

molecules are spatially arranged.

Unit cell: small repeating entity of the atomic structure. The

basic building block of the crystal structure. It defines the
entire crystal structure with the atom positions within.

Total 14 Bravais Lattices are possible; grouped into 7 more

general symmetry
Lattice Point Group 14 Bravais Lattices
Primitive (P) Base- Body-centered (I) Face-centered (F)
Centered (C)

Cubic Oh

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Lattice Point 14 Bravais Lattices
Group Primitive (P) Base- Body-centered (I) Face-centered (F)
Centered (C)

Tetragonal D4h

Orthorhombic D2h

Monoclinic C2h

Ci
Triclinic
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Lattice Point 14 Bravais Lattices
Group Primitive (P) Base- Body-centered (I) Face-centered (F)
Centered (C)

Rhombohedral D3h

Hexagonal
D6h

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 Diffraction, Refraction, Reflection, Interference

➢ Reflection is when light bounces off an object. If the surface is

smooth and shiny, like glass, water or polished metal, the light will
reflect at the same angle as it hit the surface. This is
called specular reflection.

➢ Refraction is the bending of light (it also happens with sound, water and other waves) as it
passes from one transparent substance into another.

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➢ Diffraction refers to various phenomena that occur when a wave
encounters an obstacle or opening. It is defined as the bending of waves
around the corners of an obstacle or through an aperture into the region
of geometrical shadow of the obstacle/aperture.
➢ The obstacle of dimension should be in the order of their
wavelength

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➢ Interference is a phenomenon in which two
waves superpose to form a resultant wave of
greater, lower, or the same amplitude.

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 X-rays?...

➢ In 1895, Wilhelm Roentgen accidently discovered X-rays when cathode tube was covered
in heavy black paper but surprisingly Incandescent green light passed through and
projected onto a nearby fluorescent screen.

➢ He found that the mysterious light could pass through most substances but leaves a
shadow of solid objects

➢ He did not know what rays were, he called them ‘X’, meaning ‘UNKNOWN’ rays.

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First X-ray Picture 1895. Roentgen Wife’s Hand

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 Introduction to XRD

➢ Why crystals appear in a regular shapes?

If it is because of, regular arrangement of building
blocks (atoms)
➢ Are X-rays waves or particles?
If X-rays are waves.
Crystals should acts as 3D-diffraction grating for x-rays.

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 Bragg’s Law

William and Lawrence Bragg (Father and Son)

Received Noble Prize in 1915

Lawrence the Youngest Scientist in the world who

ever been received Noble
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XRD Patten = Peak Position + Peak Intensity

Crystal structure= Lattice + Motif: Atom Positions

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 Preliminary aim of XRD?

➢ Interatomic distance.. ➢ Why..? Interatomic distance is vary with plane

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 Diffraction Methods

Method Wavelength Angle Specimen

Laue Variable Fixed Single

Crystal
Rotating Fixed Variable (in Single
Crystal part) Crystal
Powder Fixed Variable Powder

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 Laue Method

Zone axis
Transmission Zone axis Reflection

crystal
crystal

Film Incident beam Film

Incident beam

• Uses Single crystal

• Uses White Radiation
• Used for determining crystal orientation and quality

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 Rotating Crystal Method

◼ Determination of unknown crystal structures

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 Powder Method

Incident Beam Sample

Film

➢ Useful for determining lattice parameters with high precision

and for identification of phases 17
 Bragg’s Law
Diffracted beam

Incident beam Transmitted beam

Braggs' law: n = 2dhkl sin hkl

Bragg’s Law (Part 1): For every diffracted beam, there exists a set of
crystal lattice planes such that the diffracted beam appears to be
specularly reflected from this set of plane.
Reason for Noble: calling reflection as diffraction
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 Powder Method

I R

𝜃 𝜃
Plane

Specular reflection: Angle of Incidence = Angle of Reflection

Both angles should be measured from the plane and not from the normal

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How XRD pattern produced?
• Crystalline atoms are a periodic array of coherent scatterers and can diffract X-

rays.
• The wavelength of X-rays are similar to the distance between atoms.

• Diffraction from different planes of atoms produces a diffraction pattern, which

contains information about the atomic arrangement within the crystal.

• When X-ray hits the crystal planes at specific angles and the diffracted waves are

in the same phase, then constructive interference (a peak) will be produced.

• Based on structure of the

(Interference
crystal (and crystal planes),

pattern)
the angles at which
diffraction occurs may vary.
XRD patterns for 3 different forms of SiO2

▪ These three phases of SiO2 are

chemically identical.
▪ The amorphous glass does not
have long-range atomic order and
therefore produces only broad
pattern.
▪ Cristobalite form polycrystalline
structure.
▪ Quartz form single crystal structure.
Bragg model of diffraction
• Crystals are regular arrays of atoms, whilst X-rays are waves of EM radiation. Crystal atoms
scatter incident X-rays, primarily through interaction with the atom’s electrons. This
phenomenon is known as elastic scattering; the electron is known as the scatterer.
• A regular array of scatterers produces a regular array of spherical waves. In the majority of
directions, these waves cancel each other out through destructive interference, however,
they add constructively in a few specific directions, as determined by Bragg’s law:
• nλ = 2dsinθ , where “n” is an integer, and “λ” is the beam wavelength, “d” is the spacing
between diffracting planes and “θ” is the incident angle.
• X-rays scattered from adjacent planes will
combine constructively (constructive
interference) when angle θ between plane and
X-ray results in path-length difference that is
integer multiple “n” of X-ray wavelength “λ”.

Constructive interference Destructive interference

• In this model, a given reflection is associated with a set of evenly spaced sheets running
through the crystal, usually passing through the centres of the atoms of the crystal lattice.
• Orientation of a particular set of sheets is identified by its three Miller indices (h, k, l), and let
their spacing be noted by “d”.
• Specific directions appear as spots on the diffraction pattern called reflections. Consequently,
XRD patterns result from EM waves impinging on a regular array of scatterers.
• X-rays are used to produce the diffraction pattern because their wavelength, λ, is often the
same order of magnitude as the spacing “d” between the crystal planes (1-100 Ǻ).

• The path difference between Ray 1

and 2: 2a = 2d sinθ
• For constructive interference
2a = nλ = 2d sinθ
• Because crystal structures contain planes of atoms, each plane will reflect incident X-rays
differently. For ex. let two monochromatic X-ray beams (of a specific wavelength) strike a
crystal structure at an incoming angle of θ.
• Ray 1 will reflect off of the top atomic plane while Ray 2 will reflect from the second atomic
plane. However, because Ray 2 has to cross deeper into the atomic plane, it travels a
distance “2a” farther than Ray 1.
• If the distance “2a” is equal to the integral number (n*λ) of wavelength of 2 waves, then Ray
1 and 2 will be in-phase (constructively interfere) when they both exit the crystal.
• If we know wavelength λ of X-rays going into crystal and also measure angle θ of diffracted
X-rays coming out of crystal, then we can determine d-spacing between atomic planes.
• If we now reorient the crystal to a different atomic plane, we can measure d-spacing in other
planes. By doing multiple x-ray diffractions at different crystal orientations, we can
determined crystal structure and size of crystal unit cell.

• Incident angle (ω) is defined between the X-ray

tube
X-ray source and sample.
Detect
• Diffracted angle (2θ) is defined between the or
incident beam and the detector angle.
ω θ 2
• Incident angle (ω) is always ½ of the
θ
detector angle 2θ i.e. θ.
• In a typical XRD instrument, the X-ray tube
is fixed, the sample rotates at θ°/min and
detector rotates at 2θ°/min.
XRD Instrumentation

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1
1111111 1111111
1111111 1111111
1111111 1111111
1111111 1111111
1111111 1111111
1111111 1111111
1111111 1111111
111111 111111

1111111 1111111
1111111 1111111
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Powder X-ray Diffraction

Single Crystal X-ray Diffraction

• Powder diffraction data consists of a record of photon intensity vs detector angle 2θ

• Diffraction data can be reduced to a list of peak positions and intensities.
• Diffraction patterns are best reported using dhkl and relative intensity rather than 2θ and
absolute intensity.
• Each dhkl corresponds to a family of atomic planes {hkl}
• Individual planes cannot be resolved. This is a limitation of p-XRD vs single crystal diffraction.
Calculation of Crystallite Size using p-XRD data
Crystallites smaller than ~120 nm create broadening of diffraction peaks. This peak broadening
can be used to quantify the average crystallite size of nanoparticles using the Scherrer equation
- used for nanoparticles characterization. Must know the contribution of peak width from the
instrument by using a calibration curve

Scherrer equation can be written as:

o τ is mean size of ordered (crystalline) domains, which may be smaller or equal to grain size;
o K is a dimensionless shape factor, with a value close to unity. The shape factor has a typical
value of about 0.9, but varies with the actual shape of the crystallite;
• β is the line broadening at half the maximum intensity (FWHM), after
subtracting the instrumental line broadening, given in radians
• λ is the X-ray wavelength
• θ is the Bragg angle.
• This quantity is also
denoted as Δ(2θ)
Fig. Simulated p-XRD
patterns for wurtzite CdS
spherical particles of different
sizes from 1 μm to 1 nm. The
inset shows the 1, 2, and 5
nm XRD patterns on an
expanded y-axis scale for
clarity.
 XRD Numericals
Q. 1. In a NaCl crystal, there is a family of planes 0.252 nm apart. If the first-order maximum is
observed at an incidence angle of 18.1°, what is the wavelength of the X-ray scattering from this
crystal?
Ans.: Use the Bragg equation nλ = 2dsinθ to solve for θ.
For the first-order, n=1. Then λ = 2dsinθ/n = 2dsinθ/1
λ = 2(0.252×10−9 m)sin(18.1°)/1
= 0.504*0.31068 = 1.57×10−10m or 0.157 nm.

Q. 2. Estimate the crystallite size of the given nanomaterial using p-XRD data:
Peak position 2θ = 21.61o, FWHM of sample = 2.51o, k = 0.9 and λ = 1.5406 Å (degree to radian =
Degree × π/180).
Ans.: 2θ = 21.61o (θ = 10.805o) and FWHM = 2.51o (0.043825 radian)
Crystalline grain size calculation by Scherrer’s equation: k*λ/β*cosθ
k = 0.9, λ = 1.5406 Å (0.15406 nm), β = FWHM in radian and 2θ = Bragg’s angle in o obtained from
p-XRD data.
Crystallite size = (0.9*0.15406)/(0.043825*0.982257) nm = 3.22 nm
 X-ray Production
➢ X-rays are generated when high velocity electrons
impinge on a metal target
➢ Approximately 1% of the total energy of the
electron beam is converted into x-radiation
➢ The remainder being dispatched as heat
➢ Many types of x-rays tubes are available which are
used for producing x-rays.
➢ A positive voltage in the form of anode having a target
➢ Battery to emit thermoionic electrons
➢ Cathode – filament of tungsten 31
➢ A positive voltage in the form of anode having a target
➢ Battery to emit thermoionic electrons
➢ Cathode – filament of tungsten
➢ The electrons are accelerated toward the target
➢ On striking the target the electrons transfer their energy to its metallic
Surface which gives off x-rays radiation

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 Collimator, Filter and Detector
➢ Collimator: In order to get a narrow beam of x-rays, the x-rays generated by the target material
are allowed to pass through a collimator which consists of two sets of closely packed metal
plates separated by a small gap
➢ The collimator absorbs all the x-rays except the narrow beam passes between the slit
➢ Filter: X-ray beam may be partly monochromatized by insertion of suitable filter
➢ A filter is a window material that absorbs undesirable radiation but allows the radiation of
required wavelength to pass
➢ Detector: The x-ray intensities can be measured and recorded by various techniques
➢ 1. Photographic method
➢ 2. Counter methods: Geiger-Muller tube counter, proportional counter, scintillation counter,
➢ Solid-state semi conductor detector,

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 Derivation of Bragg’s law
Braggs' law: n = 2dhkl sin hkl
Where
• n is an integer determined by the order given,
• λ is the wavelength of x-rays, and moving electrons, protons and neutrons,
• d is the spacing between the planes in the atomic lattice, and
• θ is the angle between the incident ray and the scattering planes.

n = AB+ BC

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 Derivation of Bragg’s law

Sinθ = AB/BZ
= AB/d
AB = dsinθ

n = AB+ BC
Similarly, in ΔBCZ, BC = d Sinθ

Therefore, n  = 2dSinθ 35
Diffraction from Different Materials

“Elements of X-ray Diffraction”, B.D.

Cullity, Addison Wesley)
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Interpretation of XRD peaks

➢ International Committee on Power Diffraction Standards

(JCPDS)
➢ Software: Xpert High Score or some other free tools
ICDD

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Applications of X-Ray Diffraction (XRD) technique
• XRD is a versatile, non-destructive characterization technique widely used in

materials science and engineering for identifying unknown crystalline

materials.
• XRD works by irradiating a material with incident X-rays, and then measuring

the intensities and scattering angles of the X-rays that leave the material.
• XRD is used to study the structure and function of many biological

molecules, including vitamins, drugs, proteins and nucleic acids such as

DNA.
• XRD is also used to determine structural properties like lattice parameters,

strain, grain size, epitaxy, phase composition, preferred orientation, to

measure thickness of thin films and multi-layers and to determine atomic
arrangement.
• XRD also yields information on how the actual structure deviates from the

ideal one, owing to internal stresses and defects.

 Information in a Diffraction Pattern

➢Phase Identification

➢Crystal Size

➢Crystal Quality

➢Texture (to some extent)

➢Crystal Structure
 Analysis 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
I1: Intensity of the strongest peak
Solution
• 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 d 2 but only 4 have d1: 2.82 Å
• Out of these, only NaCl has d3: 1.63 Å
• It is NaCl……………Hurrah

Specimen and Intensities Substance File Number

2.829 1.999 2.26x 1.619 1.519 1.499 3.578 2.668 (ErSe)2Q 19-443
2.82x 1.996 1.632 3.261 1.261 1.151 1.411 0.891 NaCl 5-628
2.824 1.994 1.54x 1.204 1.194 2.443 5.622 4.892 (NH4)2WO2Cl4 22-65
2.82x 1.998 1.263 1.632 1.152 0.941 0.891 1.411 (BePd)2C 18-225
If multiple phases are present..

• More Complex
• Several permutations combinations possible d (Å) I/I1

• e.g. d1; d2; and d3, the first three strongest lines Pattern of Cu2O Remaining
3.01 Lines 5
show several alternatives d (Å) I/I1 d 2.47 I/I1 72
(Å) 2.13 28
• Then take any of the two lines together and match
3.020 9 Observed Normalized
2.09 * 100
• It turns out that 1st and 3rd strongest lies belong to2.465 100 3.01 5
1.80 *
7
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Cu and then all other peaks for Cu can be
2.135 37Pattern2.47 72 1.50 20
100
separated out for Cu
1.29 9
• Now separate the remaining lines and normalize 1.743 1 d (Å) 2.13
I/I1 28 39
2.088 100 1.28 * 18
the intensities 1.510 27 1.50 20 28
1.808 46 1.22 4
• Look for first three lines and it turns out that the 1.287 171.278 1.29
20
9 1.08 * 13
20
phase is Cu2O
1.233 4 1.09 1.22 17 4 1.04 * 36

• If more phases, more pain to solve  1.0674 2

1.0436
0.9038
5
0.98
3
5
0.98
0.91
5
4
7

0.9795 4 0.8293 9 0.83 * 8

0.8083 8 0.81 * 10
 Lattice strain

do

No Strain 2

Uniform Strain
  d  strain 2

Non-uniform Strain
2
d
Broadeing b = 2 = −2 tan 
d
 Texture in Materials

• Grains with in a polycrystalline are not completely randomly distributed

• Clustering of grains about some particular orientation(s) to a certain degree

• Examples:

• Present in cold-rolled brass or steel sheets

• Cold worked materials tend to exhibit some texture after recrystallization

• Affects the properties due to anisotropic nature

 Texture

• Fiber Texture
• A particular direction [uvw] for all grains is more or less parallel to the wire or fiber axis
• e.g. [111] fiber texture in Al cold drawn wire

• Double axis is also possible

• Example: [111] and [100] fiber textures in Cu wire

• Sheet Texture
• Most of the grains are oriented with a certain crystallographic plane (hkl) roughly parallel
to the sheet surface and certain direction [uvw] parallel to the rolling direction
• Notation: (hkl)[uvw]
THANK YOU

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