Diffraction

UNIT- 1
Determination of crystal structure using X-rays
Disclaimer: The above material is purely for teaching purpose

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What is Diffraction?
When light passing through a tiny opening such as slit or aperture

produces alternate regions of darkness and brightness beyond the
region of geometric shadow. Such alternate bright and dark bands are
known as the diffraction pattern.
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What is Diffraction Pattern?
Diffraction of light is noticeable only when the size of the obstacle is
comparable to wavelength of light.

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What is Diffraction?
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

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A bit of History
• William Roentgen discovered X-rays in
1895 and determined they had the
following properties
1. Travel in straight lines
2. Are exponentially absorbed in
matter with the exponent
proportional to the mass of the
absorbing material
3. Darken photographic plates
4. Make shadows of absorbing
material on photosensitive paper
• Roentgen was awarded the Nobel
Prize in 1901
• Debate over the wave vs. particle
nature of X-rays led the development
of relativity and quantum mechanics

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X-rays Tube Schematic
 Schematic cross section of an X-ray tube as used in our lab
 Cathode is made of tungsten W.
 The anode is a pure metal. Cu, Mo, Fe, Co and Cr are in common use in XRD
applications. Cu, Co and Mo will be available on our new systems.
 The tube is cooled by water and housed in a shielding aluminium tower.

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Generation of X-rays
c • X-rays may be described as
 (1) waves and particles, having
 both wavelength () and energy
(E)
E  h
• In the equations at left:
(2) • E is the energy of the electron flux in KeV
• h is Planck’s constant (4.135 x 10-15 eVs)
• v is the frequency
• c is the speed of light (3 x 1018 Å/s)
hc •  is the wavelength in Å
E (3) • Substituting (1) into (2) yields

 (3), the relationship between
wavelength and energy.
• In (4) all constants are
12.398
E (4) substituted
 Disclaimer: The above material is purely for teaching purpose

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Continuous Spectrum
X-rays are produced whenever matter is irradiated with a beam
of high-energy charged particles or photons
In an x-ray tube, the interactions are between the electrons

and the target. Since energy must be conserved, the energy
loss from the interaction results in the release of x-ray photons
The energy (wavelength) will be equal to the energy loss

(Equation 4).
This process generates a broad band of continuous radiation

(a.k.a. bremsstrahlung or white radiation)

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Continuous Spectrum
hc 12.398
 min  
V V
• The minimum wavelength ( in
angstroms) is dependent on the
accelerating potential ( in KV)
of the electrons, by the
equation above.
• The continuum reaches a
maximum intensity at a
wavelength of about 1.5 to 2
times the min as indicated by
the shape of the curve

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Generating Characteristic Radiation
• The photoelectric effect is
responsible for generation of
characteristic x-rays.
Qualitatively here’s what is
happening:
• An incoming high-energy
photoelectron disloges a k-shell
electron in the target, leaving a
vacancy in the shell
• An outer shell electron then “jumps”
to fill the vacancy
• A characteristic x-ray (equivalent to
L-shell to K-shell jump the energy change in the “jump”) is
generated
produces a K X-ray
M-shell to K-shell jump
produces a K X-ray
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Continuous and Characteristic Spectrum
Target  Of K
Metal radiation (Å)
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
The high intensity nearly monochromatic K x-rays can be used as a radiation source for X-ray
diffraction (XRD) studies  a monochromator
Disclaimer: The above materialcan
is purelybe used
for teaching to further decrease the spread of
purpose
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wavelengths in the X-ray
X-ray Diffraction: Generation of X-ray
(a) Schematic design of a filament X-ray tube. (b) Use of Ni to filter out Cu Kβ and
white radiation.
Generation of Cu Kα X-rays. A 1s electron is

ionised; a 2p electron falls into the empty 1s
level and the excess energy is released as X-
rays.
X-rays are electromagnetic radiation of wavelength

∼1 A (10-10m)
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X-ray Diffraction: Concept
 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
Disclaimer: The above material is purely for teaching purpose only

X-ray diffraction patterns
Diffraction peaks are associated
with planes of atoms
 Miller indices (hkl) are used to identify different

planes of atoms.
 Observed diffraction peaks can be related to

planes of atoms to assist in analysing the atomic
structure and microstructure of a sample.

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Sir William Henry Bragg:
•William Henry and William Lawrence Bragg Bragg’s law
(father and son) found a simple interpretation
of von Laue’s experiment.
• They assume that each crystal plane reflects
radiation as a mirror and analyze this situation for
cases of constructive and destructive interference.
Noble
prize
1915!
Conditions for reflection: 2d sin   n 

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Let us consider scattering across planes
BRAGG’s EQUATION
 A portion of the crystal is shown for clarity- actually, for destructive interference to occur many planes are
required (and the interaction volume of x-rays is large as compared to that shown in the schematic).
 The scattering planes have a spacing ‘d’.
 Ray-2 travels an extra path as compared to Ray-1 (= ABC). The path difference between Ray-1 and Ray-2
= ABC = (d Sin + d Sin) = (2d.Sin).
 For constructive interference, this path difference should be an integral multiple of :
n = 2d Sin  the Bragg’s equation.
 The path difference between Ray-1 and Ray-3 is = 2(2d.Sin) = 2n = 2n. This implies that if Ray-1
and Ray-2 constructively interfere Ray-1
Disclaimer:and Ray-3
The above materialwill also
is purely constructively
for teaching purpose interfere. (And so forth).
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Understanding the Bragg’s equation
 n = 2d Sin
The equation is written better with some descriptive subscripts:
n Cu K  2 d hkl Sin hkl If this equation is satisfied, then  is Bragg
 n is an integer and is the order of the reflection

(i.e. how many wavelengths of the X-ray go on to make the path difference between
planes). Note: if hkl reflection (corresponding to n=1) occurs at hkl then 2h 2k 2l reflection (n=2) will occur at a higher angle 2h 2k
2l.
 Bragg’s equation is a negative statement

 If Bragg’s eq. is NOT satisfied  NO ‘reflection’ can occur
 If Bragg’s eq. is satisfied  ‘reflection’ MAY occur
 The interplanar spacing appears in the Bragg’s equation, but not the interatomic spacing ‘a’
along the plane (which had forced incident = scattered); but we are not free to move the atoms
along the plane ‘randomly’.
  For large interplanar spacing the angle of reflection tends towards zero → as d increases, Sin
decreases (and so does ).
 The smallest interplanar spacing from which Bragg diffraction can be obtained is /2 → maximum
value of  is 90, Sin is 1  from Bragg
Disclaimer: equation
The above d =for/2.
material is purely teaching purpose
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In XRD nth order reflection from (h k l) is considered as 1st order reflection from (nh nk nl)
n  2dhkl sin hkl

d nh nk nl 1
d  d 200 1
  2 hkl sin  d hkl n 
d100 2
n
  2dnh nk nl sin nh nk nl All these form the (200) set
Hence, (100) planes are a subset of (200) planes
d300 1

d100 3
Important point to note:

In a simple cubic crystal, 100, 200, 300… are all allowed ‘reflections’. But, there are no atoms in the planes
lying within the unit cell! Though, first order reflection from 200 planes is equivalent (mathematically) to the
second order reflection from 100 planes; for visualization purposes of scattering, this is better thought of as
the later process (i.e. second order reflection from (100).
Note:
Technically, in Miller indices we factor out the common factors. Hence, (220)  2(110)  (110).
In XRD we extend the usual concept of Miller indices to include planes, which do not pass through lattice
points (e.g. every alternate plane belonging to the (002) set does not pass through lattice points) and we
allow the common factors to remain in the indices.
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The missing ‘reflections’
 We had mentioned that Bragg’s equation is a negative statement: i.e. just because Bragg’s equation is
satisfied a ‘reflection’ may not be observed.
 Let us consider the case of Cu K radiation ( = 1.54 Å) being diffracted from (100) planes of Mo (BCC,
a = 3.15 Å = d100).
 1.54
  2 d100 Sin100 Sin100    0.244 100  14.149 But this reflection
2 d100 2(3.15) is absent in BCC Mo
The missing reflection is due to the presence of additional atoms in the unit cell
(which are positions at lattice points)  which we shall consider next.
The wave scattered from the middle plane is out

of phase with the ones scattered from top and
bottom planes. I.e. if the green rays are in phase
(path difference of ) then the red ray will be
exactly out of phase with the green rays (path
difference of /2).
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Crystal structure determination
 As diffraction occurs only at specific Bragg angles, the chance that a reflection is observed
when a crystal is irradiated with monochromatic X-rays at a particular angle is small (added to
this the diffracted intensity is a small fraction of the beam used for irradiation).
 The probability to get a diffracted beam (with sufficient intensity) is increased by either
varying the wavelength () or having many orientations (rotating the crystal or having
multiple crystallites in many orientations).
 The three methods used to achieve high probability of diffraction are shown below.
Many s (orientations) POWDER λ  fixed

Monochromatic X-rays Powder specimen METHOD θ  variable
LAUE λ  variable
Panchromatic X-rays Single 
TECHNIQUE θ  fixed
ROTATING λ  fixed
Monochromatic X-rays  Varied by rotation CRYSTAL
METHOD θ  rotated
Only the powder method (which is commonly used in materials science) will be considered in this text.
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New powder method
OLD powder method

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The powder diffractometers typically use the
Bragg-Brentano 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.
Disclaimer: The above material is purely for teaching purpose only

Polycrystalline sample showing grains in
different orientation
Electron backscattered diffraction (EBSD)

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XRD of a single crystal
 Produce only one family of peaks in the diffraction pattern.
2
At 20.6 °2, Bragg’s law The (110) planes would diffract at 29.3 The (200) planes are parallel to the (100)
fulfilled for the (100) planes, °2; however, they are not properly planes. Therefore, they also diffract for this
producing a diffraction peak. aligned to produce a diffraction peak crystal. Since d200 is ½ d100, they appear at
(the perpendicular to those planes does 42 °2.
not bisect the incident and diffracted
beams). Only
Disclaimer: Thebackground
above material isis observed.
purely for teaching purpose
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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 crystallitesDisclaimer:
thatThewill diffract
above material is purely and that
for teaching purposethere is a statistically relevant
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number of crystallites, not just one or two.
How to visualize the occurrence of peaks at various angles?
It is ‘somewhat difficult’ to actually visualize a random assembly of crystallites giving peaks at various angels in a XRD
scan. The figures below are expected to give a ‘visual feel’ for the same. [Hypothetical crystal with a = 4Å is assumed with
=1.54Å. Only planes of the type xx0 (like (100,110)are considered].
Random assemblage of
As the scan takes place at increasing
crystallites in a material angles, planes with suitable ‘d’, which
diffract are ‘picked out’ from
favourably oriented crystallites
h2 hkl d Sin() 

1 100 4.00 0.19 11.10
2 110 2.83 0.27 15.80
3 111 2.31 0.33 19.48
4 200 2.00 0.39 22.64
5 210 1.79 0.43 25.50
6 211 1.63 0.47 28.13
8 220 1.41 0.54 32.99
9 300 1.33 0.58 35.27
10 310 1.26 0.61 37.50 Disclaimer: The above material is purely for teaching purpose
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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
Either,  h, k and l are all odd or
DC  all are even & (h + k + l)
only divisible by 4
h2 + k2 + l2 SC FCC BCC DC
1 100
2 110 110
Allowed reflections in SC,
FCC, BCC & DC crystals 3 111 111 111
4 200 200 200
5 210
6 211 211
7
8 220 220 220 220
9 300, 221
Cannot be expressed as (h2+k2+l2)
10 310 310
11 311 311 311
12 222 222 222
13 320
14 321 321
15
16 400 400 400 400
17 410, 322
18 411, 330 411, 330
19 331
331 331
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The ratio of (h2 + k2 + l2) derived from extinction rules (earlier page)
As we shall see soon the ratios of (h2 + k2 + l2) is proportional to Sin2

 which can be used in the determination of the lattice type
SC 1 2 3 4 5 6 8 …
BCC 2 4 6 8 10 12 … …
FCC 3 4 8 11 12 …
DC 3 8 11 16 …
 Note that we have to consider the ratio of only two lines to distinguish FCC and DC.
I.e. if the ratios are 3:4 then the lattice is FCC.
 But, to distinguish between SC and BCC we have to go to 7 lines!

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Given the positions of the Bragg peaks we find the lattice type
Whole
2→  Sin Sin2  Sin2θ/Sin2θ1 number d a
ratios
1 21.5 0.366 0.134 1 3
2 25 0.422 0.178 1.32 4
3 37 0.60 0.362 2.70 8
4 45 0.707 0.500 3.73 11
5 47 0.731 0.535 3.99 12
6 58 0.848 0.719 3.86 16
7 68 0.927 0.859 6.41 19 FCC

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Determination of Crystal Structure (lattice type) from 2 versus Intensity Data
Let us assume that we have the 2 versus intensity plot from a diffractometer
 To know the lattice type we need only the position of the peaks (as tabulated below)
# 2  Sin Sin2  ratio Index d

1 38.52 19.26 0.33 0.11 3 111 2.34
2 44.76 22.38 0.38 0.14 4 200 2.03
3 65.14 32.57 0.54 0.29 8 220 1.43
4 78.26 39.13 0.63 0.40 11 311 1.22
5 82.47 41.235 0.66 0.43 12 222 1.17
6 99.11 49.555 0.76 0.58 16 400 1.01
7 112.03 56.015 0.83 0.69 19 331 0.93
8 116.60 58.3 0.85 0.72 20 420 0.91
9 137.47 68.735 0.93 0.87 24 422 0.83
10 163.78 81.89 0.99 0.98 27 333 0.78
Note that Sin cannot be > 1

From the ratios in column 6 we conclude that FCC
Using Note
  2 d Sin a
o 1.54  2 d111 Sin111  2 0.33 (h 2  k 2  l 2 )  sin 2 
a  4.04 A  Al 3
Note: Error in d spacing decreases with  → so we should use high angle lines for lattice parameter
calculation only
What happens when we increase or decrease?
We had pointed out that  ~ a is preferred for diffraction. Let us see what happens if we ‘drastically’
increase or decrease .
(This is only a thought experiment!!)
Aluminium  = 1.54 Å =3Å  = 0.1 Å

hkl d Sin()  2 Sin()  2 Sin()  2
111 2.34 0.33 19.26 38.52 0.64 39.87 79.74 0.02 1.22 2.45
200 2.03 0.38 22.38 44.76 0.74 47.64 95.28 0.02 1.41 2.82
220 1.43 0.54 32.57 65.14 1.05 - - 0.03 2.00 4.01
311 1.22 0.63 39.13 78.26 1.23 - - 0.04 2.35 4.70
222 1.17 0.66 41.24 82.47 1.28 - - 0.04 2.45 4.90
400 1.01 0.76 49.56 99.11 1.49 - - 0.05 2.84 5.68
331 0.93 0.83 56.02 112.03 1.61 - - 0.05 3.08 6.16
420 0.91 0.85 58.30 116.60 1.65 - - 0.05 3.15 6.30
422 0.83 0.93 68.74 137.47 1.81 - - 0.06 3.45 6.91
333 0.78 0.99 81.89 163.78 1.92 - - 0.06 3.68 7.35
With CuK  = 1.54 Å If we make  small→ all the

peaks get crowded to small
If we ~double  → we angles
get too few peaks
And the detector may not be able to resolve these peaks if they come too close!
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Crystal
Intensity →
Schematics
Schematic of difference between

the diffraction patterns of various phases
Sharp peaks
0 90 180
Diffraction angle (2) →
Monoatomic gas
Intensity →
No peak
Diffraction angle (2) → Diffraction angle (2) →

Liquid / Amorphous solid
Intensity →
0 90 180
Diffuse Peak
0 90 180

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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……………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
Caution: It could be much more tricky if the sample is oriented or textured or your goniometer is not
calibrated
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Numerical Problem
For BCC iron, compute (a) the interplanar spacing and (b) the diffraction angle for
the (220) set of planes. The lattice parameter for Fe is 0.2866 nm. Also, assume
that monochromatic radiation having a wavelength of 0.1790 nm is used, and the
order of reflection is 1.
Ans : (a) 0.1013 nm (b) 2θ = (2)(62.13◦) = 124.26◦

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Using the extinction rules, identity the crystal structure of the following
diffractogram. Find the out the lattice parameter. ( wavelength = 1.54 Ǻ)

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An element, BCC or FCC, shows diffraction peaks at 2θ: 40, 58, 73, 86.8,100.4 and
114.7. Determine:(a) Crystal structure?(b) Lattice constant?(c) What is the
element?

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Figure shows the first five peaks of the x-ray diffraction pattern for tungsten,
which has a BCC crystal structure; monochromatic x-radiation having a
wavelength of 0.1542 nm was used.
(a) Index (i.e., give h, k, and l indices) for each of these peaks.
(b) Determine the interplanar spacing for each of the peaks.
(c) For each peak, determine the atomic radius for W

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Determine the indices for the directions shown in the
following cubic unit cell:

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Determine the for the indices of following plane shown in the hexagonal unit cell:

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UNIT- 1

Determination of crystal structure using X-rays

Disclaimer: The above material is purely for teaching purpose

When light passing through a tiny opening such as slit or aperture

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

 Cathode is made of tungsten W.

 The tube is cooled by water and housed in a shielding aluminium tower.

Disclaimer: The above material is purely for teaching purpose

E (3) • Substituting (1) into (2) yields

 Disclaimer: The above material is purely for teaching purpose

In an x-ray tube, the interactions are between the electrons

The energy (wavelength) will be equal to the energy loss

This process generates a broad band of continuous radiation

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Generation of Cu Kα X-rays. A 1s electron is

X-rays are electromagnetic radiation of wavelength

 The electrons in an atom coherently scatter light.

Disclaimer: The above material is purely for teaching purpose only

 Miller indices (hkl) are used to identify different

 Observed diffraction peaks can be related to

Disclaimer: The above material is purely for teaching purpose

Conditions for reflection: 2d sin   n 

 n is an integer and is the order of the reflection

 Bragg’s equation is a negative statement

n  2dhkl sin hkl

Hence, (100) planes are a subset of (200) planes

Important point to note:

The wave scattered from the middle plane is out

Many s (orientations) POWDER λ  fixed

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose only

Electron backscattered diffraction (EBSD)

Disclaimer: The above material is purely for teaching purpose

h2 hkl d Sin() 

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

As we shall see soon the ratios of (h2 + k2 + l2) is proportional to Sin2

Disclaimer: The above material is purely for teaching purpose

1 21.5 0.366 0.134 1 3

2 25 0.422 0.178 1.32 4

3 37 0.60 0.362 2.70 8

4 45 0.707 0.500 3.73 11

5 47 0.731 0.535 3.99 12

6 58 0.848 0.719 3.86 16

7 68 0.927 0.859 6.41 19 FCC

Disclaimer: The above material is purely for teaching purpose

# 2  Sin Sin2  ratio Index d

Note that Sin cannot be > 1

Aluminium  = 1.54 Å =3Å  = 0.1 Å

With CuK  = 1.54 Å If we make  small→ all the

Schematic of difference between

Diffraction angle (2) → Diffraction angle (2) →

Disclaimer: The above material is purely for teaching purpose

2(˚) d (Å) (I/I1)*100