X-ray Diffraction: Principles and Practice

Ashish Garg and Nilesh Gurao

Department of Materials Science and Engineering
Indian Institute of Technology Kanpur
Layout of the Lecture

 Materials Characterization
 Importance of X-ray Diffraction
 Basics
 Diffraction
 X-ray Diffraction
 Crystal Structure and X-ray Diffraction
 Different Methods
 Phase Analysis
 Texture Analysis
 Stress Analysis
 Particles Size Analysis
 ………..
 Summary
Materials Characterization

 Essentially to evaluate the structure and

properties
 Structural Characterization
 Diffraction
 X-ray and Electron Diffraction
 Microscopy
 Spectroscopy
 Property Evaluation
 Mechanical
 Electrical
 Anything else
Time Line

 1665: Diffraction effects observed by Italian

mathematician Francesco Maria Grimaldi
 1868: X-rays Discovered by German Scientist
Röntgen
 1912: Discovery of X-ray Diffraction by
Crystals: von Laue
 1912: Bragg’s Discovery
Electromagnetic Spectrum
Generation of X-rays
Commercial X-ray Tube
 X-ray Spectrum from an Iron target
12400
 Short Wavelength Limit SWL (nm) 
V
 Continuous spectrum I CS  AiZV m

 Characteristic X-ray Moseley’s Law

  C(Z   )
I K  Bi (V V k) n

λSWL
 Use of Filter

 Ni filter for Cu Target

Crystal Systems and Bravais Lattices
 Structure of Common Materials

 Metals
 Copper: FCC
 -Iron: BCC
 Zinc: HCP
 Silver: FCC
 Aluminium: FCC
 Ceramics
 SiC: Diamond Cubic
 Al2O3: Hexagonal
 MgO: NaCl type
 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
 Scattering Modes

 Random arrangement of atoms in space gives rise

to scattering in all directions: weak effect and
intensities add
 By atoms arranged periodically in space
 In a few specific directions satisfying Bragg’s law: strong
intensities of the scattered beam :Diffraction
 No scattering along directions not satisfying Bragg’s law
Diffraction of light through an aperture

0.9

0.8

0.7

0.6

Intensity
0.5

0.4

0.3

0.2

0.1

0
-15 -10 -5 0 5 10 15
 1

0.9

0.8

0.7

0.6

Intensity
0.5

0.4

0.3

0.2

0.1

0
-15 -10 -5 0 5 10 15

Minima Maxima

sinθ n sin  2n  1
  n = 1, 2,..
λ a
n = 0, 1,..  2a
Young’s Double slit experiment

d sinθ = mλ, m = 1,2,3….. Constructive Interference

d sinθ = (m+½)λ, m = 1,2,3….. Destructive Interference

Interference
Phase Difference = 0˚ Phase Difference = 90˚

Phase Difference = 180˚

Interference and Diffraction
 Bragg’s Law

n=2d.sin in out
n: Order of reflection
d: Plane spacing 2
a
= 2 2 2
h k l
: Bragg Angle

Path difference must be integral multiples of the wavelength

in=out
 Braggs Law

n 1
d sin   d
2 sin  2

 Geometry of Bragg’s law

 The incident beam, the normal to the reflection plane,

and the diffracted beam are always co-planar.

 The angle between the diffracted beam and the

transmitted beam is always 2 (usually measured).

 Sin  cannot be more than unity; this requires

nλ < 2d, for n=1, λ < 2d

λ should be less than twice the d spacing we want to study

 Order of reflection

 Rewrite Bragg’s law λ=2 sin d/n

 A reflection of any order as a first order reflection from planes,
real or fictitious, spaced at a distance 1/n of the previous spacing
 Set d’ = d/n
λ=2d’ sin
 An nth order reflection from (hkl) planes of spacing d may be
considered as a first order reflection from the (nh nk nl) plane of
spacing d’ = d/n

*The term reflection is only notional due to symmetry between incoming and
outgoing beam w.r.t. plane normal, otherwise we are only talking of diffraction.
 Reciprocal lattice vectors
Used to describe Fourier analysis of electron concentration
of the diffracted pattern.

Every crystal has associated with it a crystal lattice and a

reciprocal lattice.

A diffraction pattern of a crystal is the map of reciprocal

lattice of the crystal.
 Real space Reciprocal space

Crystal Lattice Reciprocal Lattice

Crystal structure Diffraction pattern

Unit cell content Structure factor

x’
y y’

x’
x y’
 Reciprocal space

bc
a*  Reciprocal lattice of FCC is BCC
a  (b  c ) and vice versa
ca
b* 
a  (b  c ) 001

a b a
c*  010
a  (b  c ) b

100
Ewald sphere

1 2
d hkl 
1 k'
 2 hkl
 hkl
k
Ewald sphere

Limiting sphere
Ewald sphere

J. Krawit, Introduction to Diffraction in Materials Science and Engineering, Wiley New York 2001
 Two Circle Diffractometer

 For polycrystalline Materials

 Four Circle Diffractometer

For single crystals

2 Circle diffratometer  2 and 
3 and 4 circle diffractometer  2θ, ω, φ, χ
 6 circle diffractometer  θ, φ, χ and δ, γ, µ

www.serc.carleton.edu/
Hong et al., Nuclear Instruments and Methods in Physics Research A 572 (2007) 942
NaCl crystals in a tube facing X-ray beam
Powder Diffractometer
 (100)

(110)

(111)
(200)
(210)
(211)

(220)
(330)(221)
(310)
(311)
(222)
(320)
(321)
Calculated Patterns for a Cubic Crystal

(400)
(410)
 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
 Systematic Absences

Permitted Reflections

Simple Cubic (100), (110), (111), (200), (210), (211),

(220), (300), (221) ………
BCC (110), (200), (211), (220), (310), (222)….
FCC (111), (200), (220), (311)…..
 Diffraction Methods

Method Wavelength Angle Specimen

Laue Variable Fixed Single

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

 Determination of unknown crystal structures

 Powder Method

Incident Beam Sample

Film

• Useful for determining lattice parameters with high precision and for
identification of phases
 Indexing a powder pattern

Bragg’s Law
n = 2d sin

For cubic crystals

a
d hkl  2
h  k 2  l2
which gives rise to
sin 2 θ 2
 2
 S1 h k l
2 2 2
4a
θ (for front reflections) or which is a constant
2W
  S2 
θ  1   (for back reflections)
2 W
 Indexing
FCC; wavelength=1.54056Å
Simple
BCCCubic
SS1 (mm) () () sin2 h22+k
sin
2 2
 +l hsin
2/
22+k 22 2+k2sin
22+lh +l2 22/ Lattice
h22+k22+l22Parameter, a (Å)
1
(mm)
38 19.0 0.11 21 0.11
0.055
38 19.0 0.11 3 0.037 4.023
45 22.5 0.15 42 0.75
0.038
45 22.5 0.15 4 0.038 3.978
66 33.0 0.30 63 0.10
0.050
66 33.0 0.30 8 0.038 3.978
78 39.0 0.40 84 0.10
0.050
78 39.0 0.40 11 0.036 4.039 Not
NotSimple
BCC
83 41.5 0.45 5
10 0.09
0.045
Cubic
83 41.5 0.45 12 0.038 3.978
97 49.5 0.58 6
12 0.097
0.048
97 49.5 0.58 16 0.036 4.046
113 56.5 0.70 8
14 0.0925
0.050
113 56.5 0.70 19 0.037 But what is the lattice
4.023
118 59.0 0.73 9
16 0.081
0.046 parameter?
118 59.0 0.73 20 0.037 4.023
139 69.5 0.88 10
18 0.088
0.049
139 69.5 0.88 24 0.037 4.023
168 84.9 0.99 11
20 0.09
0.050
168 84.9 0.99 27 0.037 4.023
Not Constant
Constant; so it is FCC
Diffraction from a variety of materials

(From “Elements of X-ray

Diffraction”, B.D. Cullity,
Addison Wesley)
 Reality

Crystallite size can be

calculated using
Scherrer Formula

0.9
t
B cos  B

Instrumental broadening must be subtracted

(From “Elements of X-ray Diffraction”, B.D. Cullity, Addison Wesley)
 Intensity of diffracted beam
• polarization factor
• structure factor (F2)
• multiplicity factor
• Lorentz factor
• absorption factor
• temperature factor

For most materials the peaks and their intensity are

documented
 JCPDS
 ICDD
 Name and formula
Reference code: 00-001-1260
PDF index name: Nickel
Empirical formula: Ni
Chemical formula: Ni
Crystallographic parameters
Crystal system: Cubic
Space group: Fm-3m
Space group number: 225
a (Å): 3.5175
b (Å): 3.5175
c (Å): 3.5175
Alpha (°): 90.0000
Beta (°): 90.0000
Gamma (°): 90.0000
Measured density (g/cm^3): 8.90
Volume of cell (10^6 pm^3): 43.52
Z: 4.00
RIR: -
Status, subfiles and quality
Status: Marked as deleted by ICDD
Subfiles: Inorganic
Quality: Blank (B)
References
Primary reference: Hanawalt et al., Anal. Chem., 10, 475, (1938)
Optical data: Data on Chem. for Cer. Use, Natl. Res. Council Bull. 107
Unit cell: The Structure of Crystals, 1st Ed.
Stick pattern from JCPDS

http://ww1.iucr.org/cww-top/crystal.index.html
Actual Pattern

Lattice parameter, phase diagrams

Texture, Strain (micro and residual)
Size, microstructure (twins and
dislocations)

Bulk electrodeposited nanocrystalline nickel

 Powder X-ray diffraction
is essentially a misnomer and should be replaced by

Polycrystalline X-ray diffraction

 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
 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
 Presence of Multiple phases
d (Å) I/I
1
 More Complex
Pattern of Cu2O Remaining
3.01 Lines 5
 Several permutations combinations possible 2.47 I/I1 72
d (Å) I/I1 d
 e.g. d1; d2; and d3, the first three strongest lines (Å) 2.13 28
3.020 9 Observed Normalized
show several alternatives 2.09 * 100
Then take any of the two lines together 2.465 and 100 match 3.01 5 7
 1.80 * 52
 It turns out that 1st and 3rd strongest lies belong
2.135 37Patternto
2.47
for Cu
72 1.50 20
100
Cu and then all other peaks for Cu1.743 can be 1d (Å) 2.13I/I1 28
1.29 9
39
separated out 2.088 100 1.28 * 18
1.510 27 1.50 20 28
 Now separate the remaining lines and normalize 1.808 46 1.22 4
171.278 1.29 9 1.08 * 13 20
the intensities 1.287 20

 Look for first three lines and it turns out that

1.233 4 1.09the1.22
17 4 1.04 * 36

1.0436 5 0.98 5
phase is Cu2O 1.0674 2 0.98 5 7
0.9038 3 0.91 4

 If more phases, more pain to solve0.9795  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]
Texture in materials


 
 Also, if the direction [u1v1w1]
is parallel for all regions, the

 structure is like a single
However, the direction
crystal
 [u1v1w1] is not aligned for all
 regions, the structure is like a
 mosaic structure, also called
 as Mosaic Texture

 [uvw] i.e. perpendicular to

the surface of all grains is
parallel to a direction [uvw]
Pole Figures

(100) pole figures for a sheet material

(a) Random orientation (b) Preferred orientation
 Thin Film Specimen

B B
Grazing angle (very small, ~1-5)
Film or Coating

Substrate

 Smaller volume i.e. less intensity of the scattered

beam from the film
 Grazing angle
 Useful only for polycrystalline specimens
 Thin Film XRD
 Precise lattice constants measurements derived from 2- scans, which
provide information about lattice mismatch between the film and the
substrate and therefore is indicative of strain & stress
 Rocking curve measurements made by doing a q scan at a fixed 2 
angle, the width of which is inversely proportionally to the dislocation
density in the film and is therefore used as a gauge of the quality of the
film.
 Superlattice measurements in multilayered heteroepitaxial structures,
which manifest as satellite peaks surrounding the main diffraction peak
from the film. Film thickness and quality can be deduced from the data.
 Glancing incidence x-ray reflectivity measurements, which can
determine the thickness, roughness, and density of the film. This
technique does not require crystalline film and works even with
amorphous materials.
 Thin Films Specimens

B1B2
Diffraction
i.e. from hkl
No Diffraction plane
from hkl
occurs
plane
B1B B2
B

(hkl) plane of the Single Crystal Substrate

substrate

 If the sample and substrate is polycrystalline, then

problems are less
 But if even if one of them is oriented, problems arise
 In such situations substrate alignment is necessary
 Oriented thin films
SrTiO3 (100)


008

0014
006

0016
0010
0012

0022


0018
004

0028
0026

0024
0020
△
△ *
 Bismuth Titanate thin △

films on oriented

Log Intensity (a.u.)

SrTiO3 substrates 10 20 30 40 50 60 70 80 90


 Only one type of peaks

2216
△ △
 It apparent that films
SrTiO3 (110)
are highly oriented
10 20 30 40 50 60 70 80 90


4016/
0416
△
014

SrTiO3 (111)
10 20 30 40 50 60 70 80 90
o
2 ( )
 Degree of orientation
[uvw] corresponding
to planes parallel to
Film the surface
Substrate
Side view

But what if the planes when looked from top have random orientation?

Top view
 Pole Figure
SrTiO3 (100) SrTiO3 (110) SrTiO3 (111)

2 1

1
1 2
2
1 3
2 1
1 2 3
1
2 3 2
2
1 3

 4 Peaks at ~50  2 sets of peaks at ~ 5, 65  3 sets of peaks

 Excellent in-plane and 85° at ~ 35 and 85°
orientation  Indicating a doublet or  indicating a
opposite twin growth triplet or triple
twin growth
(117) Pole Figures for Bismuth Titanate Films
 Texture Evolution

3 (100) planes
Film inclined at 54.7°
to (110) plane,
SrTiO3 (100) Two (100) planes
separated by
inclined at 45° to (110)
120°
plane in opposite
directions STO(111)

BNdT(001)
STO [100] 45
54.7°
STO(110)
STO(111)

STO(100)

BNdT/SrTiO3 (100) BNdT/SrTiO3 (110) BNdT/SrTiO3 (111)

 Rocking Curve
 An useful method for evaluating the quality of oriented samples such as
epitaxial films
  is changed by rocking the sample but B is held constant
 Width of Rocking curve is a direct measure of the range of orientation present in
the irradiated area of the crystal

(0010) Rocking curve of (001)-

(2212) SrBi
oriented Rocking
2Ta2Ocurve
9 thin of (116)-
film
oriented SrBi2Ta2O9 thin film
Normal
FWHM = 0.07°

(a.u.)
(a.u.)
FWHM = 0.171°

Intensity
B 
Intensity

32.432.4 33.0
32.6 32.832.8
17.833.233.2
17.4 17.6 32.6 17.8 18.0
33.0 18.2
17.5 17.6 17.7
 ()  ()
Order Disorder Transformation
 Structure factor is dependent on the presence
of order or disorder within a material
 Present in systems such as Cu-Au, Ti-Al, Ni-
Fe
 Order-disorder transformation at specific
compositions upon heating/cooling across a
critical temperature
 Examples: Cu3Au, Ni3Fe
 Order Disorder Transformation
 Structure factor is dependent on the presence
of order or disorder within a material.
 Complete Disorder
 Example: AB with A and B atoms
randomly distributed in the lattice
 Lattice positions: (000) and (½ ½ ½)
Atomic scattering factor
favj= ½ (fA+fB)
Structure Factor, F, is given by
F = Σf exp[2i (hu+kv+lw)]
= favj [1+e( i (h+k+l))] A
= 2. favj when h+k+l is even B
= 0 when h+k+l is odd
 The expected pattern is like a BCC crystal
 Order Disorder Transformation
 Complete Order
 Example: AB with A at (000) and B at (½ ½ ½)

Structure Factor, F, is given by

F = fA e[2i (h.0+k.0+l.0)]+ fA e[2i (h. ½+k. ½+l. ½)]

= fA+fB when h+k+l is even
= fA-fB when h+k+l is odd

 The expected pattern is not like a BCC crystal, A

rather like a simple cubic crystal where all the
B
reflections are present.
 Extra reflections present are called as
superlattice reflections
Order-Disorder Transformation

Disordered Cu3Au

Ordered Cu3Au
Instrumentation
 Diffractometer

 Source

 Optics

 Detector

Incident Beam Part Diffracted Beam Part

Sample Diffracted Beam

Optics
Source Incident Beam Detector
Optics
 Geometry and Configuration
 Theta-Theta Source and detector move θ, sample fixed

 Theta-2Theta Sample moves θ and detector 2θ , source fixed

 Vertical configuration Horizontal sample

 Horizontal configuration Vertical sample

Incident Beam Part Diffracted Beam Part

Sample Diffracted Beam

Optics
Source Incident Beam Detector
Optics
 Sample translation

 XYZ translation

 Z translation sample alignment

 Sample exactly on the diffractometer circle

 Knife edge or laser

 Video microscope with laser

 XY movement to choose
area of interest
 X-ray generation
 X-ray tube (λ = 0.8-2.3 Ǻ)

 Rotating anode (λ = 0.8-2.3 Ǻ)

 Liquid metal

 Synchrotron (λ ranging from infrared to X-ray)

X-ray tube X-rays
Be window

W cathode Metal anode

Electrons

Rotating anode
Small angle anode Large angle anode

Small focal spot Large focal spot

 Rotating anode of W or Mo for high flux

 Microfocus rotating anode 10 times brighter

 Liquid anode for high flux 100 times brighter

and small beam size

 Gallium and Gallium, indium, tin alloys

 Synchrotron provides intense beam but access is limited

 Brighter than a thousand suns

 Synchrotron
 High brilliance and coherence

 X-ray bulb emitting all radiations from IR to X-rays

http://www.coe.berkeley.edu/AST/srms
 Moving charge emits radiation

 Electrons at v~c

 Bending magnet, wiggler and undulator

 Straight section wiggler and undulator

 Curved sections Bending magnet

 Filter to remove Kβ For eg. Ni filter for Cu Kβ

 Reduction in intensity of Kα

 Choice of proper thickness

 Slits To limit the size of beam (Divergence slits)

To alter beam profile

(Soller slit angular divergence )

 Narrow slits Lower intensity

+
Narrow peak
Mirror focusing and remove Kα2

Mono-chromator remove Kα2

Si Graphite
Beam Profile
Mirror Parallel beam
Source

Soller slit

Detector Mirror

Sample

Para-focusing Source

Detector

Sample
 Point focus Source

Detector

Sample
Comparison
Parallel beam Para-focusing
X-rays are aligned X-rays are diverging
Lower intensity for bulk Higher intensity
samples
Higher intensity for small Lower intensity
samples
Instrumental broadening Instrumental broadening
independent of orientation dependent of orientation of
of diffraction vector with diffraction vector with
specimen normal specimen normal

Suitable for GI-XRD Suitable for Bragg-Brentano

Texture, stress Powder diffraction
 Detectors

 Single photon detector (Point or 0D)

 scintillation detector NaI
 proportional counter, Xenon gas
 semiconductor
 Position sensitive detector (Linear or 1D)
 gas filled wire detectors, Xenon gas
 charge coupled devices (CCD)
 Area detectors (2D)
 wire
 CCD
 3D detector

Photoelectron or Photomultiplier tube or

X-ray photon Electrical signal
Electron-hole pair amplifier
 Resolution: ability to distinguish between energies

 Energy proportionality: ability to produce signal proportioanl to

energy of x-ray photon detected

 Sensitivity: ability to detect low intensity levels

 Speed: to capture dynamic phenomenon

 Range: better view of the reciprocal space

 Data collection and analysis

 Choose 2θ range

 Step size and time per step

 Hardware: slit size, filter, sample alignment

 Fast scan followed with a slower scan

 Look for fluorescence

 Collected data: Background subtraction, Kα2 stripping

 Normalize data for comparison I/Imax
 Summary

 X-ray Diffraction is a very useful to characterize materials

for following information
 Phase analysis
 Lattice parameter determination
 Strain determination
 Texture and orientation analysis
 Order-disorder transformation
 and many more things
 Choice of correct type of method is critical for the kind of
work one intends to do.
 Powerful technique for thin film characterization