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
Rntgen
1912: Discovery of X-ray Diffraction by
Crystals: von Laue
1912: Braggs 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 Moseleys Law

C(Z )
I K Bi (V V k) n

SWL
 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 Braggs law: strong
intensities of the scattered beam :Diffraction
No scattering along directions not satisfying Braggs 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

sin n sin 2n 1
n = 1, 2,..
a
n = 0, 1,.. 2a
Youngs Double slit experiment

d sin = m, m = 1,2,3.. Constructive Interference

d sin = (m+), m = 1,2,3.. Destructive Interference

Interference
Phase Difference = 0 Phase Difference = 90

Phase Difference = 180

Interference and Diffraction
 Braggs 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 Braggs 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

n < 2d, for n=1, < 2d

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

 Order of reflection

Rewrite Braggs law =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
=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

bc
a* Reciprocal lattice of FCC is BCC
a (b c ) and vice versa
ca
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 2, , ,
6 circle diffractometer , , and , ,

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

Braggs Law
n = 2d sin

For cubic crystals

a
d hkl 2
h k 2 l2
which gives rise to
sin 2 2
2
S1 h k l
2 2 2
4a
(for front reflections) or which is a constant
2W
S2
1 (for back reflections)
2 W
 Indexing
FCC; wavelength=1.54056
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 ()
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 (): 3.5175
b (): 3.5175
c (): 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 () (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
Search JCPDS manual to find the d group belonging to the
strongest line: between 2.84-2.80
There are 17 substances with approximately similar d2 but only 4
have d1: 2.82
Out of these, only NaCl has d3: 1.63
It is NaClHurrah
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 () I/I
1
More Complex
Pattern of Cu2O Remaining
3.01 Lines 5
Several permutations combinations possible 2.47 I/I1 72
d () I/I1 d
e.g. d1; d2; and d3, the first three strongest lines () 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 () 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

B1B2
Diffraction
i.e. from hkl
No Diffraction plane
from hkl
occurs
plane
B1B 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 ( )
Atomic scattering factor
favj= (fA+fB)
Structure Factor, F, is given by
F = f exp[2i (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 ( )

Structure Factor, F, is given by

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

= 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 , sample fixed

Theta-2Theta Sample moves and detector 2 , 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 ( = 0.8-2.3 )

Rotating anode ( = 0.8-2.3 )

Liquid metal

Synchrotron ( 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 K For eg. Ni filter for Cu K

Reduction in intensity of K

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 K2

Mono-chromator remove K2

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 2 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, K2 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