X-ray Diffraction:

Basics and Applications

Dr. T. K. Chaudhuri, Professor and Head

Dr. K. C. Patel Research and Development Centre
INTRODUCTION:
HISTORY
 What are X-rays?

Soft X-rays: 0.12 to 12 keV (10 to 0.10 nm)

Hard X-rays: 12 to 120 keV (0.10 to 0.01 nm) -------- penetrates solid
objects; used for diagnostic radiography and crystallography.
 History of X-ray : Timeline
1895 X-rays discovered by Roentgen

1914 First diffraction pattern of a crystal made by Knipping and

von Laue

1915 Theory to determine crystal structure from diffraction

pattern developed by Bragg

1916 First to study polycrystalline powder : Debye and Scherrer

1953 DNA structure solved by Watson and Crick

Now Diffraction improved by computer technology; methods

used to determine atomic structures and in medical
applications
• Wilhelm Conrad Röntgen
discovered X-Rays in 1895
• X-ray : unknown ray
• Won 1901 Nobel prize in
Physics
Wilhelm Conrad Röntgen (1845-1923)

Bertha Röntgen’s Hand 8 Nov, 1895 A modern radiograph of a hand

 The first kind of scatter process to be
recognised was discovered by Max
von Laue who was awarded the
Nobel prize for physics in 1914 "for
his discovery of the diffraction of X-
rays by crystals". His collaborators
Walter Friedrich and Paul Knipping
took the picture on the bottom left in
1912. It shows how a beam of X-rays
Max von Laue (1897-1960) is scattered into a characteristic
pattern by a crystal. In this case it is
copper sulphate.
The X-ray diffraction pattern of
a pure substance is like a
fingerprint of the substance.
The powder diffraction method
is thus ideally suited for
characterization and
identification of polycrystalline
phases.
 The father and son team of Sir
Bragg’s Law William Henry and William
Lawrence Bragg were awarded the
Nobel prize for physics "for their
services in the analysis of crystal
structure by means of Xrays“ in
1915.
Bragg's law was an extremely
Sir William Henry
Bragg (1862-1942)
William Lawrence
Bragg (1890-1971)
important discovery and formed
the basis for the whole of what is
now known as crystallography.
This technique is one of the most
widely used structural analysis
techniques and plays a major role
in fields as diverse as structural
biology and materials science.
BASICS
 Crystalline materials are characterized by the
orderly periodic arrangements of atoms.
The (200) planes The (220) planes
of atoms in NaCl of atoms in NaCl

• 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.
The atoms in a crystal are a periodic array of coherent
scatterers and thus can diffract X-rays

• Diffraction occurs when each object in a periodic array scatters

radiation coherently, producing concerted constructive
interference at specific angles.
• The electrons in an atom coherently scatter light.
– The electrons interact with the oscillating electric field of the
light wave.
• Atoms in a crystal form a periodic array of coherent scatterers.
– 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
• X Rays are also reflected, scattered incoherently, absorbed,
refracted, and transmitted when they interact with matter.
 Bragg’s law

  2d hkl sin   

d hkl d hkl
• Bragg’s law: condition for constructive interference
• dhkl determines peak positions.
• Type of atoms determines peak intensity
 X-RAY DIFFRACTION METHODS

X-Ray Diffraction Method

Laue Rotating Crystal Powder

Orientation Lattice constant Lattice Parameters

Single Crystal Single Crystal Polycrystal (powdered)
Polychromatic Beam Monochromatic Beam Monochromatic Beam
Fixed Angle Variable Angle Variable Angle
 Single Crystals
Individual reciprocal lattice points (with specific hkl) projected onto the
detector

Used to determine the electron density within a unit cell

 Powder XRD
Random crystallites combine to form spheres of reflection
spheres will always intersect the Ewald sphere, at the detector:
diffraction rings at angle 
 Debye Scherrer Camera
A very small amount of powdered material is sealed into a fine
capillary tube made from glass that does not diffract x-rays.

The specimen is placed in the Debye Scherrer camera and is

accurately aligned to be in the centre of the camera. X-rays enter the
camera through a collimator.
• Powder Diffraction or polycrystalline diffraction
Samples: powder, sintered pellets, coatings, engine blocks, …
• True random sample results into continuous Debye cone.
• linear diffraction pattern: detector scans through an arc that
intersects each Debye cone at a single point
MEASUREMENT OF XRD:
DIFFRACTOMETERS
 Bragg-Brentano geometry

Detector
X-ray tube

  

• Incident angle  is always ½ of the detector angle 2 .

:2 instrument, the tube is fixed, the sample rotates at  °/min

and the detector rotates at 2 °/min.
: instrument, the sample is fixed and the tube rotates at a rate
- °/min and the detector rotates at a rate of  °/min.
Phillips X’Pert

1.Quantitative Phase
Analysis and Transmission
2.Thin film analysis
3.Reflectivity
4.Small angle Xray scattering
Rigaku Ultima IV

1. Powder diffraction
2. Thin film diffraction
3. Small angle
scattering
4. In-plane scattering
Bruker D8 Advance

1. powder samples
2. crystallite size determination
3. micro strain analysis
4. residual stress analysis
5. preferred orientation
Shimadzu LabX XRD-6000

1. Powder Diffraction
2. Independent dual axis θ-2θ
linkage drive
3. independent 2θ axis and θ
axis drives are selectable
Scintag xrd 2000 pole figure

1.Quantitative Phase
Analysis and Transmission
2.Thin film analysis
3.Reflectivity
4.Small angle Xray scattering
5. Pole Figure (phi-omega scan)
 Bruker D2 Phaser
1. Faster desktop unit
2. Powder diffraction
3. No external chiller unit
4. Accurate and faster solid state detector
5. Useful for cement, industrial mineral, chemistry, pharma
applications
Rigaku Miniflex II
1. General XRD
2. Phase composition analysis
X-ray diffractographs: Analysis
 Bragg-Brentano diffractometer
For single crystals

2

Only those family of planes whose normal bisect the angle made by
incident and reflected rays will give peaks
Here only (100) and (200) but not (110)
 For polycrystalline / powder sample

2 2 2

• Randomly oriented crystallites throughout: peaks due to all

families of planes
• Basic assumption of powder diffraction: equal no. of crystallites
for all families of planes oriented to diffract
 X-Ray Diffraction pattern Particle size
and defects

Peak shapes

Peak relative
intensities

Background Atomic
Peak distribution in
positions the unit cell
10 20 30 40
2

Unit cell Diffuse scattering,

c Symmetry sample holder,
matrix, amorphous
b and size phases, etc...
a
Powder diffraction data consists of a record of photon
intensity versus detector angle 2.
• Diffraction data can be reduced to a list of peak positions and intensities
– Each dhkl corresponds to a family of atomic planes {hkl}
– individual planes cannot be resolved- this is a limitation of powder
diffraction versus single crystal diffraction
Raw Data Reduced dI list
Position Intensity
[°2q] [cts] hkl dhkl (Å) Relative
25.2000 372.0000 Intensity
(%)
25.2400 460.0000
25.2800 576.0000 {012} 3.4935 49.8
25.3200 752.0000
{104} 2.5583 85.8
25.3600 1088.0000
25.4000 1488.0000 {110} 2.3852 36.1
25.4400 1892.0000
{006} 2.1701 1.9
25.4800 2104.0000
25.5200 1720.0000 {113} 2.0903 100.0
25.5600 1216.0000
{202} 1.9680 1.4
25.6000 732.0000
25.6400 456.0000
25.6800 380.0000
25.7200 328.0000
 Diffraction patterns are best reported using dhkl and
relative intensity rather than 2 and absolute intensity.

Why?

- 2 depends on instrumental characteristics such as 

- dhkl is an intrinsic, instrument-independent, material property

- absolute intensity can vary due to instrumental and

experimental parameters
- relative intensities should be instrument independent.

Peak areas are much more reliable than peak heights as a measure
of intensity
APPLICATIONS OF X-ray Diffraction
 Application of XRD
Differentiation between crystalline and amorphous materials

Intensit
Gas

y
Diffraction angle 2

Intensit
Liquid
Amorphous

y
Diffraction angle 2

Crystal
Intensit
y

Diffraction angle 2
 Applications of Powder XRD
• Phase Composition of a Sample
– Quantitative Phase Analysis: relative amount of each phase

• Unit cell lattice parameters and Bravais lattice symmetry

– Index peak positions
– Lattice parameters also effect of stress and doping
– Residual Strain (macrostrain)

• Crystal Structure
– By full profile Rietveld refinement

• Epitaxy/Texture/Orientation

• Crystallite Size and Microstrain

– by peak broadening
– Other defects (stacking faults, etc.) from peak shapes and width
 Diffraction peak parameters and their applications
Peak position
-Unit cell parameter
refinement
-Pattern indexing
-Space group determination
-Anisotropic thermal
exapansion
-Microstress analysis
(sin2method)
-Phase identification
Intensity
-Phase abundance
-Reaction kinetics
-crystal structure analysis
(full profile)
-phase identification
-texture analysis
Width and shape
-Instrumental resolution
function
-Microstructure
-Crystallite size
-Size distribution
-Lattice distortion
-Structure mistakes
-Dislocations
-Composition gradient
Non ambient and
dynamic diffraction
-Reaction kinetics
 Phase Identification

• Diffraction pattern of each phase is its fingerprint

Phases with the same chemical composition can have

drastically different diffraction patterns.

peak position and intensity used to detect particular phase

 Powder Diffraction File (PDF) or JCPDS File

• Maintained by Joint Committee on Powder Diffraction Standards

• Standard for thousands of crystalline phases.
• Over 200,000 diffraction patterns.
• Quicker phase search by computer assistance
• Other useful information like reference also
 Quantitative Phase Analysis

• To Know amount of each 60

phase 50
• Relative peak intensity

I(phase a)/I(phase b) ..
proportional to relative 40
phase amount 30
• Thus quantitative phase 20
analysis: to find const. of
proportionality 10
• RIR method: fast and semi- 0
quantitative results 0 0.2 0.4 0.6 0.8 1
• Whole pattern
X(phase a)/X(phase b)
fitting/Rietveld refinement:
accurate but complicated
 Unit Cell Lattice Parameter Refinement

• By accurate measurement of peak positions over long range

• measure peak positions with a peak search algorithm or profile
fitting
• profile fitting is more accurate but more time consuming
• Can be use to quantify the effect due to alloying, substitutional
doping, temperature and pressure, etc
• identify and correct for systematic errors such as specimen
displacement and zero shift
 Crystallite Size and Microstrain
• Both small crystallite (<120nm) & microstrain cause peak
broadening
• Crystallite size from peak broadening using Scherrer relation
• must know contribution of peak width from the instrument
• Williamson-Hull plot can let you separate microstrain and crystallite
size

K
B2  
00-043-1002> Cerianite-
2-
CeO

L cos 
Intensity (a.u.)

23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41
2 (deg.)
 What is Crystallite size?

Crystallite size
βｓ Particle size
 Preferred Orientation (texture)

• Preferred orientation of crystallites can create a systematic

variation in diffraction peak intensities
– can qualitatively analyze using a 1D diffraction pattern
– a pole figure maps the intensity of a single peak as a
function of tilt and rotation of the sample
• this can be used to quantify the texture

10.0 (111) 00-004-0784> Gold - Au

8.0
Intensity(Counts)

(311)
6.0 (200)
(220)
4.0

2.0
(222)
(400)
3
x10
40 50 60 70 80 90 100
Two-Theta (deg)
COMPONENTS OF X-RAY DIFFRACTOMETER
 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
Parafocusing geometry of Bragg-Brentano Diffractometer

• Detector moves maintaining 2

angle wrt incident ray

• Sample maintains angle  wrt

incident ray

• Parafocussing: reflected rays

from again collimated onto
detector
F: X-ray source
DS: incident-beam divergence-limiting slit
SS: Soller slit assembly
S: sample
RS: diffracted-beam receiving slit
C: monochromator crystal
AS: the anti-scatter slit
 X-radiation sources

H2O In H2O Out

• Sealed X-ray tubes operate at
1.8 to 3 kW.
• Rotating anode X-ray tubes
have efficient heat distribution: Cu ANODE
operate at 9-18 kW >produce Be
window
Be
window
much more flux . e-
XRAYS XRAYS
FILAMENT
– X-ray generation: rapid (cathode)

metal
decceleration of e’s onto W
target glass
(vacuum) (vacuum)

– The target must be water

cooled.
– The target and filament must
be contained in a vacuum.
AC CURRENT
 X rays production

• Electrons from the filament strike the target anode, producing

characteristic radiations of anode via the photoelectric effect.
• Monochromator for filtering particular wavelength

K
L
M
 Spectral Contamination in Diffraction Patterns

K1 K1

K2 K2
K1

K2

• The K1 & K2 doublet will almost always be present

– Very expensive optics can remove the K2 line
W L1 – K1 & K2 overlap heavily at low angles and are more
K separated at high angles
• W lines form as the tube ages: the W filament contaminates
the target anode and becomes a new X-ray source
• W and K lines can be removed with optics
 Wavelengths for X-Radiation are Sometimes Updated
Copper Bearden Holzer et al. Cobalt Bearden Holzer et al.
Anodes (1967) (1997) Anodes (1967) (1997)
Cu K1 1.54056Å 1.540598 Å Co K1 1.788965Å 1.789010 Å
Cu K2 1.54439Å 1.544426 Å Co K2 1.792850Å 1.792900 Å
Cu K 1.39220Å 1.392250 Å Co K 1.62079Å 1.620830 Å

Molybdenum Chromium
Anodes Anodes
Mo K1 0.709300Å 0.709319 Å Cr K1 2.28970Å 2.289760 Å

Mo K2 0.713590Å 0.713609 Å Cr K2 2.293606Å 2.293663 Å

Mo K 0.632288Å 0.632305 Å Cr K 2.08487Å 2.084920 Å
 X-ray Shutter

• X-rays exit the tube through X-ray

transparent Be windows.

• X-Ray safety shutters contain the beam

so that you may work in the
diffractometer without being exposed
to the X-rays.

• Being aware of the status of the

shutters is the most important factor in
working safely with X rays.
 Requirement of X-ray optics

  2d hkl sin 

• X Rays from an X-ray tube are:

– divergent
– contain multiple characteristic wavelengths as well as
Bremmsstrahlung radiation
• Optics are used to:
– limit divergence of the X-ray beam
– refocus X rays into parallel paths
– remove unwanted wavelengths
 Divergence slits

• The slits block X-rays that have too

great a divergence.
• The size of the divergence slit
influences peak intensity and peak
shapes.
• Narrow divergence slits:
– reduce the intensity of the X-ray
beam
– reduce the length of the X-ray beam
hitting the sample
– produce sharper peaks
• the instrumental resolution is
improved so that closely spaced
peaks can be resolved.
 Monochromators

• crystal monochromator: to select one wavelength of radiation

and provide energy discrimination.

• An incident-beam monochromator might be used to select only

K1 radiation for the tube source.

• A diffracted-beam monochromator, may be used to remove

fluoresced photons, K, or W-contimination photons from
reaching the detector.
 Other optics:

• limit divergence of the X-ray

Parallel Plate Collimator & Soller
beam Slits block divergent X-rays, but
– Divergence limiting slits do not restrict beam size like a
– Parallel plate collimators divergent slit
– Soller slits
• refocus X rays into parallel paths
– “parallel-beam optics”
– parabolic mirrors and capillary
lenses
– focusing mirrors and lenses
• remove unwanted wavelengths
– monochromators
– K filters Göbel Mirrors and capillary
lenses collect a large portion of
the divergent beam and refocus it
into a nearly parallel beam
 Detectors
• point detectors
– observe one point of space at a time
• slow, but compatible with most/all optics
– scintillation and gas proportional detectors count all photons,
within an energy window, that hit them
– Si(Li) detectors can electronically analyze or filter wavelengths
• position sensitive detectors
– linear PSDs observe all photons scattered along a line from 2 to 10°
long
– 2D area detectors observe all photons scattered along a conic
section
– gas proportional (gas on wire; microgap anodes)
• limited resolution, issues with deadtime and saturation
– CCD
• limited in size, expensive
– solid state real-time multiple semiconductor strips
• high speed with high resolution, robust
SAMPLE / SPECIMEN PREPARATION
 Preparing a powder specimen

• An ideal powder sample should have many crystallites in random

orientations
– the distribution of orientations should be smooth and equally
distributed amongst all orientations
• If the crystallites in a sample are very large, there will not be a smooth
distribution of crystal orientations. You will not get a powder average
diffraction pattern.
– crystallites should be <10m in size to get good powder statistics
• Large crystallite sizes and non-random crystallite orientations both
lead to peak intensity variation
– the measured diffraction pattern will not agree with that expected
from an ideal powder
– the measured diffraction pattern will not agree with reference
patterns in the Powder Diffraction File (PDF) database
 Important characteristics of samples for XRPD

• a flat plate sample for XRPD should have a smooth flat surface
– if the surface is not smooth and flat, X-ray absorption may
reduce the intensity of low angle peaks
– parallel-beam optics can be used to analyze samples with
odd shapes or rought surfaces
• Densely packed
• Randomly oriented grains/crystallites
• Grain size less than 10 microns
• ‘Infinitely’ thick
XRD EXAMPLES
XRD of ZnO powder : polycrystalline ZnO powder JCPDF:36 -1451
Miller
2 indices 2 I/Io
I/Io % d, nm (hkl) d (nm)
(degree) (degree) %
31.569 56.91 0.2831 (100) 31.769 57 0.2814
34.228 61.39 0.2617 (002) 34.421 44 0.2603
36.054 100.00 0.2489 (101) 36.252 100 0.2475
47.281 22.60 0.1920 (102) 47.538 23 0.1911
56.396 38.92 0.1630 (110) 56.602 32 0.1624

62.607 34.37 0.1482 (103) 62.862 29 0.1477

66.124 5.52 0.1411 (200) 66.378 4 0.1407
67.704 28.75 0.1382 (112) 67.961 23 0.1378
68.997 12.50 0.1359 (201) 69.098 11 0.1358
72.295 2.91 0.1305 (004) 72.560 2 0.1301
76.828 3.84 0.1239 (202) 76.953 4 0.1238
81.207 2.17 0.1183 (104) 81.368 1 0.1181
89.303 7.95 0.1096 (203) 89.605 7 0.1093
92.487 2.73 0.1066 (210) 92.781 3 0.1063
95.050 8.83 0.1044 (211) 95.301 6 0.1042

98.802 2.97 0.1014 (114) 98.609 4 0.1015

102.742 3.55 0.0986 (212) 102.942 2 0.0984
103.981 6.22 0.0977 (105) 104.130 5 0.0976
107.313 0.65 0.0956 (204) 107.426 1 0.0955
110.033 3.82 0.0940 (300) 110.388 3 0.0938
ZnO flowers 3-5 m
116.078 7.98 0.0907 (213) 116.274 8 0.0906
(302) 121.567 4 0.0882
(006) 125.183 1 0.0867
(205) 133.925 3 0.0837
(106) 136.513 1 0.0829
(214) 138.505 2 0.0823
(220) 142.910 3 0.0812
 ZnO nanorod-array films deposited on glass substrate: preferred orientation

Texture Coefficient, TC
TC(002) = I(002)/I o(002)
____________________________________________________________________________________________________________

1/3 {I(100)/Io(100)+I(002)/Io(002) + I(101)/Io(101)}

where
I = the measured intensity;
Io = the standard intensity (JCPDS: 36-1451)

Aligned ZnO nanorod-array

ZnO rod-array film JCPDF:36-1451

Miller
2 I/Io indices 2 I/Io
d, nm (hkl) d (nm)
(degree) % (degree) %
31.80 2.31 0.2852 (100) 31.769 57 0.2814
35.10 100 0.2595 (002) 34.421 44 0.2603
36.8 2.21 0.2482 (101) 36.252 100 0.2475
48.1 2.11 0.1944 (102) 47.538 23 0.1911
63.45 6.0 0.1535 (103) 62.862 29 0.1477
200 nm
73.1 3.5 0.1374 (004) 72.560 2 0.1301
 Biaxially textured YBa2Cu3O7 (YBCO) film on STO substrate
Spray pyrolysis, Thickness: 2 μm, JC ~ 1 MA/sq. cm, Orthorhombic
3
80x10
50x103
70 YBCO, (005) reflection

(006) + STO
40 FWHM = 1°
Intensity (cps)

60
Out of plane

Intensity (cps)
(005)
(003)+ STO

50 30
40 texturing /
20
orientation
(002)

30
(001)

20 10

(007)
(004)

<--(008)
10
0
0 17 18 19 20 21 22°
10 20 30 40 50 60°
Omega (degrees)
2 Theta (degrees)

3
50x10
YBCO (103) reflection

40 FWHM = 1.2°
In plane
texturing / Intensity (cps)
30

orientation 20

10

YBCO, (103) reflection

0
0 50 100 150 200 250 300 350°
Phi (degrees)
XRD of ZnO nanopowder : use of Scherrer equation

FWHM  = 36.5 -35.93 = 0.57o= ~0.01 rad.

Peak Position 2 = 36.218o
= 18.019o= ~ 0.316 rad.; Cos  = 0.999
Scherrer relation (<100 nm)
d K  
K = 0.89, λ =1.5406 ×10-10 m  cos
Crystallite size = 15 nm
 Varying Irradiated area of the sample

• the area of your sample that is illuminated by the X-ray beam

varies as a function of:
– incident angle of X rays
– divergence angle of the X rays
• at low angles, the beam might be wider than your sample
– “beam spill-off”
 The constant volume assumption

• In a polycrystalline sample of ‘infinite’ thickness, the change in the

irradiated area as the incident angle varies is compensated for by the
change in the penetration depth
• These two factors result in a constant irradiated volume
– (as area decreases, depth increase; and vice versa)
• This assumption is important for many aspects of XRPD
– Matching intensities to those in the PDF reference database
– Crystal structure refinements
– Quantitative phase analysis
• This assumption is not necessarily valid for thin films or small
quantities of sample on a ZBH
 Sources of Error in XRD Data

• Sample Displacement
– occurs when the sample is not on the focusing circle
(or in the center of the goniometer circle)
– Can be minimized by using a zero background sample
holder
– Can be corrected by using an internal calibration
standard
– Can be analyzed and compensated for with many data
analysis algorithms
– can be eliminated by using parallel-beam optics
 Texture analysis Using Pole figures
Totally different setup: 4 circle goniometer
 Scan Axes



ψ

Sample

2

Detector Source
 Pole Figures
z-axis
(sample normal)

(hkl) plane
Projected
distance from
Equatorial plane origin is given
Projected position
 of the (hkl) plane by:
-axis r tan (psi/2)
(where r is the
radius )

South pole

Schematic diagram showing the construction of a pole figure.

 Choosing which planes
• Often necessary to use a number of different crystal planes to
determine a complicated texture.
• The planes should be chosen from the theta 2 theta pattern. We
need:
• strongly diffracting planes (high intensity in theta 2 theta)
• discrete peaks preferably at 2 theta values between 20 degrees
and 50 degrees for optimum results.
(110)

o x Ag o
LaNiO3

(200)
(111)

x x

(200)
Holder

(211)
(111)
(100)

(210)
o
Holder

o o
o
 Interpretation
•No general methods
• sometimes by visual comparisons with known sample
•an unknown texture or combination of textures can be identified by
carrying out a series of pole figures and calculating an Orientation
Distribution Function (ODF).
Example: c-axis aligned superconducting thin films.

(a) (b)

 

Biaxial Texture (105 planes) Random in-plane alignment