X-ray Diffraction

(301)
(310)
Intensity

(611) (321)
(600) (411) (002)
(200) (110) (400)

2 degrees
 CHARACTERIZATION OF THE STRUCTURE OF SOLIDS

Three main techniques:

X-ray diffraction Electron diffraction Neutron diffraction

Single crystal
Powder
Principles of x-ray diffraction
X-rays are passed through a crystalline material and the patterns produced give
information of size and shape of the unit cell
X-rays passing through a crystal will be bent at various angles: this process is called
diffraction

X-rays interact with electrons in matter, i.e. are scattered by the electron clouds of
atoms

The angles at which x-rays are diffracted depends on the distance between adjacent
layers of atoms or ions.
 Scattering of x-rays by crystallographic planes
We need to consider how x-rays are diffracted by parallel crystallographic planes

incident x-rays  diffracted x-rays

lattice planes d

atoms on
lattice planes

X-rays diffracted in phase will give a signal. “In phase” means that the peak of one
wave matches the peak of the following wave
A single monochromatic wave (of any type) is incident on aligned planes of lattice
points, with separation d, at angle θ,

There will be a path difference

between the ray that gets reflected
along AC' and the ray that gets
transmitted, then reflected, along AB
and BC respectively. This path
difference is:

(AB + BC) - AC'

The two separate waves will arrive at a point with the same phase, and hence
undergo constructive interference, if and only if this path difference is equal to any
integer value of the wavelength

(AB + BC) - AC' = n

Expressing AB, BC and AC’ in terms of d and 

AB = BC = d/sin AC = 2d/tan AC' = (2d/sin)cos2

 According to the 2θ deviation, the phase shift causes:

constructive interferences. destructive interferences.

The constructive interference condition is expressed by by Bragg's law:

n = 2dsin

where n is an integer number, λ is the wavelength of the X-rays, d is the spacing

between the planes in the atomic lattice, and θ is the angle between the incident
ray and the scattering planes.
A single monochromatic wave (of any type) is incident on aligned planes of lattice
points, with separation d, at angle θ,

AB = BC = d/sin

AC = 2d/tan

AC' = (2d/sin)cos2

(AB + BC) - AC' = n

2d/sin(1-cos2) = n

2dsin = n
 Inter-Planar Spacing, dhkl, and Miller Indices

The inter-planar spacing (dhkl) between crystallographic planes belonging

to the same family (h,k,l) is denoted (dhkl)

Distances between planes defined by the same set of Miller indices are
unique for each material

dhkl

d'h’k’l’

Inter-planar spacings can be measured by x-ray diffraction (Bragg’s Law)

 Inter-Planar Spacing, dhkl, and Miller Indices

The inter-planar spacing (dhkl) between crystallographic planes belonging

to the same family (h,k,l) is denoted (dhkl)

Distances between planes defined by the same set of Miller indices are
unique for each material

dhkl

Inter-planar spacings can be measured by x-ray diffraction (Bragg’s Law)

The lattice parameters a, b, c of a unit cell can then be calculated

The relationship between d and the lattice parameters can be determined

geometrically and depends on the crystal system

Crystal system dhkl, lattice

parameters and
Miller indices
Cubic 1 h2  k 2  l 2

d 2
a2
Tetragonal 1 h2  k 2 l 2
  2
d2 a2 c
Orthorhombic 1 h2 k 2 l 2
  
d 2 a 2 b2 c2

The expressions for the remaining crystal systems are more complex
ICDD
 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)…..
 Structure Factor
Fhkl   f n e
N
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

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
 Intensity of diffracted beam
The factors governing diffracted intensity in the powder method is similar to the one
of monochromatic radiation.

Essentially there are six affecting the relative intensity of the diffraction lines on a
powder pattern:

(1) polarization factor

(2) structure factor
(3) multiplicity factor
(4) Lorentz factor
(5) absorption factor
(6) temperature factor

Under appropriate experimental condition the intensity of the diffracted beam is

given by:

 1  cos 2 2  2 M
I  F p 2 e
2

 sin  cos  
 Structure Factor

 1  cos 2 2  2 M
I  F p 2 e
2

 sin  cos  

Fhkl   f n e
N
2i ( hu n  kvn  lwn )

n i

To calculate F is necessary to account for the scattering waves generate for each
individual atoms of the unit cell and the scattering waves resulting from the
arrangement of the same in the diffracting planes
 Structure Factor (atoms scattering)

the coherent scattering, not from an isolated atom, but from all the atoms making up
the crystal, means that the scattered radiation is severely limited to certain definite
directions and is now referred to a set of diffracted beams.

2’ (h00)

 2 '1'  2d h 00 sin   
1’
M


A C

a
d h 00  AC 
h
N
1
2
a
x
Atom A is radiated by beam 1, at an angle , in such a way there is coherent
diffraction at h00, meaning that Bragg’s law is fulfill by the interplanar distance 2’1’
 Structure Factor (atoms scattering)
How is this reflection affected by x-rays scattered in the same direction by atom B,
located at a distance x from A?

3’ 2’ (h00) the path difference between ray 3'

and ray 1', 3’1’ will be less than ;
1’
if the path difference is , then the
M phase difference (radian) is:
R
 3'1' 2hx

A B C  (2    2hu
 a
S Where:
N
1
x
3 2  3'1'  
a a h
x

If the same analysis is done for (0h0) and (00h):   2 hu  kv  lw
 Structure Factor (plane scattering)
Not only beam interaction with atoms may change de direction of diffraction but also
affect the amplitude (electric field) of the diffracted beam; the electric field intensity is
defined as:

These waves are of the

same frequency v and
therefore same
wavelength , but
different in amplitude A

E2  A2 sin 2t  2 
and in phase .

E1  A1 sin 2t   


The dotted curve shows their addition E3 , which is also a

sine wave, but of different amplitude and phase.

E1  E2  E3
  
 Structure Factor (plane scattering)
Being E3 a sine function it may be expressed by either identities:

e ix  cos x  i sin x Ae ix  A cos x  Ai sin x

Therefore

Ae i  A cos   Ai sin 
Since the intensity of a wave is proportional to the square of its amplitude,
we now need an expression for A2

Ae i 2
 Ae i Ae i  A2

Acos  i sin  Acos  i sin    A2 cos 2  sin 2    A2

The term A2 is the wave amplitude due to the interaction of the incident beam with
the atom in the plane, is value is given by  (atomic scattering factor)
 Intensity of diffracted beam
The factors governing diffracted intensity in the powder method is similar to the one
of monochromatic radiation.

Essentially there are six affecting the relative intensity of the diffraction lines on a
powder pattern:

(1) polarization factor

(2) structure factor
(3) multiplicity factor
(4) Lorentz factor
(5) absorption factor
(6) temperature factor

Under appropriate experimental condition the intensity of the diffracted beam is

given by:

 1  cos 2 2  2 M
I  F p 2 e
2

 sin  cos  
 Structure Factor and Symmetry Absences

a) Primitive cell
 1  cos 2 2  2 M
I  F p 2 e
2

 sin  cos  

Fhkl   f n e
N
2i ( hu n  kvn  lwn )
000
n i

F  fee 2i ( 0 )
 f
F  f
2 2

ei  e 3i  e 5i  1

F2 is thus independent of fn and I is the same e 2i  e 4i  e 6i  1
for all reflections.
e i  e  i  2 cos x
 Structure Factor and Symmetry Absences

Fhkl   f n e
b) Base centered N
2i ( hu n  kvn  lwn )

n i

F  f ee 2i ( 0 )
 fee 2i ( h 2  k 2 )

 
000

½½0 F  f 1 e i ( hk )

(h,k) mixed (h,k) unmixed

F 0 F 2f ei  e 3i  e 5i  1

e 2i  e 4i  e 6i  1
F2  0 F 4f
2 2
e i  e  i  2 cos x
 Structure Factor and Symmetry Absences
c) Body centered

Fhkl   f n e 2i ( hun  kvn lwn )

N

n i

F  f e e 2i ( 0 )  f e e 2i ( h 2 k 2l 2 )

½½½

 
000

F  f 1 e i ( hk l )

(h+k+l) odd (h+k+l) even

F 0 F 2f ei  e 3i  e 5i  1

F 0
2
F2  4 f 2 e 2i  e 4i  e 6i  1
e i  e  i  2 cos x
 Structure Factor and Symmetry Absences
d) Face centered

Fhkl   f n e
0½½ N
2i ( hu n  kvn  lwn )
½0½
000 n i

½½0

F  f ee 2i ( 0 )
 fee 2i ( h 2  k 2 )
 fee 2i ( k 2  l 2 )
 fee 2i ( h 2  l 2 )

F  f 1 e  i (hk )
e i ( k l )
e i ( hl )

(h,k), (h,l), (k,l) mixed (h,k), (h,l), (k,l) unmixed ei  e 3i  e 5i  1
  1
F  0, F 0
e e e
F  4 f , F 2  16 f
2i 4i 6i
2 2
e i  e  i  2 cos x
 Structure Factor calculations
(NaCl)

Na Cl
000 ½½½
½½0 00½
½0½ 0½0
0½ ½ ½00

F  f Na e 2i ( 0 )  f Na e 2i ( h 2 k 2 )  f Na e 2i ( k 2l 2 )  f Na e 2i ( h 2l 2 )

 f Cl e 2i ( 0 )  f Cl e 2i ( h 2 k 2l / 2 )  f Cl e 2i (l 2 )  f Cl e 2i ( k 2 )  f Cl e 2i ( h 2 )

F  f Na (1  e  i ( h  k )  fe i(k  l )
 fe i(h  l )

 f Cl 1  fe i(h  k  l )
 fe  il
 fe  ik
 fe  ih

 Structure Factor calculations
(NaCl)

F  f Na (1  ei ( h  k )  ei ( k l )  ei ( h l ) ) 

f Cl ei ( h  k l ) 1  ei (  h  k )  ei (  h l )  ei (  k l ) 

 
F  1 ei(hk)  ei(kl)  ei(hl ) fNa  fClei(hkl) 
F 0 F 0
F  4 f 
2
mixed

unmixed Na  f Cl e i ( h  k  l )

F  4 f Na  f Cl 
(h+k+l) even

F  4 f Na  f Cl 
(h+k+l) odd

F  16 f Na  f Cl  F  16 f Na  f Cl 
2 2 2 2
 Intensity of diffracted beam
The factors governing diffracted intensity in the powder method is similar to the one
of monochromatic radiation.

Essentially there are six affecting the relative intensity of the diffraction lines on a
powder pattern:

(1) polarization factor

(2) structure factor
(3) multiplicity factor
(4) Lorentz factor
(5) absorption factor
(6) temperature factor

Under appropriate experimental condition the intensity of the diffracted beam is

given by:

 1  cos 2 2  2 M
I  F p 2 e
2

 sin  cos  
 Multiplicity Factor

Number of permutation of position and sign h, k, l for planes having the

same d and F2
 Intensity of diffracted beam
The factors governing diffracted intensity in the powder method is similar to the one
of monochromatic radiation.

Essentially there are six affecting the relative intensity of the diffraction lines on a
powder pattern:

(1) polarization factor

(2) structure factor
(3) multiplicity factor
(4) Lorentz factor
(5) absorption factor
(6) temperature factor

Under appropriate experimental condition the intensity of the diffracted beam is

given by:

 1  cos 2 2  2 M
I  F p 2 e
2

 sin  cos  
 Lorentz Polarization Factor

distribution of plane normals for a

particular cone of reflected rays.

1  cos 2 2
LPF 
sin   cos 
 Intensity of diffracted beam
The factors governing diffracted intensity in the powder method is similar to the one
of monochromatic radiation.

Essentially there are six affecting the relative intensity of the diffraction lines on a
powder pattern:

(1) polarization factor

(2) structure factor
(3) multiplicity factor
(4) Lorentz factor
(5) absorption factor
(6) temperature factor

Under appropriate experimental condition the intensity of the diffracted beam is

given by:

 1  cos 2 2  2 M
I  F p 2 e
2

 sin  cos  
 Temperature factor

f  f 0e  M
For cubic crystal structures where

 x 
 A
x  sin  
  x   4   
 x m
6h T  2

M T N
mk     6h T 11500T

mk 
A 

(x) is obtained from tables,  Debey temperature (tables), A molecular

weight, N is Avogadro’s number, h and k are Plank’s and Boltzmann’s
constants
 Intensity calculation for Cu (FCC)

Copper radiation (nm) Lattice   2d sin 

Equipment parameter (nm)


x
T

 1  cos 2 2  2 M
I  F p 2 e
2

From  sin  cos  

tables

Fhkl   f n e
x   sin  
  x   
6 h T 
2
2  
N
1  cos 2 2 e mk  4   
2i ( hu n  kvn  lwn )
LPF 
From tables
sin   cos 
n i From tables
Tables
Intensity calculation for Cu
Smaller Crystals Produce Broader XRD Peaks
 Scherrer’s Formula

K 
t
B  cosB

t = thickness of crystallite
K = constant dependent on crystallite shape (0.89)
 = x-ray wavelength
B = FWHM (full width at half max) or integral breadth
B = Bragg Angle
 Scherrer’s Formula
What is B?
Peak

B = (2θ High) – (2θ Low)

2θ low 2θ high

B is the difference in
angles at half max Noise
When to Use Scherrer’s Formula

• Crystallite size < 1000 Å

• Peak broadening by other factors
– Causes of broadening
• Size
• Strain
• Instrument
– If breadth consistent for each peak then assured
broadening due to crystallite size
• K depends on definition of t and B
• Within 20%-30% accuracy at best
Sherrer’s Formula References
Corman, D. Scherrer’s Formula: Using XRD to Determine Average Diameter of Nanocrystals.
 Remember, Crystallite Size is
Different than Particle Size
• A particle may be made up of several different
crystallites
• Crystallite size often matches grain size, but there are
exceptions
 Lattice Strain
do

No Strain 2

Uniform Strain
  d  strain 2

Non-uniform Strain
2
d
Broadeing b   2  2 tan 
d
 Typical artifacts and
mistakes on XRD
operation and analysis
1. Irradiated area and
penetration depth
Slit Settings
Slit Settings, effect on the XRD
profile
How to avoid irradiated area problems, sample
preparation
2. Equipment geometry
 3. Sample Preparation
(Common Mistakes and Their Problems)
• Z-Displacements
– Sample height matters
– Causes peaks to shift
• Sample orientation of single crystals
– Affects which peaks are observed
• Inducing texture in powder samples
– Causes peak integrated intensities to vary
Z-Displacements
Detector

011
θ
Disp 2θ

110

111
200
002

It is important that your sample

be at the correct height
Z-Displacements vs. Change in Lattice Parameter

Change In Lattice Parameter

• Lattice Parameters Strain/Composition?
– a=4.0215 Å a=4.07A
– c=4.1100 Å c=4.16A

101/110 Tetragonal PZT

111 002/200
Z-Displaced Fit
Disp.=1.5mm

Disp

Shifts due to z-displacements are systematically different

and differentiable from changes in lattice parameter
Sample Preparation

Crystal Orientation Matters

 Orientations Matter in Single Crystals
(a big piece of rock salt)

200

220

111 222
311

2

At 27.42 °2, Bragg’s law The (200) planes would diffract at 31.82 The (222) planes are parallel to the (111)
fulfilled for the (111) planes, °2; however, they are not properly planes.
producing a diffraction peak. aligned to produce a diffraction peak
 For phase identification you want a random powder
(polycrystalline) sample

200

220

111 222
311

2 2 2

• When thousands of crystallites are sampled, for every set of planes, there will be a small
percentage of crystallites that are properly oriented to diffract
• All possible diffraction peaks should be exhibited
• Their intensities should match the powder diffraction file
Sample Preparation

Inducing Texture In A Powder

Sample
 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 <10mm 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
 Texture in Samples
• Common Occurrences • How to Prevent
– Plastically deformed metals – Grind samples into fine
(cold rolled) powders
– Powders with particle – Unfortunately you can’t or
shapes related to their don’t want to do this to
crystal structure many samples.
• Particular planes form the faces
• Elongated in particular
directions (Plates, needles,
acicular,cubes, etc.)