X-RAY DIFFRACTION

X- Ray Sources
Diffraction: Braggs Law
Crystal Structure Determination
Elements of X-Ray Diffraction
B.D. Cullity & S.R. Stock
Prentice Hall, Upper Saddle River (2001)
Recommended websites:
http://www.matter.org.uk/diffraction/
http://www.ngsir.netfirms.com/englishhtm/Diffraction.htm
How to produce monochromatic X-rays?
How does a crystal scatter these X-rays to give a diffraction pattern?
Braggs equation
What determines the position of the XRD peaks? Ans) the lattice
What determines the intensity of the XRD peaks? Ans) the motif
What other uses can XRD be put to apart from crystal structure determination?
Grain size determination Strain in the material
What will you learn in this sub-chapter?
For electromagnetic radiation to be diffracted the spacing
in the grating (~a series of obstacles) should be of the same order as the
wavelength
In crystals the typical interatomic spacing ~ 2-3 so the suitable
radiation is X-rays
Hence, X-rays can be used for the study of crystal structures
Some Basics
Beam of electrons
Target
X-rays
A accelerating (or decelerating) charge radiates electromagnetic radiation
X-rays can be generated by decelerating electrons
Generation of X-rays
I
n
t
e
n
s
i
t
y

Wavelength ()
Mo Target impacted by electrons accelerated by a 35 kV potential shows the emission
spectrum as in the figure below (schematic)
0.2
0.6
1.0
1.4
White
radiation
Characteristic radiation
due to energy transitions
in the atom
K
|
K
o
The high intensity nearly monochromatic K
o
x-rays can be used as a radiation source for
X-ray diffraction (XRD) studies a monochromator can be used to further decrease the
spread of wavelengths in the X-ray
Intense peak, nearly monochromatic
Target Metal Of K
o
radiation ()
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
Available X-ray sources with different for doing XRD studies
Heat
Incident X-rays
SPECIMEN
Transmitted beam
Fluorescent X-rays
Electrons
Compton recoil Photoelectrons
Scattered X-rays
Coherent
From bound charges
X-rays can also be refracted (refractive index slightly less than 1) and reflected (at very small angles)
When X-rays hit a specimen, the interaction can
result in various signals/emissions/effects
The coherently scattered X-rays are the ones
important from a XRD perspective
Incoherent (Compton modified)
From loosely bound charges
Click here to know more
Now we shall consider the important topic as to how X-rays interact with a
crystalline array (of atoms, ions etc.) to give rise to the phenomenon known as X-
ray diffraction (XRD)
Diffraction (with XRD being a specific case) requires two important conditions to be met:
Coherent waves (with wavelength ) on a
Crystalline array* with spacing of the order of (~)
The waves could be
electromagnetic waves (light, X-rays),
matter waves** (electrons, neutrons) or
mechanical waves (sound, waves on water surface)
In short diffraction is coherent reinforced scattering (or reinforced scattering of coherent waves)
In a sense diffraction is nothing but a special case of constructive (& destructive)
interference
To give an analogy the results of Youngs double slit experiment is interpreted as interference, while the result of
multiple slits is categorized under diffraction
* A quasicrystalline array will also lead to diffraction (which we shall not consider in this text)
** With a de Broglie wavelength
Diffraction
A beam of X-rays directed at a crystal interacts with the
electrons of the atoms in the crystal
The electrons oscillate under the influence of the incoming
X-Rays and become secondary sources of EM radiation
The secondary radiation is in all directions
The waves emitted by the electrons have the same frequency
as the incoming X-rays coherent
The emission can undergo constructive or destructive
interference
Incoming X-rays
Secondary
emission
XRD the first step
Schematically
Sets Electron cloud into oscillation
Sets nucleus into oscillation
Small effect neglected
Schematically
Oscillating charge re-radiates In phase with the incoming x-rays
Schematically
We can get a better physical picture of diffraction by using Laues formalism (leading to the Laues
equations)
However, a parallel approach to diffraction is via the method of Bragg, wherein diffraction can be
visualized as reflections from a set of planes
As the approach of Bragg is easier to grasp we shall use that in this elementary text
We shall do some intriguing mental experiments to utilize the Braggs equation (Braggs model) with
caution
Let us consider a coherent wave of X-rays impinging on a crystal with atomic
planes at an angle u to the rays
Incident and scattered waves are in phase if the:
i) in-plane scattering is in phase and
ii) scattering from across the planes is in phase
Incident and scattered
waves are in phase if
Scattering from across planes is in phase
In plane scattering is in phase
Some points to recon with
Extra path traveled by incoming waves AY
A B
X Y
Atomic Planes
Extra path traveled by scattered waves XB
These can be in phase if
u
incident
= u
scattered

A B
X Y
But this is still reinforced scattering
and NOT reflection
Let us consider in-plane scattering
There is more to this
Click here to know more and get
introduced to Laue equations describing
diffraction
BRAGGs EQUATION
d
u
u
u
u
The path difference between ray 1 and ray 2 = 2d Sinu
For constructive interference: n = 2d Sinu the Braggs equation
Ray 1
Ray 2
u
Let us consider scattering across planes
Deviation = 2u
Click here to visualize
constructive and
destructive interference
Reflection versus Scattering
Reflection Diffraction
Occurs from surface Occurs throughout the bulk
Takes place at any angle Takes place only at Bragg angles
~100 % of the intensity may be reflected Small fraction of intensity is diffracted
Note: X-rays can be reflected at very small angles of incidence
Though diffraction (according to Braggs picture) has been visualized as a reflection
from a set of planes with interplanar spacing d diffraction should not be confused
with reflection (specular reflection)
n = 2d Sinu
The equation is written better with some descriptive subscripts:


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)
Braggs equation is a negative statement
If Braggs eq. is NOT satisfied NO reflection can occur
If Braggs eq. is satisfied reflection MAY occur
(How?- we shall see this a little later)
The interplanar spacing appears in the Braggs equation, but not the interatomic
spacing a along the plane (which had forced u
incident
= u
scattered
); but we are not
free to move the atoms along the plane randomly click here to know more
Understanding the Braggs equation
2 Sin
Cu K hkl hkl
n d
o
u =
For Cu K
o
radiation ( = 1.54 ) and d
110
= 2.22
n Sinu = n/2d u
1 0.34 20.7 First order reflection from (110) 110
2 0.69 43.92
Second order reflection from (110) planes
110
Also considered as first order reflection from
(220) planes 220
2 2 2
l k h
a
d
hkl
+ +
=
8
220
a
d =
2
110
a
d =
2
1
110
220
=
d
d
Relation between d
nh nk nl
and d
hkl

e.g.
2 2 2
( ) ( ) ( )
nhnk nl
a
d
nh nk nl
=
+ +
2 2 2
hkl
nhnk nl
d a
d
n
n h k l
= =
+ +
Order of the reflection (n)
u sin 2
hkl
d n =
In XRD n
th
order reflection from (h k l) is considered as 1
st
order reflection
from (nh nk nl)
u sin 2
n
d
hkl
=
u sin 2
n n n l k h
d =
1
nhnk nl
hkl
d
d n
=
300
100
1
3
d
d
=
200
100
1
2
d
d
=
Hence, (100) planes are a subset of (200) planes
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) planes)
Forward and Back Diffraction
Here a guide for quick visualization of forward and backward scattering (diffraction) is presented
We had mentioned that Braggs equation is a negative statement: i.e. just because
Braggs equation is satisfied a reflection may not be observed
Let us consider the case of Cu K
o
radiation ( = 1.54 ) being diffracted from
(100) planes of Mo (BCC, a = 3.15 = d
100
)
The missing reflections
100 100
2d Sin u =
100
100
1.54
0.244
2 2(3.15)
Sin
d

u = = =
100
14.149 u = But this reflection is absent in BCC Mo
However, the second order reflection from (100) planes (which is equivalent to the first order
reflection from the (200) planes is observed
100
100
2 1.54
0.488
2 3.15
Sin
d

u = = =
2 1
100 200
~ 29.267
nd nd
order order
u u =
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
Presence of additional atoms/ions/molecules in the UC
at lattice points
or as a part of the motif
can alter the intensities of some of the reflections
Important point
Intensity of the Scattered electrons
Electron
Atom
Unit cell (uc)
Scattering by a crystal can be understood in three steps
A
B
C
Polarization factor
Atomic scattering factor (f)
Structure factor (F)
To understand the scattering from a crystal leading to
the intensity of reflections (and why some reflections
go missing), three levels of scattering have to be
considered:
1) scattering from electrons
2) scattering from an atom
3) scattering from a unit cell
Click here to know the details
Structure factor calculations
Structure Factor (F): The resultant wave scattered
by all atoms of the unit cell
The Structure Factor is independent of the shape
and size of the unit cell; but is dependent on the
position of the atoms/ions etc. within the cell
The concept of a reciprocal lattice and the Ewald Sphere construction:
a lattice in which planes in the real lattice become points in the reciprocal lattice
is a very useful one in understanding diffraction
click here to go to a detailed description of these topics
Bravais Lattice Reflections which may be present Reflections necessarily absent
Simple all None
Body centred (h + k + l) even (h + k + l) odd
Face centred h, k and l unmixed h, k and l mixed
End centred
h and k unmixed
C centred
h and k mixed
C centred
Bravais Lattice Allowed Reflections
SC All
BCC (h + k + l) even
FCC h, k and l unmixed
DC
h, k and l are all odd
Or
all are even
& (h + k + l) divisible by 4
Selection / Extinction Rules
The reflections present and the missing reflections due to additional atoms in the unit cell
h
2
+ k
2
+ l
2
SC FCC BCC DC
1 100
2 110 110
3 111 111 111
4 200 200 200
5 210
6 211 211
7
8 220 220 220 220
9 300, 221
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
Allowed reflections
in SC*, FCC*, BCC*
& DC crystals
* lattice decorated with
monoatomic/monoionic motif
The ratio of (h
2
+ k
2
+ l
2
) derived from extinction rules
As we shall see soon the ratios of (h
2
+ k
2
+ l
2
) is proportional to Sin
2
u
which can be used in the determination of the lattice type
SC 1 2 3 4 5 6 8
BCC 1 2 3 4 5 6 7
FCC 3 4 8 11 12
DC 3 8 11 16
Crystal structure determination
Monochromatic X-rays
Panchromatic X-rays
Monochromatic X-rays
Many us (orientations)
Powder specimen
POWDER
METHOD
Single u
LAUE
TECHNIQUE
u Varied by rotation
ROTATING
CRYSTAL
METHOD
fixed
variable

fixed
rotated

variable
fixed

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
Only the powder method (which is commonly used in materials science) will be considered in the text
THE POWDER METHOD
u
2 2 2 2
sin ) ( + + l k h
u

2
2
2
2 2 2
sin
4
) (
a
l k h = + +
) (
sin 4
2 2 2
2
2
2
l k h a + + =
u

2 2 2
l k h
a
d
Cubic
+ +
=
2d Sin u =
2 2 2
2 2
2
sin 4
l k h
a
+ +
=
u

Cubic crystal
In the powder method the specimen has crystallites (or grains) in many
orientations (usually random)
Monochromatic* X-rays are irradiated on the specimen and the intensity of the
diffracted beams is measured as a function of the diffracted angle
In this elementary text we shall consider cubic crystals
(1)
(2)
(2) in (1)


* In reality this is true only to an extent
In the powder sample there are crystallites in different random orientations (a polycrystalline
sample too has grains in different orientations)
The coherent x-ray beam is diffracted by these crystallites at various angles to the incident direction
All the diffracted beams (called reflections) from a single plane, but from different crystallites lie
on a cone.
Depending on the angle there are forward and back reflection cones.
A diffractometer can record the angle of these reflections along with the intensities of the reflection
POWDER METHOD
Different cones for different reflections
In the power diffraction method a 2u versus intensity (I) plot is obtained from the
diffractometer (and associated instrumentation)
The intensity is the area under the peak in such a plot
A table is prepared as in the next slide to tabulate the data and make calculations
to find the crystal structure (restricting ourselves to cubic crystals for the present)
Determination of Crystal Structure from 2u versus Intensity Data in Powder Method
Powder diffraction pattern from Al
Radiation: Cu Ko, = 1.54
n 2u u Intensity Sinu Sin
2
u ratio
Determination of Crystal Structure from 2u versus Intensity Data
The following table is made from the 2u versus Intensity data (obtained from a XRD experiment on a
powder sample
Powder diffraction pattern from Al
1
1
1

2
0
0

2
2
0

3
1
1

2
2
2

4
0
0

o
1
& o
2
peaks resolved
Radiation: Cu Ko, = 1.54
Note:
Peaks or not idealized o peaks broadened
Increasing splitting of peaks with |g u
Peaks are all not of same intensity
Powder diffraction pattern from Al Radiation: Cu Ko, = 1.54
Note:
This is a schematic pattern
In real patterns peaks or not idealized o peaks broadened
Increasing splitting of peaks with |g u
(o
1
& o
2
peaks get resolved in the high angle peaks)
Peaks are all not of same intensity
n 2u u Sinu Sin
2
u ratio Index
1 38.52 19.26 0.33 0.11 3 111
2 44.76 22.38 0.38 0.14 4 200
3 65.14 32.57 0.54 0.29 8 220
4 78.26 39.13 0.63 0.40 11 311
5 82.47 41.235 0.66 0.43 12 222
6 99.11 49.555 0.76 0.58 16 400
7 112.03 56.015 0.83 0.69 19 331
8 116.60 58.3 0.85 0.72 20 420
9 137.47 68.735 0.93 0.87 24 422
Determination of Crystal Structure from 2u versus Intensity Data
From the ratios in column 6 we conclude that
FCC
Let us assume that we have the 2u versus intensity plot from a diffractometer
To know the lattice type we need only the position of the peaks (as tabulated below)
Solved example
2d Sin u =
111 111
1.54 2 2 0.33
3
a
d Sinu = =
o
4.04A a Al =
Using
We can get the lattice parameter which correspond to that for Al
1

Note: Error in d spacing decreases with u so we should use high angle lines for lattice parameter calculation
Click here to know more
2u u Sinu Sin
2
u ratio
1 21.5 0.366 0.134 3
2 25 0.422 0.178 4
3 37 0.60 0.362 8
4 45 0.707 0.500 11
5 47 0.731 0.535 12
6 58 0.848 0.719 16
7 68 0.927 0.859 19
FCC
Another example
Given the positions of the Bragg peaks we find the lattice type
Solved example
2

More Solved
Examples on XRD
Click
Bravais lattice determination
Lattice parameter determination
Determination of solvus line in phase diagrams
Long range order
Applications of XRD
Crystallite size and Strain
Determine if the material is amorphous or crystalline
We have already seen these applications
Click here to know more
Next slide
Diffraction angle (2u)
I
n
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s
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90 180
0
Crystal

90 180
0
Diffraction angle (2u)
I
n
t
e
n
s
i
t
y

Liquid / Amorphous solid

90
180
0
Diffraction angle (2u)
I
n
t
e
n
s
i
t
y

Monoatomic gas

Schematic of difference between
the diffraction patterns of various phases
Sharp peaks
Diffuse Peak
No peak