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
MATERIALS SCIENCE
&
ENGINEERING
Anandh Subramaniam & Kantesh Balani
Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
AN INTRODUCTORY E-BOOK
Part of
http://home.iitk.ac.in/~anandh/E-book.htm
A Learners Guide
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? Answer) the lattice.
What determines the intensity of the XRD peaks? Answer) the motif.
How to analyze a powder pattern to get information about the lattice type?
(Cubic crystal types).
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 or a series of scatterers) should be of the same order as the
wavelength.
In crystals the typical interatomic spacing ~ 2-3 ** so the suitable radiation
for the diffraction study of crystals is X-rays.
Hence, X-rays are used for the investigation of crystal structures.
Neutrons and Electrons are also used for diffraction studies from materials.
Neutron diffraction is especially useful for studying the magnetic ordering in
materials.
Some Basics
** Lattice parameter of Cu (a
Cu
) = 3.61
d
hkl
is equal to a
Cu
or less than that (e.g. d
111
= a
Cu
/\3 = 2.08 )
** If the wavelength is of the order of the lattice spacing, then diffraction effects will be prominent.
Click here to know more about this
Beam of electrons
Target
X-rays
An accelerating (or decelerating) charge radiates electromagnetic radiation
X-rays can be generated by decelerating electrons.
Hence, X-rays are generated by bombarding a target (say Cu) with an electron beam.
The resultant spectrum of X-rays generated (i.e.
X-rays
versus Intensity plot) is shown in
the next slide. The pattern shows intense peaks on a broad background.
The intense peaks can be thought of as monochromatic radiation and be used for X-ray
diffraction studies.
Generation of X-rays
Mo Target impacted by electrons accelerated by a 35 kV potential shows the emission
spectrum as in the figure below (schematic)
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
I
n
t
e
n
s
i
t
y
Wavelength ()
0.2 0.6 1.0 1.4
White
radiation
Characteristic radiation
due to energy transitions
in the atom
K
|
K
o
Intense peak, nearly
monochromatic
X-ray sources with different for
doing XRD studies
Target
Metal
Of K
o

radiation ()
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
Absorption (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).
Let us consider a special case of diffraction a case where we get sharp
[1]

diffraction peaks.
Diffraction (with sharp peaks) (with XRD being a specific case) requires three important conditions to
be satisfied:
Coherent, monochromatic, parallel waves (with wavelength ).
Crystalline array of scatterers* with spacing of the order of (~) .
Fraunhofer diffraction geometry
[1] The intensity-u plot looks like a o function.
* A quasicrystalline array will also lead to diffraction with sharp peaks (which we shall not consider in this text).
** Amorphous material will give diffuse peak.
Diffraction
Click here to Understand Diffraction
Coherent, monochromatic, parallel wave
Fraunhofer geometry
Diffraction pattern
with sharp peaks
Crystalline*
,
**
Aspects related to the wave
Aspects related to the material
Aspects related to the diffraction set-up
(diffraction geometry)
The waves could be:
electromagnetic waves (light, X-rays),
matter waves** (electrons, neutrons) or
mechanical waves (sound, waves on water surface).
Not all objects act like scatterers for all kinds of radiation.
If wavelength is not of the order of the spacing of the scatterers, then the number
of peaks obtained may be highly restricted (i.e. we may even not even get a
single diffraction peak!).
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 (large number) is categorized under diffraction.
Fraunhofer diffraction geometry implies that parallel waves are impinging on the scatteres
(the object), and the screen (to capture the diffraction pattern) is placed far away from the
object.
** With a de Broglie wavelength
Some comments and notes
Click here to know more about Fraunhofer and Fresnel diffraction geometries
Sets Electron cloud into oscillation
Sets nucleus into oscillation
Small effect neglected
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.
XRD the first step
Schematics
Incoming X-rays
Secondary
emission
Oscillating charge re-radiates In phase with
the incoming x-rays
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
A portion of the crystal is shown for clarity- actually, for destructive interference to occur
many planes are required (and the interaction volume of x-rays is large as compared to that shown in the schematic).
The scattering planes have a spacing d.
Ray-2 travels an extra path as compared to Ray-1 (= ABC). The path difference between
Ray-1 and Ray-2 = ABC = (d Sinu + d Sinu) = (2d.Sinu).
For constructive interference, this path difference should be an integral multiple of :
n = 2d Sinu the Braggs equation. (More about this sooner).
The path difference between Ray-1 and Ray-3 is = 2(2d.Sinu) = 2n = 2n. This implies that if Ray-1
and Ray-2 constructively interfere Ray-1 and Ray-3 will also constructively interfere. (And so forth).
Let us consider scattering across planes
Click here to visualize
constructive and
destructive interference
The previous page explained how constructive interference occurs. How about the rays just
of Bragg angle? Obviously the path difference would be just off as in the figure below.
How come these rays go missing?
Click here to understand how
destructive interference of
just of-Bragg rays occur
Interference of Ray-1 with Ray-2
Note that they almost constructively interfere!
Reflection versus Diffraction
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 ALSO 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.
For large interplanar spacing the angle of reflection tends towards zero as d increases,
Sinu decreases (and so does u).
The smallest interplanar spacing from which Bragg diffraction can be obtained is /2
maximum value of u is 90, Sinu is 1 from Bragg equation d = /2.
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
Cubic crystal
hkl
a
d
h k l
=
+ +
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).
How is it that we are able to get information about lattice parameters of the order
of Angstroms (atoms which are so closely spaced) using XRD?
Funda Check
Diffraction is a process in which
linear information (the d-spacing of the planes)
is converted to angular information (the angle of diffraction, u
Bragg
).
If the detector is placed far away from the sample (i.e. R in the figure below is large) the
distances along the arc of a circle (the detection circle) get amplified and hence we can make
easy measurements.
Forward and Back Diffraction
Here a guide for quick visualization of forward and backward scattering (diffraction) is presented
Funda Check
What is u (theta) in the Braggs equation?
u is the angle between the incident x-rays and the set of parallel atomic planes (which have
a spacing d
hkl
). Which is 10 in the above figure.
It is NOT the angle between the x-rays and the sample surface (note: specimens could be
spherical or could have a rough surface).
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
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
The wave scattered from the middle plane is out of phase
with the ones scattered from top and bottom planes. I.e. if
the green rays are in phase (path difference of ) then the
red ray will be exactly out of phase with the green rays
(path difference of /2).
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 =
This is because if the green rays have a path difference of 2 then the red ray will have path
difference of which will still lead to constructive interference!
Continuing with the case of BCC Mo
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
Some of the reflections may even go missing
Important
points
Position of the reflections/peaks tells us about the lattice type.
The Intensities tells us about the motif.
Intensity of the Scattered waves
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
&
Intensity in powder patterns
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
Click here to know more about
Braggs equation tells us about the position of the intensity peaks (in terms of u) but tells
us nothing about the intensities. The intensities of the peaks depend on many factors as
considered here.
The concept of a Reciprocal lattice and the Ewald Sphere construction:
Reciprocal lattice and Ewald sphere constructions are important tools towards
understanding diffraction.
(especially diffraction in a Transmission Electron Microscope (TEM))
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.
Reciprocal Lattice & Ewald Sphere construction Click here to know more about
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 (C centred) h and k unmixed h and k mixed
Bravais Lattice Allowed Reflections
SC All
BCC (h + k + l) even
FCC h, k and l unmixed
DC
Either, h, k and l are all odd or
all are even & (h + k + l) divisible by 4
Selection / Extinction Rules
As we have noted before even if Braggs equation is satisfied, reflections may go missing
this is due to the presence of additional atoms in the unit cell.
The reflections present and the missing reflections due to additional atoms in the unit cell are
listed in the table below.
Click here to see the derivations
Structure factor calculations
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
Cannot be expressed as (h
2
+k
2
+l
2
)
The ratio of (h
2
+ k
2
+ l
2
) derived from extinction rules (previous page)
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
Note that we have to consider the ratio of only two lines to distinguish FCC and DC. I.e. if the
ratios are 3:4 then the lattice is FCC.
But, to distinguish between SC and BCC we have to go to 7 lines!
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 this 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
The X-ray source and diffractometer move in arcs of a circle- maintaining the Bragg reflection
geometry as in the figure (right)
POWDER METHOD
Different cones
for different
reflections
How to visualize the occurrence of peaks at various angles
It is somewhat difficult to actually visualize a random assembly of crystallites giving peaks at various angels in a XRD
scan. The figures below are expected to give a visual feel for the same. [Hypothetical crystal with a = 4 is assumed with
=1.54. Only planes of the type xx0 (like (100,110)are considered].
Random assemblage of
crystallites in a material
As the scan takes place at increasing
angles, planes with suitable d,
which diffract are picked out from
favourably oriented crystallites
Eh
2
hkl d Sin(u) u
1 100 4.00 0.19 11.10
2 110 2.83 0.27 15.80
3 111 2.31 0.33 19.48
4 200 2.00 0.39 22.64
5 210 1.79 0.43 25.50
6 211 1.63 0.47 28.13
8 220 1.41 0.54 32.99
9 300 1.33 0.58 35.27
10 310 1.26 0.61 37.50
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 (NOT the height of the peak).
The information of importance obtained from such a pattern is the relative intensities
and the absolute value of the intensities is of little importance (for now).
I is really diffracted energy (as Intensity is Energy/area/time).
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
Increasing u
Increasing d
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 (empty starting table of columns is shown below- completed table shown later).
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
No brackets are used around the indexed numbers
(the peaks correspond to planes in the real space)
Powder diffraction pattern from Al
1
1
1

2
0
0

2
2
0

3
1
1

2
2
2

4
0
0

Ko
1
& Ko
2
peaks resolved in high angle peaks
(in 222 and 400 peaks this can be seen)
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
In low angle peaks Ko
1
& Ko
2
peaks merged
What is the maximum value of u possible (experimentally)?
Funda Check
How are real diffraction patterns different from the ideal computed ones?
We have seen real and ideal diffraction patterns. In ideal patterns the peaks are o
functions.
Real diffraction patterns are different from ideal ones in the following ways:
Peaks are broadened
Could be due to instrumental, residual non-uniform strain (microstrain), grain size etc. broadening.
Peaks could be shifted from their ideal positions
Could be due to uniform strain macrostrain.
Relative intensities of the peaks could be altered
Could be due to texture in the sample.
Funda Check
Ans: 90
At u = 90 the reflected ray is opposite in
direction to the incident ray.
Beyond this angle, it is as if the source and
detector positions are switched.
2u
max
is 180.
Funda Check
What will determine how many peaks I will get?
1) smaller the wavelength of the X-rays, more will be the number of peaks possible.
From Braggs equation: [=2dSinu], (Sinu)
max
will correspond to d
min
. (Sinu)
max
=1.
Hence, d
min
=/2. Hence, if is small then planes with smaller d spacing (i.e. those which
occur at higher 2u values) will also show up in a XRD patter (powder pattern). Given that
experimentally u cannot be greater than 90.
2) Lattice type in SC we will get more peaks as compared to (say) FCC/DC. Other things being
equal.
3) Lower the symmetry of the crystal, more the number of peaks (e.g., in tetragonal crystal
the 100 peak will lie at a different 2u as compared to the 001 peak).
2dSin u =
( )
min
max
2d
Sin

u
=
min
2
d

=
# 2u u Sinu Sin
2
u ratio Index d
1 38.52 19.26 0.33 0.11 3 111 2.34
2 44.76 22.38 0.38 0.14 4 200 2.03
3 65.14 32.57 0.54 0.29 8 220 1.43
4 78.26 39.13 0.63 0.40 11 311 1.22
5 82.47 41.235 0.66 0.43 12 222 1.17
6 99.11 49.555 0.76 0.58 16 400 1.01
7 112.03 56.015 0.83 0.69 19 331 0.93
8 116.60 58.3 0.85 0.72 20 420 0.91
9 137.47 68.735 0.93 0.87 24 422 0.83
10 163.78 81.89 0.99 0.98 27 333 0.78
Determination of Crystal Structure (lattice type) 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
Note that Sinu cannot be > 1
XRD_lattice_parameter_calculation.ppt
u
2 2 2 2
sin ) ( + + l k h
Note
2u u Sinu Sin
2
u
Ratios
of Sin
2
u
Dividing Sin
2
u by
0.134/3 = 0.044667
Whole
number
ratios
1 21.5 0.366 0.134 1 3
2 25 0.422 0.178 1.33 3.99 4
3 37 0.60 0.362 2.70 8.10 8
4 45 0.707 0.500 3.73 11.19 11
5 47 0.731 0.535 4 11.98 12
6 58 0.848 0.719 5.37 16.10 16
7 68 0.927 0.859 6.41 19.23 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 here
Comparison of diffraction patterns of SC, BCC & B2 structures
Click here
Aluminium
= 1.54 = 3 = 0.1
hkl d Sin(u) u 2u Sin(u) u 2u Sin(u) u 2u
111 2.34 0.33 19.26 38.52 0.64 39.87 79.74 0.02 1.22 2.45
200 2.03 0.38 22.38 44.76 0.74 47.64 95.28 0.02 1.41 2.82
220 1.43 0.54 32.57 65.14 1.05 - - 0.03 2.00 4.01
311 1.22 0.63 39.13 78.26 1.23 - - 0.04 2.35 4.70
222 1.17 0.66 41.24 82.47 1.28 - - 0.04 2.45 4.90
400 1.01 0.76 49.56 99.11 1.49 - - 0.05 2.84 5.68
331 0.93 0.83 56.02 112.03 1.61 - - 0.05 3.08 6.16
420 0.91 0.85 58.30 116.60 1.65 - - 0.05 3.15 6.30
422 0.83 0.93 68.74 137.47 1.81 - - 0.06 3.45 6.91
333 0.78
0.99 81.89 163.78 1.92 - - 0.06 3.68 7.35
Funda Check
What happens when we increase or decrease ?
We had pointed out that ~ a is preferred for diffraction. Let us see what happens if we drastically increase or decrease .
(This is only a thought experiment!!)
If we ~double we get too
few peaks
If we make small
all the peaks get
crowded to small
angles
With Cu
Ko
= 1.54
And the detector may not be able to resolve
these peaks if they come too close!
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
t
e
n
s
i
t
y

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
Diffuse peak from
Cu-Zr-Ni-Al-Si
Metallic glass
(XRD patterns) courtesy: Dr. Kallol Mondal, MSE, IITK
Actual diffraction pattern from an amorphous solid
Note
Sharp peaks are missing
Broad diffuse peak survives
the peak corresponds to the average spacing between atoms which the diffraction experiment picks
out
Funda Check
What is the minimum spacing between planes possible in a crystal?
How many diffraction peaks can we get from a powder pattern?
2 2 2
Cubic crystal
hkl
a
d
h k l
=
+ +
Let us consider a cubic crystal (without loss in generality)
As h,k, l increases, d decreases we could have planes with infinitesimal spacing
10
1
a
d a = =
11
2
a
d =
13
10
a
d =
12
5
a
d =
34
5 25
a a
d = =
With increasing indices the
interplanar spacing decreases
The number of peaks we obtain in a powder
diffraction pattern depends on the wavelength
of x-ray we are using. Planes with d < /2 are
not captured in the diffraction pattern.
These peaks with small d occur at high angles
in diffraction pattern.