X-RAY DIFFRACTION

X- Ray Sources
Diffraction: Braggs Law
Crystal Structure Determination

Part of

MATERIALS SCIENCE
& AALearners
LearnersGuide
Guide
ENGINEERING
AN INTRODUCTORY E-BOOK

Anandh Subramaniam & Kantesh Balani

Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@[Link], URL: [Link]/~anandh
[Link]

Elements of X-Ray Diffraction

B.D. Cullity & S.R. Stock
Prentice Hall, Upper Saddle River (2001)

Recommended websites:
[Link]
[Link]

What will you learn in this sub-chapter?

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

Some Basics
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.

** If the wavelength is of the order of the lattice spacing, then diffraction effects will be prominent.
** Lattice parameter of Cu (aCu) = 3.61
dhkl is equal to aCu or less than that (e.g. d111 = aCu/3 = 2.08 )

Click here to know more about this

Generation of X-rays
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.

Beam of electrons

Target

X-rays

An accelerating (or decelerating) charge radiates electromagnetic radiation

Mo Target impacted by electrons accelerated by a 35 kV potential shows the emission

spectrum as in the figure below (schematic)
X-ray sources with different for
doing XRD studies
Target
Metal

Of K
radiation ()

Mo

0.71

Cu

1.54

Co

1.79

Fe

1.94

Cr

2.29

The high intensity nearly monochromatic K 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

X-ray sources with different for doing XRD studies

Elements

(KV)

Of K1
radiation
()

Of K2
radiation ()

K-Filter
Of K
(mm)
radiation ()

Ag

25.52

0.55941

0.5638

0.49707

Mo

20

0.7093

0.71359

0.63229

Cu

8.98

1.540598

1.54439

1.39222

Ni

8.33

1.65791

1.66175

1.50014

Co

7.71

1.78897

1.79285

1.62079

Fe

7.11

1.93604

1.93998

1.75661

Cr

5.99

2.2897

2.29361

2.08487

Pd
0.0461
Zr
0.0678
Ni
0.017
Co
0.0158
Fe
0.0166
Mn
0.0168
V
0.169

[Link] Darwin, Grandson of C. Robert Darwin developed the dynamic theory of scattering of x-rays (a tough theory!) in 1912

 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.

Incident X-rays

SPECIMEN

Fluorescent X-rays

Electrons

Scattered X-rays
Coherent
Coherent
From
Frombound
boundcharges
charges

Absorption (Heat)

Compton recoil

Photoelectrons

Incoherent (Compton modified)

From loosely bound charges

Transmitted beam

Click
Clickhere
heretotoknow
knowmore
more

X-rays can also be refracted (refractive index slightly less than 1) and reflected (at very small angles)

Diffraction

Click
Clickhere
heretotoUnderstand
UnderstandDiffraction
Diffraction

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 Xray 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:
&
Radiation related Coherent, monochromatic, parallel waves (with wavelength ).
Sample related Crystalline array of scatterers* with spacing of the order of (~) .
Diffraction geometry related Fraunhofer diffraction geometry ( this is actually part of the Fraunhofer geometry)
&

Aspects related to the wave

Diffraction pattern
with sharp peaks

Aspects related to the material

Aspects related to the diffraction set-up
(diffraction geometry)

Coherent, monochromatic, parallel wave

Crystalline*,**

Fraunhofer geometry

[1] The intensity- plot looks like a function (in an ideal situation).
* A quasicrystalline array will also lead to diffraction with sharp peaks (which we shall not consider in this text).
** Amorphous material will give broadened (diffuse) peak (additional factors related to the sample can also give a diffuse peak).

Some comments and notes

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.
Click here to know more about Fraunhofer and Fresnel diffraction geometries

** With a de Broglie wavelength

XRD the first step

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.

Schematics

Some points to recon with

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 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.

In plane scattering is in phase

Incident and scattered
waves are in phase if
Scattering from across planes is in phase

Let us consider in-plane scattering

A B

Atomic Planes

There is more to this

Click here to know more and get
introduced to Laue equations describing
diffraction

Extra path traveled by incoming waves AY

Extra path traveled by scattered waves XB

But this is still reinforced scattering

and NOT reflection

A B

These can be in phase if

incident = scattered

BRAGGs EQUATION

Let us consider scattering across planes

Click
Clickhere
heretotovisualize
visualize
constructive
constructiveand
and
destructive
interference
destructive interference
See Note later

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 Sin + d Sin) = ([Link]).
For constructive interference, this path difference should be an integral multiple of :

n = 2d Sin the Braggs equation. (More about this sooner).

The path difference between Ray-1 and Ray-3 is = 2([Link]) = 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).

 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
Clickhere
heretotounderstand
understandhow
how
destructive
interference
of
destructive interference of
just
justof-Bragg
of-Braggrays
raysoccur
occur

Interference of Ray-1 with Ray-2

Which remains same
thereafter (like in the
BB plane)

Note that they almost constructively interfere!

Funda Check How to see that path difference increases with angle?

Clearly ABC > ABC

Laue versus Bragg

In Laues picture constructive and destructive interference at various points in space is
computed using path differences (and hence phase differences) given a crystalline array of
scatterers.
Bragg simplified this picture by considering this process as reflections from atomic planes.
Click
Clickhere
heretotoknow
knowmore
moreabout
aboutthe
theLaue
LauePicture
Picture

Reflection versus Diffraction

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).
Reflection

Diffraction
Occurs throughout the bulk

Occurs from surface

(though often the penetration of x-rays in only of the

order of 10s of microns in a material)

Takes place at any angle

Takes place only at Bragg angles

~100 % of the intensity may be reflected

Small fraction of intensity is diffracted

Planes are imaginary constructs

Note: X-rays can ALSO be reflected at very small angles of incidence

Understanding the Braggs equation

n = 2d Sin
The equation is written better with some descriptive subscripts:

n Cu K 2 d hkl Sin hkl

If this equation is satisfied, then is Bragg

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).

Note:

Note: if hkl reflection (corresponding to n=1) occurs at hkl then 2h 2k 2l reflection (n=2) will occur at a higher angle 2h 2k 2l.

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 incident = 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,
Sin decreases (and so does ).
The smallest interplanar spacing from which Bragg diffraction can be obtained is /2
maximum value of is 90, Sin is 1 from Bragg equation d = /2.

Order of the reflection (n)

For Cu K radiation ( = 1.54 ) and d110= 2.22
n

Sin = n/2d

0.34

20.7

0.69

43.92

First order reflection from (110) 110

Second order reflection from (110) planes 110
Also considered as first order reflection from (220) planes 220

Relation between dnh nk nl and dhkl

Cubic crystal
hkl

d nh nk nl

d nh nk nl

e.g.

h2 k 2 l 2
a

(nh) 2 (nk ) 2 (nl ) 2

a
n h2 k 2 l 2

d hkl
n

a
d 220
8
a
d110
2

d 220 1

d110 2

In XRD nth order reflection from (h k l) is considered as 1st order reflection from (nh nk nl)

n 2d hkl sin hkl

d nh nk nl

d hkl
sin
d hkl
n
2d nh nk nl sin nh nk nl

d 200 1

d100 2
All these form the (200) set

Hence, (100) planes are a subset of (200) planes

d300 1

d100 3
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).
Note:
Technically, in Miller indices we factor out the common factors. Hence, (220) 2(110) (110).
In XRD we extend the usual concept of Miller indices to include planes, which do not pass through
lattice points (e.g. every alternate plane belonging to the (002) set does not pass through lattice points)
and we allow the common factors to remain in the indices.

I have seen diagrams like in Fig.1 where rays seem to be scattered from nothing!
Funda Check What does this mean?
Few points are to be noted in this context. The ray picture is only valid in the realm of geometrical
optics, where the wave nature of light is not considered (& also the discrete nature of matter is
ignored; i.e. matter is treated like a continuum). In diffraction we are in the domain of physical optics.
The wave impinges on the entire volume of material including the plane of atoms (the effect of which
can be quantified using the atomic scattering power* and the density of atoms in the plane). Due to the
incoming wave the atomic dipoles are set into oscillation, which further act like emitter of waves
In Braggs viewpoint, the atomic planes are to be kept in focus and the wave (not just a ray) impinges
on the entire plane (some planes have atoms in contact and most have atoms, which are not in contact
along the plane see Fig.2).
Wave impinging on a crystal (parallel wavefront)

(note there are no rays)

??

Fig.
2

Fig.
1
of
ction
e
r
i
D

e
wav

* To be considered later
A plane in Braggs viewpoint can be characterized by two factors: (a) atomic density (atoms/unit area on the plane), (b) atomic scattering factor
of the atoms.

More about the Braggs viewpoint

It is difficult to give an explanation of the nature of the semi-transparent layers or

planes that is immediately convincing, as they are a concept rather than a physical
reality. Crystal structures, with their regularly repeating patterns, may be referred to a
3D grid and the repeating unit of the grid, the unit cell, can be found. The grid may be
divided up into sets of planes in various orientations and it is these planes which are
considered in the derivation of Braggs law. In some cases, with simple crystal
structures, the planes also correspond to layers of atoms, but this is not generally the
case. See Section 1.5 for further information.

Some of the assumptions upon which Braggs law is based may seem to be rather
dubious. For instance, it is known that diffraction occurs as a result of interaction
between X-rays and atoms. Further, the atoms do not reflect X-rays but scatter or diffract
them in all directions. Nevertheless, the highly simplified treatment that is used in
deriving Braggs law gives exactly the same answers as are obtained by a rigorous
mathematical treatment. We therefore happily use terms such as reflexion (often
deliberately with this alternative, but incorrect, spelling!) and bear in mind that we are
fortunate to have such a simple and picturesque, albeit inaccurate, way to describe what
in reality is a very complicated process. [1]

[1] Anthony R West, Solid State Chemistry and its Applications, Second Edition, John Wiley & Sons Ltd., Chichester, 2014.

Funda Check 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?

Diffraction is a process in which

linear information (the d-spacing of the planes)
is converted to angular information (the angle of diffraction, 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.
This also implies that in XRD we are concerned with angular resolution instead of linear
resolution.

Later we will see that in powder

diffraction this angle of deviation
(2) is plotted instead of .

Forward and Back Diffraction

Here a guide for quick visualization of forward and backward scattering (diffraction) is presented

Funda Check

What is (theta) in the Braggs equation?

is the angle between the incident x-rays and the set of parallel atomic planes (which have
a spacing dhkl). Which is 10 in the above figure.
Usually, in this context implies Bragg (i.e. the angle at which Braggs equation is
satisfied).
It is NOT the angle between the x-rays and the sample surface (note: specimens could be
spherical or could have a rough surface).

The missing reflections

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 radiation ( = 1.54 ) being diffracted from (100)
planes of Mo (BCC, a = 3.15 = d100).

2 d100 Sin100 Sin100

1.54

0.244 100 14.149

2 d100 2(3.15)

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).

Continuing with the case of BCC Mo

However, the second order reflection from (100) planes (which is equivalent to the first order
reflection from the (200) planes is observed

Sin100

2
1.54

0.48
2 d100 3.15

2nd order
100

1nd order
200

29.26

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!
Funda Check

Why does the 110 reflection not go missing? (Why is it present?)

Let us look at the (110) planes in projection.

Note that (110)blue coloured planes existed before and after introducing an
atom at unit cell centre at (, )grey coloured. Thus lattice centering does
not lead to any waves being scattered out of phase.

Important
points

Presence of additional atoms/ions/molecules in the UC

at lattice points (as we may chose a non-primitive unit cell)
or as a part of the motif
can alter the intensities of some of the reflections
Some of the reflections may even go missing
Position of the reflections/peaks tells us about the lattice type.
The Intensities tells us about the motif.

Intensity of the Scattered Waves

Braggs equation tells us about the position of the diffraction peaks (in terms of ) but
tells us nothing about the intensities. The intensities of the peaks depend on many factors as
considered here.
Scattering by a crystal can be understood in three steps

A
Electron Polarization factor

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

B
Atom Atomic scattering factor (f)

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

C
Unit cell (uc) Structure factor (F)
Click here to know more about

Structure factor calculations

&
Intensity in powder patterns

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.

Click here to know more about

Reciprocal Lattice & Ewald Sphere construction

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

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

Allowed reflections
in SC*, FCC*, BCC*
& DC crystals

h2 + k2 + l2

SC

FCC

100

110

111

111

200

200

210

211

BCC

DC

110
111
200
211

7
Cannot be expressed as (h2+k2+l2)

220

220

300, 221

10

310

11

311

311

12

222

222

13

320

14

321

220

220

310
311
222
321

15

* lattice decorated with

monoatomic/monoionic motif

16

400

17

410, 322

18

411, 330

19

331

400

400

400

411, 330
331

331

Crystal structure determination

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.

Monochromatic X-rays

Panchromatic X-rays

Monochromatic X-rays

Many s (orientations)
Powder specimen
Single

Varied by rotation

POWDER
METHOD

fixed
variable

LAUE
TECHNIQUE

variable
fixed

ROTATING
CRYSTAL
METHOD

fixed
rotated

Only the powder method (which is commonly used in materials science) will be considered in this text.

THE POWDER METHOD

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.

2 d Sin

Cubic crystal

(1)

d hkl Cubic

a
h2 k 2 l 2

(2) in (1)
2
2
4
a
sin

2
2
h k2 l2

2
2
2
a2
(
h

l
)
2
4 sin

* In reality this is true only to an extent

2
4
a
(h 2 k 2 l 2 ) 2 sin 2

(h 2 k 2 l 2 ) sin 2

(2)

The ratio of (h2 + k2 + l2) derived from extinction rules (earlier page)
As we shall see soon the ratios of (h2 + k2 + l2) is proportional to Sin2
which can be used in the determination of the lattice type

SC

BCC

FCC

11

12

DC

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!

POWDER METHOD
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
Usually the source is
geometry as in the figure (right)
Different cones
for different
reflections

Also called Debye ring

fixed and the

detector and sample
are rotated

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].
T
rota he sa
ting mp
le
and
o
det nly th is not
arc ector e sou
so
f a move rce
circ
i
le n

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
h2

hkl

Sin()

100

4.00

0.19

11.10

110

2.83

0.27

15.80

111

2.31

0.33

19.48

200

2.00

0.39

22.64

210

1.79

0.43

25.50

211

1.63

0.47

28.13

220

1.41

0.54

32.99

300

1.33

0.58

35.27

10

310

1.26

0.61

37.50

For convenience the source

may be stationary (and the
sample and detector may
rotate but the effect is
equivalent)

Determination of Crystal Structure from 2 versus Intensity Data in Powder Method

In the power diffraction method a 2 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 (the longer we irradiate the sample the more will be
the intensity under the peak) (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).
* Relative intensity: Intensity of any peak divided by
the intensity of the strongest peak.

Intensity (I) has units of

[Energy/area/time] but here it
is plotted as arbitrary units.

Usually in degrees ()

Powder diffraction pattern from Al

Radiation: Cu K, = 1.54
Increasing d

This is peak (sometimes called a

line- a hangover from Debye
Scherrer camera usage)

Increasing

Determination of Crystal Structure (lattice type) from 2 versus Intensity Data

The following table is made from the 2 versus Intensity data (obtained from a XRD experiment on a
powder sample (empty starting table of columns is shown below- completed table shown later).

Intensity

Sin

Sin2

ratio

Powder diffraction pattern from Al

Radiation: Cu K, = 1.54

These are Miller indices in reciprocal

space (these are not planes they
correspond to panes in real space)

Note:
This is a schematic pattern
In real patterns peaks or not idealized peaks broadened
Increasing splitting of peaks with g
(1 & 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)

Note that there are no brackets

around the indices!

Radiation: Cu K, = 1.54

Powder diffraction pattern from Al

In low angle peaks K1 & K2 peaks merged

400

222

311

220

200

111

Note:
Peaks or not idealized peaks broadened.
Increasing splitting of peaks with g .
Peaks are all not of same intensity.
There is a noisy background.

K1 & K2 peaks resolved in high angle peaks

(in 222 and 400 peaks this can be seen)

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 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

Note peak splitting has not

been included here as this
comes from symmetry
lowering (i.e. crystal with
lower symmetry)

Could be due to uniform strain macrostrain.

Relative intensities of the peaks could be altered

Could be due to texture in the sample.
Instrumental broadening
Peak Broadening

Small crystallite size

Crystal defects (bent planes)

Funda Check

Including those coming from strain

fields associated with these defects

Click
Click here
here to
to know more

What is the maximum value of possible (experimentally)?

At = 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.
2max is 180.

Ans: 90

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: [=2dSin], (Sin)max will correspond to dmin. (Sin)max=1.
Hence, dmin=/2. Hence, if is small then planes with smaller d spacing (i.e. those which
occur at higher 2 values) will also show up in a XRD patter (powder pattern). Given that
experimentally 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 2 as compared to the 001 peak).

2dSin

2d min
Sin max

d min
2

Determination of Crystal Structure (lattice type) from 2 versus Intensity Data

Solved example

Let us assume that we have the 2 versus intensity plot from a diffractometer
To know the lattice type we need only the position of the peaks (as tabulated below)
#

Sin

Sin2

ratio

Index

38.52

19.26

0.33

0.11

111

2.34

44.76

22.38

0.38

0.14

200

2.03

65.14

32.57

0.54

0.29

220

1.43

78.26

39.13

0.63

0.40

11

311

1.22

82.47

41.235

0.66

0.43

12

222

1.17

99.11

49.555

0.76

0.58

16

400

1.01

112.03

56.015

0.83

0.69

19

331

0.93

116.60

58.3

0.85

0.72

20

420

0.91

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

From the ratios in column 6 we conclude that

Using 2 d Sin
o

a 4.04 A Al

FCC

1.54 2 d111 Sin111 2

Note that Sin cannot be > 1

a
0.33
3

Note

(h 2 k 2 l 2 ) sin 2

We can get the lattice parameter which correspond to that for Al

Note: Error in d spacing decreases with so we should use high angle lines for lattice parameter calculation
Click here to know more

XRD_lattice_parameter_calculation.ppt

Solved example

Another example
Given the positions of the Bragg peaks we find the lattice type
Dividing Sin2 by
0.134/3 = 0.044667

Whole
number
ratios

Sin

Sin

Ratios
of Sin2

21.5

0.366

0.134

25

0.422

0.178

1.33

3.99

37

0.60

0.362

2.70

8.10

45

0.707

0.500

3.73

11.19

11

47

0.731

0.535

11.98

12

58

0.848

0.719

5.37

16.10

16

68

0.927

0.859

6.41

19.23

19

FCC

Comparison of diffraction patterns of SC, BCC & B2 structures

Click here

More Solved
Examples on XRDClick here

What happens when we increase or decrease ?

Funda Check 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!!)

With CuK = 1.54

If we ~double we get
too few peaks

If we make small
all the peaks get
crowded to small
angles

And the detector may not be able to resolve

these peaks if they come too close!

Applications of XRD
Bravais lattice determination

We have already seen these applications

Lattice parameter determination

Determination of solvus line in phase diagrams
Long range order
Crystallite size and Strain

Click here to know more

Determine if the material is amorphous or crystalline

Next slide

And
More.

Intensity
0

Crystal

Schematic
s

Schematic of difference between

the diffraction patterns of various phases
Sharp peaks

90

180

Diffraction angle (2)

Intensity

Monoatomic gas
No peak

Intensity

Diffraction angle (2)

Liquid / Amorphous solid

90

0
Diffuse Peak

90

180

Diffraction angle (2)

180

Amorphous solid
Diffuse peak from
Cu-Zr-Ni-Al-Si
Metallic glass

Actual diffraction
pattern from an
amorphous solid

A amorphous solid which shows glass transition in a Differential Scanning Calorimetry (DSC)
plot is also called a glass. In general usage a glass may be considered equivalent to a
amorphous solid (at least loosely in the structural sense).
Sharp peaks are missing. Broad diffuse peak survives
the peak corresponds to the average spacing between atoms which the diffraction experiment picks
out
(XRD patterns) courtesy: Dr. Kallol Mondal, MSE, IITK

 What is the minimum spacing between planes possible in a crystal?

How many diffraction peaks can we get from a powder pattern?

Funda Check

Let us consider a cubic crystal (without loss in generality)

Cubic crystal
d hkl

a
h2 k 2 l 2

As h,k, l increases, d decreases we could have planes with infinitesimal spacing

d13

a
10

d34

a
a

25 5

With increasing indices the

interplanar spacing decreases

d10

a
d12
5

a
a
1

d11

a
2

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.

Q&A

How to increase the number of peaks in a XRD pattern?

We have noted that (e.g. for DC crystal) the number of available peaks in the 2 regime
could be insufficient for a given analysis.
The number of peaks can be increased in two ways:
1) using Mo K instead of Cu K
2) first obtain pattern with filter and then remove the filter to get more lines.