CHAPTER 3

X-RAY DIFFRACTION
IN CRYSTAL
I. X-Ray
II. Diffraction
III. Diffraction of Waves by Crystals
IV. X-Ray Diffraction
V. Bragg Equation
VI. X-Ray Methods
VII. Neutron & Electron Diffraction
Bertha Röntgen’s
Hand 8 Nov, 1895
1
 X-RAY
 X-rays were discovered in
1895 by the German
physicist Wilhelm Conrad
Röntgen and were so named
because their nature was
unknown at the time.

 He was awarded the Nobel

prize for physics in 1901.
Wilhelm Conrad Röntgen
(1845-1923)

2
 X-RAY PROPERTIES
 X ray, invisible, highly penetrating electromagnetic radiation of
much shorter wavelength (higher frequency) than visible light.
The wavelength range for X rays is from about 10-8 m to about
10-11 m, the corresponding frequency range is from about 3 ×
1016 Hz to about 3 × 1019 Hz.

3
 X-RAY ENERGY
 Electromagnetic radiation described as having packets of
energy, or photons. The energy of the photon is related to its
frequency by the following formula:

E  h
hc c
E
  


hc
 =Wavelength , ‫ = ע‬Frequency , c = Velocity of light E 


 x-ray ≈ 10-10 ≈ 1A° E ~ 104 ev

4
 PRODUCTION OF X-RAYS

 Visible light photons and X-ray photons are both

produced by the movement of electrons in atoms.
Electrons occupy different energy levels, or orbitals,
around an atom's nucleus.

 When an electron drops to a lower orbital, it needs to

release some energy; it releases the extra energy in the
form of a photon. The energy level of the photon depends
on how far the electron dropped between orbitals.

5
6
 X-RAY TUBE
 X rays can be produced in a highly evacuated glass bulb, called
an X-ray tube, that contains essentially two electrodes—an
anode made of platinum, tungsten, or another heavy metal of
high melting point, and a cathode. When a high voltage is
applied between the electrodes, streams of electrons (cathode
rays) are accelerated from the cathode to the anode and
produce X rays as they strike the anode.
Evacuated glass bulb

Cathode
Anode

7
 Monochromatic and Broad
Spectrum of X-rays
 X-rays can be created
4
by bombarding a metal target with
high energy (> 10 ) electrons.

 Some of these electrons excite electrons from core states in

the metal, which then recombine, producing highly
monochromatic X-rays. These are referred to as
characteristic X-ray lines.

 Other electrons, which are decelerated by the periodic

potential of the metal, produce a broad spectrum of X-ray
frequencies.

 Depending on the diffraction experiment, either or both of

these X-ray spectra can be used. 10 4

8
 ABSORPTION OF X-RAYS

 The atoms that make up your body ...something

tissue absorb visible light photons you won't
very well. The energy level of the see very
photon fits with various energy often
differences between electron (Visible
positions. Light)

 Radio waves don't have enough

energy to move electrons between
orbitals in larger atoms, so they pass
through most stuff. X-ray photons also X-ray
pass through most things, but for the
opposite reason: They have too much
energy.

9
 Generation of X-rays (K-Shell
Knockout)
An electron in a higher orbital immediately falls to the lower energy
level, releasing its extra energy in the form of a photon. It's a big drop,
so the photon has a high energy level; it is an X-ray photon.

The free electron collides

with the tungsten atom,
knocking an electron out of a
lower orbital. A higher orbital
electron fills the empty
position, releasing its excess
energy as a photon.

10
 Absorption of X-rays

 A larger atom is more likely to absorb an X-ray photon in

this way, because larger atoms have greater energy
differences between orbitals -- the energy level more
closely matches the energy of the photon. Smaller atoms,
where the electron orbitals are separated by relatively low
jumps in energy, are less likely to absorb X-ray photons.

 The soft tissue in your body is composed of smaller

atoms, and so does not absorb X-ray photons particularly
well. The calcium atoms that make up your bones are
much larger, so they are better at absorbing X-ray
photons.

11
 DIFFRACTION

 Diffraction is a wave phenomenon in

which the apparent bending and
spreading of waves when they meet an
obstruction.
 Diffraction occurs with electromagnetic
waves, such as light and radio waves,
and also in sound waves and water
waves. Width b Variable
(500-1500 nm)
 The most conceptually simple example of
diffraction is double-slit diffraction, that’s Wavelength Constant
why firstly we remember light diffraction. (600 nm)
Distance d = Constant

12
 LIGHT DIFFRACTION

 Light diffraction is caused by light bending around the edge of

an object. The interference pattern of bright and dark lines from
the diffraction experiment can only be explained by the additive
nature of waves; wave peaks can add together to make a
brighter light, or a peak and a through will cancel each other out
and result in darkness.

Thus Young’s light interference

experiment proves that light
has wavelike properties.

13
LIGHT INTERFERENCE

14
 Constructive & Destructive Waves

 Constructive interference is  Destructive İnterference .

the result of synchronized results when two out-of-phase
light waves that add light waves cancel each other
together to increase the light out, resulting in darkness.
intensity.

15
Light Interference

16
 Diffraction from a particle and solid

Single particle
 To understand diffraction we also have
to consider what happens when a wave
interacts with a single particle. The
particle scatters the incident beam
uniformly in all directions

Solid material
 What happens if the beam is incident
on solid material? If we consider a
crystalline material, the scattered
beams may add together in a few
directions and reinforce each other
to give diffracted beams
17
 Diffraction of Waves by Crystals

A crystal is a periodic structure

( unit cells are repeated regularly)

Solid State Physics deals how the waves are propagated

through such periodic structures. In this chapter we study the
crystal structure through the diffraction of photons (X-ray),
nuetrons and electrons.

Diffraction
X-ray Neutron Electron

The general princibles will be the same for each type of waves.
18
 Diffraction of Waves by Crystals

 The diffraction depends on the crystal structure and on

the wavelength.
 At optical wavelengths such as 5000 angstroms the
superposition of the waves scattered elastically by the
individual atoms of a crystal results in ordinary optical
refraction.
 When the wavelength of the radiation is comparable
with or smaller than the lattice constant, one can find
diffracted beams in directions quite different from the
incident radiation.

19
 Diffraction of Waves by Crystals

 The structure of a crystal can be determined by

studying the diffraction pattern of a beam of radiation
incident on the crystal.

 Beam diffraction takes place only in certain specific

directions, much as light is diffracted by a grating.

 By measuring the directions of the diffraction and the

corresponding intensities, one obtains information
concerning the crystal structure responsible for
diffraction.
20
 X-RAY CRYSTALLOGRAPHY

 X-ray crystallography is a technique in crystallography in

which the pattern produced by the diffraction of x-rays through
the closely spaced lattice of atoms in a crystal is recorded and
then analyzed to reveal the nature of that lattice.

 X-ray diffraction = (XRD)

21
 X-Ray Crystallography

 The wavelength of X-rays is

typically 1 A°, comparable to the
interatomic spacing (distances
between atoms or ions) in solids.

 We need X-rays:

hc hc
Exray    h    12.3 x103
eV
10
 1x10 m
22
 Crystal Structure Determination

A crystal behaves as a 3-D diffraction grating for x-rays

 In a diffraction experiment, the spacing of lines on the grating
can be deduced from the separation of the diffraction maxima
Information about the structure of the lines on the
grating can be obtained by measuring the relative
intensities of different orders
 Similarly, measurement of the separation of the X-ray
diffraction maxima from a crystal allows us to determine
the size of the unit cell and from the intensities of
diffracted beams one can obtain information about the
arrangement
23 of atoms within the cell.
 X-Ray Diffraction

W. L. Bragg presented a simple

explanation of the diffracted beams from a
crystal.
The Bragg derivation is simple but is
convincing only since it reproduces the
correct result.

24
 X-Ray Diffraction & Bragg Equation

 English physicists Sir W.H. Bragg

and his son Sir W.L. Bragg
developed a relationship in 1913 to
explain why the cleavage faces of
crystals appear to reflect X-ray
beams at certain angles of incidence
(theta, θ).This observation is an Sir William Henry  Bragg (1862-1942),
example of X-ray wave interference. William Lawrence  Bragg (1890-1971)

o 1915, the father and son were awarded the Nobel prize for physics
"for their services in the analysis of crystal structure by means of
Xrays".

25
 Bragg Equation
 Bragg law identifies the angles of the incident
radiation relative to the lattice planes for which
diffraction peaks occurs.
 Bragg derived the condition for constructive
interference of the X-rays scattered from a set of
parallel lattice planes.

26
 BRAGG EQUATION
 W.L. Bragg considered crystals to be made up of parallel
planes of atoms. Incident waves are reflected specularly from
parallel planes of atoms in the crystal, with each plane is
reflecting only a very small fraction of the radiation, like a
lightly silvered mirror.
 In mirrorlike reflection the angle of incidence is equal to the
angle of reflection.

ө ө

27
 Diffraction Condition

 The diffracted beams are found to occur

when the reflections from planes of atoms
interfere constructively.
 We treat elastic scattering, in which the
energy of X-ray is not changed on reflection.

28
 Bragg Equation
 When the X-rays strike a layer of a crystal, some of them will
be reflected. We are interested in X-rays that are in-phase
with one another. X-rays that add together constructively in x-
ray diffraction analysis in-phase before they are reflected and
after they reflected.


Incident angle

Reflected angle

Wavelength of X-ray

  2

Total Diffracted
Angle  2
29
 Bragg Equation
 These two x-ray beams travel slightly different distances. The
difference in the distances traveled is related to the distance
between the adjacent layers.
 Connecting the two beams with perpendicular lines shows the
difference between the top and the bottom beams.

The line CE is equivalent

to the distance between
the two layers (d)

DE  d sin 

30
 Bragg Law
 The length DE is the same as EF, so the total distance
traveled by the bottom wave is expressed by:

EF  d sin 
DE  d sin 

DE  EF  2d sin 
n  2d sin 

 Constructive interference of the radiation from successive

planes occurs when the path difference is an integral
number of wavelenghts. This is the Bragg Law.
31
 Bragg Equation
2d sin   n
where, d is the spacing of the planes and n is the order of diffraction.

 Bragg reflection can only occur for wavelength

n  2 d
 This is why we cannot use visible light. No diffraction occurs when
the above condition is not satisfied.

 The diffracted beams (reflections) from any set of lattice planes

can only occur at particular angles pradicted by the Bragg law.
32
 Scattering of X-rays from adjacent
lattice points A and B
X-rays are incident at an angle on one of the planes
of the set.
There will be constructive interference of the waves
scattered from the two successive lattice points A and B in
the plane if the distances AC and DB are equal.

D C

  2
A B
33
 Constructive interference of waves
scattered from the same plane
If the scattered wave makes the same angle to the plane as
the incident wave

The diffracted wave looks as if it has been reflected from the

plane

We consider the scattering from lattice points rather

than atoms because it is the basis of atoms associated with
each lattice point that is the true repeat unit of the crystal;
The lattice point is analoque of the line on optical diffraction
grating and the basis represents the structure of the line.

34
 Diffraction maximum
Coherent scattering from a single plane is not
sufficient to obtain a diffraction maximum. It is also
necessary that successive planes should scatter
in phase

 This will be the case if the path difference for

scattering off two adjacent planes is an integral
number of wavelengths

2d sin   n
35
 Labelling the reflection planes

 To label the reflections, Miller indices of the planes

can be used.
 A beam corresponding to a value of n>1 could be
identified by a statement such as ‘the nth-order
reflections from the (hkl) planes’.
 (nh nk nl) reflection
Third-order reflection from (111) plane

(333) reflection
36
 n-th order diffraction off (hkl)
planes
 Rewriting the Bragg law
d 
2  sin   
n
which makes n-th order diffraction off (hkl) planes of
spacing ‘d’ look like first-order diffraction off planes
of spacing d/n.

 Planes of this reduced spacing would have Miller

indices (nh nk nl).

37
 X-ray structure analysis of NaCl
and KCl
The GENERAL PRINCIBLES of X-RAY STRUCTURE ANALYSIS to
DEDUCE the STRUCTURE of NaCl and KCl
Bragg used an ordinary spectrometer and measured the intensity of
specular reflection from a cleaved face of a crystal

found six values of  for which a sharp peak in intensity occurred,

corresponding to three characteristics wavelengths (K,L and M x-
rays) in first and second order (n=1 and n=2 in Bragg law)
 By repeating the experiment with a different crystal face he could
use his eqn. to find for example the ratio of (100) and (111) plane
spacings, information that confirmed the cubic symmetry of the
atomic arrangement.
38
 Details of structure
Details of structure were than deduced from the differences
between the diffraction patterns for NaCl and KCl.
 Major difference; absence of (111) reflection in KCl compared to a
weak but detectable (111) reflection in NaCl.

 This arises because the K and Cl ions both

have the argon electron shell structure and
hence scatter x-rays almost equally whereas
Na and Cl ions have different scattering
strengths. (111) reflection in NaCl corresponds
to one wavelength of path difference between
neighbouring (111) planes.

39
 Experimental arrangements
for x-ray diffraction
 Since the pioneering work of Bragg, x-ray
diffraction has become into a routine
technique for the determination of crsytal
structure.

40
 Bragg Equation
Since Bragg's Law applies to all sets of crystal planes,
the lattice can be deduced from the diffraction pattern,
making use of general expressions for the spacing of the
planes in terms of their Miller indices. For cubic structures

a
d
h2  k 2  l 2

Note that the smaller the spacing the higher the angle
of diffraction, i.e. the spacing of peaks in the diffraction
pattern is inversely proportional to the spacing of the planes
in the lattice. The diffraction pattern will reflect the
symmetry properties of the lattice.
2d sin   n
41
Bragg Equation
A simple example is the difference between
the series of (n00) reflections for a simple
cubic and a body centred cubic lattice. For the
simple cubic lattice, all values of n will give Bragg
peaks.
However, for the body centred cubic lattice
the (100) planes are interleaved by an equivalent
set at the halfway position. At the angle where
Bragg's Law would give the (100) reflection the
interleaved planes will give a reflection exactly out
of phase with that from the primary planes, which
will exactly cancel the signal. There is no signal
from (n00) planes with odd values of n. This kind
of argument leads to rules for identifying the
lattice symmetry from "missing" reflections, which
are often quite simple.
42
 Types of X-ray camera

There are many types of X-ray camera to

sort out reflections from different crystal
planes. We will study only three types of X-ray
photograph that are widely used for the simple
structures.
1. Laue photograph
2. Rotating crystal method
3. Powder photograph

43
 X-RAY DIFFRACTION METHODS

X-Ray Diffraction Method

Laue Rotating Crystal Powder

Orientation Lattice constant Lattice Parameters

Single Crystal Single Crystal Polycrystal (powdered)
Polychromatic Beam Monochromatic Beam Monochromatic Beam
Fixed Angle Variable Angle Variable Angle

44
 LAUE METHOD
 The Laue method is mainly used to determine the
orientation of large single crystals while radiation is
reflected from, or transmitted through a fixed crystal.

 The diffracted beams form arrays of

spots, that lie on curves on the film.

 The Bragg angle is fixed for every

set of planes in the crystal. Each set
of planes picks out and diffracts the
particular wavelength from the white
radiation that satisfies the Bragg law
for the 45
values of d and θ involved.
 Back-reflection Laue Method

 In the back-reflection method, the film is placed between the

x-ray source and the crystal. The beams which are diffracted
in a backward direction are recorded.

 One side of the cone of Laue

reflections is defined by the
transmitted beam. The film
intersects the cone, with the
diffraction spots generally lying
on an hyperbola. Single
Crystal
X-Ray Film

46
 Transmission Laue Method

 In the transmission Laue method, the film is placed behind

the crystal to record beams which are transmitted through
the crystal.

 One side of the cone of Laue

reflections is defined by the
transmitted beam. The film
intersects the cone, with the
diffraction spots generally
lying on an ellipse.
Single Film
X-Ray
Crystal
47
 The symmetry of the
Laue Pattern spot pattern reflects the
symmetry of the crystal
when viewed along the
direction of the incident
beam. Laue method is
often used to determine
the orientation of single
crystals by means of
illuminating the crystal
with a continuos spectrum
of X-rays;
 Single crystal
 Continous spectrum of x-
rays
48  Symmetry of the crystal;
orientation
 Crystal structure
determination by Laue
method
 Therefore, the Laue method is mainly used to
determine the crystal orientation.
 Although the Laue method can also be used to
determine the crystal structure, several
wavelengths can reflect in different orders from the
same set of planes, with the different order
reflections superimposed on the same spot in the
film. This makes crystal structure determination by
spot intensity diffucult.
 Rotating crystal method overcomes this problem.
How?

49
 ROTATING CRYSTAL METHOD

 In the rotating crystal method, a

single crystal is mounted with
an axis normal to a
monochromatic x-ray beam.
A cylindrical film is placed
around it and the crystal is
rotated about the chosen axis. 

 As the crystal rotates, sets of lattice planes will at some

point make the correct Bragg angle for  the monochromatic
incident beam, and at that point a diffracted beam will be
formed.  
50
 ROTATING CRYSTAL
METHOD
Lattice constant of the crystal can be
determined by means of this method; for a
given wavelength if the angle  at which a
reflection occurs is
d hklknown,
can be determined.
a
d 
h2  k 2  l 2

51
 Rotating Crystal Method

The reflected beams are located on the surface of imaginary

cones. By recording the diffraction patterns (both angles and
intensities) for various crystal orientations, one can determine the
shape and size of unit cell as well as arrangement of atoms inside
the cell.

Film

52
 THE POWDER METHOD

If a powdered specimen is used, instead of a

single crystal, then there is no need to rotate
the specimen, because there will always be
some crystals at an orientation for which
diffraction is permitted. Here a monochromatic
X-ray beam is incident on a powdered or
polycrystalline sample.
This method is useful for samples that are
difficult to obtain in single crystal form.

53
 THE POWDER METHOD

The powder method is used to determine the value

of the lattice parameters accurately. Lattice parameters
are the magnitudes of the unit vectors a, b and c which
define the unit cell for the crystal.

For every set of crystal planes, by chance, one or

more crystals will be in the correct orientation to give
the correct Bragg angle to satisfy Bragg's equation.
Every crystal plane is thus capable of diffraction. Each
diffraction line is made up of a large number of small
spots, each from a separate crystal. Each spot is so
small as to give the appearance of a continuous line .
54
 The Powder Method

 Aa
If the
sample
monochromatic
sampleof someconsists
hundreds
x-ray
of beam
some of
is directed
tens
crystals of randomly
(i.e.
at a a singleorientated
powdered
crystal,
then only
single
sample) one that
crystals,
show or the
two
the diffracted
beams may are result.
form seen
continuous
to lie oncones.
the
surface
A circle ofof film
several
is used cones.
to record
The
cones
the diffraction
may patternemergeas shown.
in all
directions,
Each cone intersects
forwards the and film
backwards.
giving diffraction lines. The lines
are seen as arcs on the film.

55
 Debye Scherrer Camera
A very small amount of powdered material is sealed
into a fine capillary tube made from glass that does not
diffract x-rays.

The specimen is placed

in the Debye Scherrer
camera and is accurately
aligned to be in the centre
of the camera. X-rays enter
the camera through a
collimator.

56
 Debye Scherrer Camera

The powder diffracts

the x-rays in accordance
with Braggs law to
produce cones of
diffracted beams. These
cones intersect a strip of
photographic film located
in the cylindrical camera to
produce a characteristic
set of arcs on the film.

57
 Powder diffraction film

When the film is removed from the camera,

flattened and processed, it shows the diffraction
lines and the holes for the incident and
transmitted beams.

58
 Application of XRD
XRD is a nondestructive technique. Some of the uses of
x-ray diffraction are;

1. Differentiation between crystalline and amorphous

materials;
2. Determination of the structure of crystalline materials;
3. Determination of electron distribution within the atoms, and
throughout the unit cell;
4. Determination of the orientation of single crystals;
5. Determination of the texture of polygrained materials;
6. Measurement of strain and small grain size…..etc

59
Advantages and
disadvantages of X-rays
Advantages;
 X-ray is the cheapest, the most convenient and
widely used method.
 X-rays are not absorbed very much by air, so
the specimen need not be in an evacuated
chamber.
Disadvantage;
 They do not interact very strongly with lighter
elements.

60
 Difraction Methods

Diffraction
X-ray Neutron Electron

Different radiation source of neutron or

electron can also be used in diffraction
experiments.
The physical basis for the diffraction of
electron and neutron beams is the same as that
for the diffraction of X rays, the only difference
being
61 in the mechanism of scattering.
 Neutron Diffraction

 Neutrons were discovered in 1932 and their wave

properties was shown in 1936.
E = p2/2m p = h/λ
E=Energy λ=Wavelength
p=Momentum
mn=Mass of neutron = 1,67.10-27kg

 λ ~1A°; Energy E~0.08 eV. This energy is of the same

order of magnitude as the thermal energy kT at room
temperature, 0.025 eV, and for this reason we speak of
thermal neutrons.

62
 Neutron Diffraction

 Neutron does not interact with electrons in the crystal.

Thus, unlike the x-ray, which is scattered entirely by
electrons, the neutron is scattered entirely by nuclei

 Although uncharged, neutron has an intrinsic magnetic

moment, so it will interact strongly with atoms and ions in
the crystal which also have magnetic moments.

 Neutrons are more useful than X-rays for determining the

crystal structures of solids containing light elements.

 Neutron sources in the world are limited so neutron

diffraction is a very special tool.

63
 Neutron Diffraction

Neutron diffraction has several advantages over its x-

ray counterpart;
 Neutron diffraction is an important tool in the investigation
of magnetic ordering that occur in some materials.

 Light atoms such as H are better resolved in a neutron

pattern because, having only a few electrons to scatter
the X ray beam, they do not contribute significantly to the
X ray diffracted pattern.

64
 Electron Diffraction
Electron diffraction has also been used in the analysis of
crystal structure. The electron, like the neutron, possesses wave
properties;

E
 2k 2

h2
 40eV   2A 0
2me 2me 2

Electrons are charged particles and interact strongly with

all atoms. So electrons with an energy of a few eV would be
completely absorbed by the specimen. In order that an
electron beam can penetrate into a specimen , it necessitas a
beam of very high energy (50 keV to 1MeV) as well as the
specimen must be thin (100-1000 nm)
65
 Electron Diffraction

If low electron energies are used, the penetration depth will

be very small (only about 50 A°), and the beam will be reflected
from the surface. Consequently, electron diffraction is a useful
technique for surface structure studies.

Electrons are scattered strongly in air, so diffraction

experiment must be carried out in a high vacuum. This brings
complication and it is expensive as well.

66
 Diffraction Methods

X-Ray Neutron Electron

λ = 1A° λ = 1A° λ = 2A°

E ~ 104 eV E ~ 0.08 eV E ~ 150 eV

interact with electron interact with nuclei interact with electron

Penetrating Highly Penetrating Less Penetrating

67