7) SSP 2

fiziks
Institute for CSIR‐UGC JRF/NET, GATE, IIT‐JAM, GRE in PHYSICAL SCIENCES
2. X-Ray diffraction
2.1 Structure Factor
The atomic scattering factor or form factor f describes the scattering power of a single
atom in relation to the scattering power of a single electron and given by:
amplitude of radiation scattered from an atom
f =
amplitude of radiation scattered from an electron
In general f < Z, it approaches Z (atomic no.) in the limit case. The phase difference
between the wave scattered from the charge ρ(r) dv and that scattering from electron, in
accordance equation is given by
N n̂L
Geometric Structure Factor
The intensity of an x-ray beam n̂1
diffracted from a crystal not only n̂2 n̂2
n
depends upon the atomic θ θ
scattering
scattering factor of the various phase
atom involved but also on the
contents of the unit cell, i.e. on
the number. The total scattering amplitude F(h' k' l') for the reflection (h' k' l') is defined
as the ratio of the amplitude of radiation scattered by a single point electron placed at
origin for the same wavelength. It is given by:
⎛ 2π ⎞
i⎜ ⎟( rj ⋅N )
F ( h' k ' l ' ) = ∑ f j e iφj
= ∑ f je ⎝ λ ⎠
where fj is the atomic scattering factor for the jth atom αφ j is the phase difference if (uj,
vj, wj) represents the co-ordinate of jth atom we can write rj = uja + vjb +wjc, and
(u j h + v j k + w j l )
rj .N = λ (ujh + vjk + wjl) i.e. F (hkl ) = ∑ f j e i 2π
i
For identical atoms, all the fj’s have the same value f. Therefore, equation (i) take a
simple form. F(hkl) = f S
where S = ∑ e
2πi ( u j h + v j k + w j l )
is called Geometrical Structure Factor.
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Now since the intensity of a radiation is proportional to the square of its amplitude, the
intensity of diffracted beam may be written by I = |F|2 = F* F
The structure factor for some simple crystals are calculated below and the intensity of
various order of reflections associated with these structures is discussed.
Note: i) We can by find the structure factor allowed reflection by given crystal structure
either wise zero.
ii) eiθ = cos θ + i sin θ or eiπ = cos π + i sin π
(a) Simple cubic crystal: Unit cell contains only one atom at the origin
i.e. (u, v, w) = (0, 0, 0)
∴ F = fe2πi(0) = f
And therefore intensity which is the square of the amplitude is F2 = f2.
Thus F2 is thus independent of h, k & l and the same for all reflection.
∴ All h, k, l are possible in SC.
1 1
(b) Base centered cell: It has 2 atoms at 0, 0, 0 & , ,0
2 2
∴ F = f[1 + eπi(h + k)]
And F = 2f ⇒ F2 = 4f2: for h & k unmixed
While F = 0 ⇒ F2 = 0: for h & k mixed
Note : The value of l index has no effect on the structure factor
∴ Present planes are: (111), (112), (113) & (021), (022), (023)
Absent planes are: (011), (012), (013) & (101), (102), (103)
⎛1 1 1⎞
(c) Body Centered cell: It has 2 atoms at (0 0 0) & ⎜ ⎟
⎝2 2 2⎠
∴ F = f[1 + eπi(h + k + l)]
And F = 2f ⇒ F2 = 4f2: when (h + k + l) = Even
While F = 0 ⇒ F2 = 0: when (h + k + l) = odd
∴ Present planes are: (1 1 0), (2 0 0), (2 2 2) etc
Absent planes are: (1 0 0), (1 1 1), (2 1 0) etc

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⎛1 1 ⎞ ⎛1 1⎞ ⎛ 1 1⎞
(d) Face centered cell: It has 4 atoms at (0 0 0), ⎜ 0⎟ , ⎜ 0 ⎟ and ⎜ 0 ⎟
⎝22 ⎠ ⎝2 2⎠ ⎝ 2 2⎠
∴ F = f [1 + eπi(h + k) + eπi(h + l) + eπi(k + l)]
And F = 4f ⇒ F2 = 16f2 : If h, k, l are unmixed
While F = 0 ⇒ F2 = 0 : If h, k, l are mixed
∴ Present planes are: (1 1 1), (2 0 0), (2 2 0) etc
Absent planes are: (1 0 0), (1 1 0), (2 1 1) etc.
Simplified Table
Bravais lattice Reflection possibly Present Reflection necessarily absent
Simple cubic All None
Base centered cubic h & k unmixed h & k mixed
Body centered cubic (h + k + l) even (h + k + l) odd
Face centered cubic h, k & l unmixed h, k & l mixed
Note: (1) The first order reflection from (1 0 0) planes in a bcc crystal is absent, while
second order reflections from (1 0 0) plane is present and it is this reflection
which appears at the position of the 1st order reflection from (2 0 0) planes.
(2) The ratio of (h2 + k2 + l2) values for all allowed reflection from cubic crystal as
obtained from the extinction rules are given as follows.
SC :: 1 : 2 : 3 : 4 : 5 : 6 : 8 : 9 : 10 : 11 : 12
BCC : : 2 : 4 : 6 : 8 : 10 : 12 : 14 : 16 : 18 : 20
FCC :: 3 : 4 : 8 : 11 : 12 : 16 : 19 : 20 :
DC :: 3 : 8 : 11 : 16 : 19 : 20

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2.2 Braggs Law

X-rays are a form of electromagnetic radiation and these are used for determining the
crystal structures are they have high energy and short wavelengths. The wavelengths of
x-rays are of the order of the atomic spacing for solids. When a beam of x-rays impinges
on a solid material, a portion of this beam will be scattered in all direction by the
electrons associated with each atom or ion that lies within the beam path.
θ Αθ
θ θ
d hkl
C D
θ θ
B
From figure n λ = CB + BD
In ∆ ABC,
CB = AB sin θ = dhkl sin θ
BD = AD sin θ = dhkl sin θ
∴ d hkl sin θ = nλ
2dhkl sin θ = nλ
This is known as Bragg’s law, n is order of reflection. For SC a = b = c
nλ
sin θ = h2 + k 2 + l 2
2a

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2.3 Methods of X-ray Diffraction

In x-ray diffraction studies, the probability that the atomic planes with right orientations
are exposed to x-rays is increased by adopting there of crystal structure studies method.
1) Law Method
2) Rotating Method
3) Powder Method
1) Laue’s Technique
The single crystal is held stationary and a beam of white radiations is inclined on it at a
fixed glacing angle θ i.e. θ is fixed while λ is varies different wavelengths present in the
white radiations select the appropriate reflecting planes out of the numerous present in
the crystal such that the Bragg’s condition is satisfied this technique is called the Laue’s
technique.
2) Rotating Crystal Method
A single crystal is held in the path of monochromatic radiations and is rotated about an
axis i.e. λ is fixed while θ varies. Different sets of parallel atomic planes are exposed to
incident radiations for different values of θ and reflections take place from those atomic
planes for which d and θ satisfied the Bragg’s law. This method is known as the rotating
crystal method.
3) Powder Method
Modern x-ray crystal analysis uses an x-ray diffractometer which has a radiation counter
to detect the angle and intensity of the diffraction beam.
100
Intensity (a.u.)
X-ray
001
X-ray
detector
110
source
102
101
θ 2θ
002
201
112
Sample
stage
20 30 40 50 60 70 80
2θ (degree)

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A recorder automatically plots the intensity of the diffracted beam as the counter moves
on a Goniometer circle. Figure shows an x-ray diffraction recorder chart for the intensity
of the diffracted beam verses the diffraction angle 2θ for a powdered pure metal
specimen.
Characteristics of the Bragg’s law:
(i). It is the consequence of the periodicity of the space lattice.
(ii). The Bragg’s law does not refer to the arrangement or basis of the atoms associated
with the lattice points.
(iii). For a given order n and spacing d, the angle θ decreases with decrease in the
wavelength λ.
(iv). The relative intensity of the various orders n of diffraction from a given set of
parallel planes is determine by the composition of the basis of the crystal results in
the change in d. This in turn changes the phase difference between the interfering
waves and hence the resulting amplitude. Being proportional to the square of the
amplitude the intensity is therefore affected.
(v). Bragg’s reflection occur only for the wavelength λ ≤ 2d . That’s why crystal cannot
diffract visible rays.
(vi). For X-ray photons,
hc 12400
E=hv = hc/λ or λ ( A0 ) =
=
E E (eV )
Therefore the energy of X-rays of wavelength 1A0 is 12.4keV.

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Electron Diffraction by Crystal

According to de-Broglie, a particle of momentum p (= mv) is associated with a wave of
wavelength
h h
λ ( A0 ) = =
P 2mE
Where h is the Planck constant. M is the mass of the electron and E is the energy of the
electron. Since m = 9.1x10-31kg.
12
Therefore λ ( A 0 ) =
E
Thus the energy of electrons of wavelength 1A0 is 144eV.
Characteristic of Electron Diffraction
(i). Incident electrons are not only diffracted by the electrons but also by the nuclei of the
atoms of the crystal. So the electron diffraction is much more intense than X-ray
diffraction.
(ii). An electron beam has very low penetration power as it experiences repulsion from
atomic electrons. Therefore this technique is useful for thin films.
Neutron diffraction by Crystal
Using the de-Broglie relation for neutron (mass m=1.675x10-27kg) the associated
wavelength
0.28
λ ( A0 ) =
E
This shows that the energy associated with neutrons of wavelength 1A0 is approximately
0.08eV. This energy is much less than of X-rays of the same wavelength.
Characteristic of Neutron Diffraction
(i) Neutrons are scattered only by the nuclei of the atoms of the crystal.
(ii) Scattering cross section does not vary with increasing atomic number.
(iii) Lighter elements such as hydrogen and carbon produces strong neutron scattering
which is almost absent in X-ray diffraction.


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fiziks

Institute for CSIR‐UGC JRF/NET, GATE, IIT‐JAM, GRE in PHYSICAL SCIENCES

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2.2 Braggs Law

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2.3 Methods of X-ray Diffraction

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Electron Diffraction by Crystal

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