Solid State Physics

Course no: PHY F341

2nd Sem (2019-20)

by
Subhashis Gangopadhyay
Department of Physics
(Room 3242-A)
 X-ray diffraction

Diffraction techniques exploit the scattering of radiation

from large numbers of sites makes pattern

Patterns are the outcome of the diffracted beams

helps to determine the structure

 X-ray diffraction

 Electron diffraction
 X-ray diffraction from crystalline solid

 measure the average spacing between

layers or rows of atoms

 determine the orientation of a single crystal

or grain

 find the crystal structure of an unknown

material

 measure the size, shape and internal stress

of small crystalline regions
 X-RAY DIFFRACTION

•X- Ray Sources

•Diffraction: Bragg’s Law
•Crystal Structure Determination
 Why X-RAY for DIFFRACTION

For electromagnetic radiation to be diffracted, the

spacing in the grating should be of the same order as
the wavelength

In crystals, the typical inter-atomic spacing is about ~ 2-3 Å

 X-rays: a suitable radiation to study the crystal structures
 How to produce X-RAY

Beam of electrons X-rays

Target

A accelerating charge radiates electromagnetic radiation

X-RAY tube
Synchrotron radiation source
Electrons accelerated by a 35 kV potential and hit metal targets

K

Characteristic
White K
Intensity

radiation
radiation

0.2 0.6 1.0 1.4

Wavelength ()
Characteristic radiation → due to energy transitions in the atom
 Characteristic X-rays

Vacuum
Knocked out electron
from inner shell

E L3 L3
Energy
E L2 L2
levels
EL1 L1
Characteristic x-rays
EK K (Fluorescent X-rays)
(10−16s later  seems like scattering!)
Nucleus
Characteristic X-rays energies

Target Metal  of K radiation (Å)

Mo 0.71

Cu 1.54

Co 1.79

Fe 1.94

Cr 2.29
 Scattering of X-rays
X-rays beam directed, interacts with the electrons of the crystal atoms
 Electrons oscillate under the influence of the incoming X-Rays
 Become secondary sources of EM radiation, in all directions
The waves emitted by the electrons have the same frequency  coherent
 The emission undergo constructive or destructive interference

Secondary
Incoming X-rays emission
 Scattering of X-ray by an atom

Electron cloud oscillates Nucleus also oscillates

weak effect  neglected
 Emission from secondary source

 Oscillating charge (electron cloud) re-radiates

 Radiation is in phase with the incoming x-rays
Scattering of X-ray by atomic planes
 Scattering of X-rays: phase relation

Incident and scattered waves are in phase if

In plane scattering is in phase
Scattering from across planes is in phase
 In plane scattering

Extra path traveled by incoming waves  AY These can be in phase if and only if
Extra path traveled by scattered waves  XB  incident = scattered

A B A B

X Y X Y
Atomic Planes

But this is still reinforced scattering and NOT reflection

 BRAGG’s law for constructive interferences

Deviation = 2

Incident ray 1 Scattered ray 1

Incident ray 2 Scattered ray 2

 

 d
Incident ray 3 Scattered ray 3

 The path difference between Ray 1 and Ray 2 is = 2d Sin

 For constructive interference: 2d Sin = n
Bragg’s law: 2d Sin = n
 n is an integer and is the order of the reflection
 For Cu K radiation ( = 1.54 Å) and d110= 2.22 Å

n Sin 
1 0.34 20.7º First order reflection from (110)
Second order reflection from (110)
2 0.69 43.92º
Also written as (220)

a
d hkl 
h k l
2 2 2
 Different lattice planes

(220) Plane in NaCl crystal (200) Plane in NaCl crystal

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

a
n  2d hkl sin  d 220 
8
d hkl
2 sin  a
n d110 
  2d nh nk nl sin  2
d 220 1

d110 2
 Crystal structure determination

LAUE
Panchromatic X-rays Single 
TECHNIQUE

ROTATING
Monochromatic X-rays  Varied by rotation CRYSTAL
METHOD

Monochromatic X-rays Many s (orientations) POWDER

Powder specimen METHOD
X-RAY diffraction pattern
The Rotating Crystal Method
 2 2 2

 For every set of planes, there will be a small percentage of crystallites that are
properly oriented to diffract (the plane perpendicular bisects the incident and
diffracted beams).
 Basic assumptions of powder diffraction are that for every set of planes there are an
equal number of crystallites that will diffract and that there are a statistically relevant
number of crystallites, not just one or two.
The Powder Method

Cone of diffracted rays

The Powder Method
The Powder Method

The film shows the

recordings of the
diffraction pattern
as dark arcs.
 Peak properties

• Peak position: inter planar spacing

• Peak intensity: number of atoms on plane

• Peak width: number of planes.

• Peak broadening: non-uniform lattice parameter

(imperfections, lattice strains) and instrumental error
 Intensity of the Scattered wave

A B C
Scattering by a crystal Electron Atom Unit cell (uc)

Structure factor (F)

Polarization factor

Atomic scattering factor (f)

 Scattering of x-ray by an Electron

(0 , 0 )
Sets electron into oscillation

Coherent
(definite phase relationship) (0 , 0 ) Scattered beams
 Scattering of x-ray by an Electron: polarized wave
z
P
For a wave oscillating in z direction  r

Intensity of the scattered beam due to an electron (I)

e 4  Sin 2 
I  I 0 2 4  2 
mc  r 
Very small number
 Scattering of x-ray by an Electron: unpolarized wave

E is amplitude of the wave

E2 = I = Intensity

E 2  E y2  Ez2 I0
 I0 y  I0z
2

I Py  I 0 y
e 4  Sin 2 
   I
2 e4  1 
2 4  2 
IPy = Intensity at P due to Ey
m 2c 4   0y
r2 m c r 
 

IPz = Intensity at P due to Ez

I Pz  I 0 z
4
e   Sin 2 

2
 2   I e 4  Cos 2 2  
 
2 4 
m 2c 4   0z
r2 mc  r 2

 
 Scattering of x-ray by an Electron: unpolarized wave

4  I 
e  0 y 0zI Cos 2
2  
I P  I Py  I Pz  2 4
m c  r2 

I 0 e 4  1  Cos 2 2  
IP  
2 4  2
  Scattered beam is not unpolarized
2 mc  r 
Very small number

I 0 e 4  1  Cos 2 2   Polarization factor

I P  2 2 4   Comes into being as we used
r mc  2  unpolarized beam
 Scattering of x-ray by an Atom

Scattering by an atom  [Atomic number, (path difference

(due to scattering by all electron), wave length )]
30

Scattering by an atom  [Z, (, )]

Sin( ) 20 Schematic

f →

Angle of scattering leads to path differences 10
All scattered waves are in phase (forward direction)

0.2 0.4 0.6 0.8 1.0

Sin( )
 (Å−1) →

f  Atomic Scattering Factor

Amplitude of wavescatteredby an atom

Amplitude of wavescatteredby an electron
 Scattering of x-ray by THE Unit cell (UC)
 Coherent Scattering
 Unit Cell (uc) representative of the crystal structure
 Scattered waves from various atoms in the uc interfere to create
the diffraction pattern

The wave scattered from the middle plane is out of phase with the
ones scattered from top and bottom planes
 Ray 1 = R1 R1'

Ray 3 = R3 R3'
 A 
x
R S
Ray 2 = R2 B R2'
d(h00)
M N a
(h00) plane
C
Unit Cell
 Scattering of x-ray by THE Unit cell (UC)

2 x
  R R  2 h
 1 3
a
x
 fractional coordinate  x R R  2 h x
1 3
a

  2 (h x  k y  l z)
Extending to 3D

Independent of the shape of the unit cell ‘a’

R1 and R2 are from corner atoms

R3 is from atoms in additional positions within unit cell
 Scattering of x-ray by unit cell (UC)

  2 (h x  k y  l z)

i i[ 2 ( h x  k y   l z  )]
  Ae  fe

Scattering by an unit cell = f(position of the atoms, atomic scattering factors)

Scattering of x-ray by unit cell (UC): structure factor
 The resultant amplitude of all the waves scattered by all the atoms in the
uc gives the scattering factor for the unit cell
 The unit cell scattering factor is called the Structure Factor (F)
 If atom B is different from atom A  the amplitudes must be weighed by
the respective atomic scattering factors (f)

Amplitude of wave scattered by all atoms in uc

F  Structure Factor 
Amplitude of wave scattered by an electron

n n
 fj e  fj e
hkl i j i[ 2 ( h xj  k yj l z j )]
F n
j 1 j 1

Structure factor is independent of the shape and size of the unit cell
 Structure factor calculations e ni  (1) n
Simple Cubic
A Atom at (0,0,0) and equivalent positions e( odd n) i  1
e( evenn ) i  1
e ni  e  ni

i j i[ 2 ( h xj  k yj l zj )]

F  fj e  fj e
i[ 2 ( h0 k 0l 0)]
F f e  fe  f 0

I  F2  f 2  F is independent of the scattering plane (h k l)

 B Atom at (0,0,0) & (½, ½, 0) and equivalent positions C- centered
Orthorhombic
F  fj e  fj e
i j i[ 2 ( h xj  k yj l z j )]

j j
1 1
i[ 2 ( h   k   l  0 )]
i[ 2 ( h 0  k  0  l  0 )]
F fe  fe 2 2

hk
i [ 2 ( )]
 f e0  f e 2
 f [1  e i ( h  k ) ]

Real
F 2f F2  4 f 2
i ( h  k )
F  f [1  e
e.g. (001), (110), (112); (021), (022), (023
]
F 0 F2  0
e.g. (100), (101), (102); (031), (032), (03
 F is independent of the ‘l’ index
 Body centered
C Atom at (0,0,0) & (½, ½, ½) and equivalent positions
cubic

i j i[ 2 ( h xj  k yj l zj )]

F  fj e  fj e
1 1 1
i[ 2 ( h   k   l  )]
i[ 2 ( h 0  k  0  h 0 )]
F fe fe 2 2 2

h  k l
i [ 2 ( )]
 f e0  f e 2
 f [1  ei ( h  k l ) ]
Real

F 2f I  F2  4 f 2
i ( h  k  l )
F  f [1  e
e.g. (110), (200), (211); (220), (022), (310)
]
F 0 F2  0
e.g. (100), (001), (111); (210), (032), (133)
E
Na+ at (0,0,0) + Face Centering Translations  (½, ½, 0), (½, 0, ½), (0, ½, ½)
Cl− at (½, 0, 0) + FCT  (0, ½, 0), (0, 0, ½), (½, ½, ½)
 i[ 2 ( 0 )] i[ 2 ( h 2 k )] i[ 2 ( k 2l )] i[ 2 ( l 2h )]  NaCl: Face
F  f Na  e e e e  Centered Cubic
 
 i[ 2 ( h2 )] i[ 2 ( k2 )] i[ 2 ( 2l )] i[ 2 ( h 2k l )] 
f Cl   e e e e 
 
F  f Na  [1  ei ( h k )  ei ( k l )  ei (l  h ) ] 
f Cl  [ei ( h )  ei ( k )  ei (l )  ei ( h k l ) ]

F  f Na  [1  ei ( h k )  ei ( k l )  ei (l  h ) ] 

f Cl  ei ( h k l ) [ei (  k l )  ei ( l h)  ei (  hk )  1]

F  [ f Na   fCl  ei ( hk l ) ][1  ei ( hk )  ei ( k l )  ei (l h) ]

F  [ f Na   fCl  ei ( hk l ) ][1  ei ( hk )  ei ( k l )  ei (l h) ]

(h, k, l) mixed F 0 F2  0 e.g. (100), (211); (210), (032), (033)

(h, k, l) unmixed F  4[ f Na   fCl  ei ( hk l ) ]

F  4[ f Na   fCl  ] If (h + k + l) is even F 2  16[ f Na   fCl  ]2

F  4[ f Na   fCl  ] If (h + k + l) is odd F 2  16[ f Na   fCl  ]2

Presence of additional atoms/ions/molecules in the uc (basis) can alter

the intensities of some of the reflections
 Scattering from unit cell of a Crystal (Lattice + Basis)

 In crystals based on a particular lattice the intensities of

particular reflections are modified  they may even go missing

Diffraction Pattern

Position of the Lattice points Intensity of the diffraction spots

 LATTICE  BASIS

Structure Factor (F):

The resultant wave scattered by all atoms of the unit cell
It is independent of the shape and size of the unit cell
Depends on the position of the atoms within the cell
 Extinction Rules for different Bravais lattices
Reflections which Reflections
Bravais Lattice
may be present necessarily absent
Simple SC all None
Body centered BCC (h + k + l) even (h + k + l) odd
Face centered FCC h, k and l unmixed h, k and l mixed
h and k unmixed h and k mixed
Base centered
C centered C centred

h, k and l mixed
Diamond crystal DC h, k and l are all odd Or
Or
(Si, Ge) all are even but
all are even
(h + k + l) =4n (h + k + l) not
divisible by 4
Allowed reflection planes from different Bravais lattices
h2 + k2 + l2 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
The ratio of (h2 + K2 + l2) derived from extinction rules

SC 1 2 3 4 5 6 8 …

BCC 2 4 6 8 10 12 14 …
FCC 3 4 8 11 12 …
DC 3 8 11 16 …
 Peak width: determination of crystallite size

K Peak width (B) is inversely proportional

B2   to crystallite size (L)

L cos
Effect of lattice strain: Peak position and width
Applications of XRD

Bravais lattice determination Scattering from uc

Lattice parameter determination Number of equivalent scattering planes

Determination of solvus line in phase diagrams Effect of wave polarization

 
I P  1  Cos 2 2 

Long range order Combination of 3 geometric factors

 1   1 
Lorentz factor   Cos  
 Sin2   Sin2 

Crystallite size and Strain Specimen absorption

Temperature factor Thermal diffuse scattering

 Reciprocal Lattice (3D)
 1   Area(OAMB ) 1
b3*  b3*   a1  a2   
V Area(OAMB )  Height of Cell OP

 a 3

b3
C
P 
a2
1 b is  to a and a
b3  3 1 2
BB d 001
M

O A 
a1

 2    2    2  
b1  a2  a3  2
b  a3  a1  b3  a1  a2 
V V V

The reciprocal lattice is created by interplanar spacings

 Reciprocal Lattice (3D)

Some properties of the reciprocal lattice and its relation to the real lattice
 A reciprocal lattice vector is  to the corresponding    
real lattice plane ghkl  h b1  k b2  l b3
 The length of a reciprocal lattice vector is the reciprocal  2
of the spacing of the corresponding real lattice plane g hkl  g hkl 
d hkl
 Planes in the crystal become lattice points in the reciprocal lattice
 Note that this is an alternate geometrical construction of the real lattice.
 Reciprocal lattice point represents the orientation and spacing of a set of planes.
 Reciprocal Lattice (3D)

   = 0 when m ǂ n
am .bn  = 2 when m = n
The powder method for cubic system

  2dSin
d a
h k l
2 2 2

4a sin 
2 2
  2 2 2
2

h k l
2
4a
(h  k  l )  2 sin 
2 2 2 2


(h  k  l )  sin 
2 2 2 2
Allowed reflection planes from different Bravais lattices
h2 + k2 + l2 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
XRD pattern: determine the crystal structure

Radiation: Cu K,  = 1.54 Å

Peak position: determination of crystal structure

n 2  Sin Sin2  ratio Index

1 38.52 19.26 0.33 0.11 3 111
2 44.76 22.38 0.38 0.14 4 200
3 65.14 32.57 0.54 0.29 8 220
4 78.26 39.13 0.63 0.40 11 311
5 82.47 41.235 0.66 0.43 12 222
6 99.11 49.555 0.76 0.58 16 400
7 112.03 56.015 0.83 0.69 19 331
8 116.60 58.3 0.85 0.72 20 420
9 137.47 68.735 0.93 0.87 24 422
XRD pattern of Al: FCC crystal structure

111

311
220
200

331

422
420
222

400

Radiation: Cu K,  = 1.54 Å

Consider a monoclinic crystal of lattice parameter
a, b, and c: a and b are in X-Y plane making angle
45°, b along Y-axis

Write down the primitive translation vectors in terms of

cartesian unit vectors

Find the reciprocal lattice vectors also in terms of

cartesian unit vectors
 Prove it

 A reciprocal lattice vector is G (hkl)  to the corresponding real

lattice plane (hkl)

ghkl  (hkl)
 The length of a reciprocal lattice vector is the reciprocal of
the spacing of the corresponding real lattice plane
 2
g hkl 
d hkl
 Zone: Zonal planes and zonal axis

 Zone axis: [u v w]
 Zone planes (h k l)

uh +vk + wl = 0

All shaded plane s belong to same zone

Parallel to an axis called zone axix
 Ewald’s sphere construction:
Bragg’s law in reciprocal lattice

 Consider a length 2/

along incident x-ray (PO)
 Construct a sphere of radius
PO centered at P
 Find intercepts of it with
reciprocal lattice points
(reflection direction)
Brillouin zones: primitive unit cell in reciprocal lattice
As index of the plane increases, the interplanar spacing decreases
Electron diffraction patterns from different crystal planes
 Reciprocal Lattice (1D)

Real Lattice

Reciprocal Lattice

Real Lattice

Reciprocal Lattice
Reciprocal Lattice (1D)
 Reciprocal Lattice (1D)
I f2

 Intensity represents by height

 Reciprocal Lattice (2D)

02 12 22
(01)

(11) 01 11
(10) 21
(21) * *
g11 g 21

a 10 20
00 2
a
Reciprocal Lattice (2D)
 Reciprocal Lattice (2D)

 Intensity represents by radius of the spots

 Reciprocal Lattice (3D)
 1   Area(OAMB ) 1
b3*  b3*   a1  a2   
V Area(OAMB )  Height of Cell OP

 a 3

b3
C
P 
a2
1 b is  to a and a
b3  3 1 2
BB d 001
M

O A 
a1

 1    1    1  
b1  a2  a3  2
b  a3  a1  b3  a1  a2 
V V V

The reciprocal lattice is created by interplanar spacings

 2  
b1  a2  a3 
V
 2  
b2  a3  a1 
V
 2  
b3  a1  a2 
V