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by
Subhashis Gangopadhyay
Department of Physics
(Room 3242-A)
X-ray diffraction
X-ray diffraction
Electron diffraction
X-ray diffraction from crystalline solid
K
Characteristic
White K
Intensity
radiation
radiation
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
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
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
Deviation = 2
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
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
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
A B C
Scattering by a crystal Electron Atom Unit cell (uc)
(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
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 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
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
f →
Angle of scattering leads to path differences 10
All scattered waves are in phase (forward direction)
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
2 (h x k y l z)
i i[ 2 ( h x k y l z )]
Ae fe
n n
fj e fj e
hkl i j i[ 2 ( h xj k yj 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
j j
1 1
i[ 2 ( h k l 0 )]
i[ 2 ( h 0 k 0 l 0 )]
F fe fe 2 2
hk
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
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 2l )] 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 ) ]
Diffraction Pattern
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
L cos
Effect of lattice strain: Peak position and width
Applications of XRD
I P 1 Cos 2 2
1 1
Lorentz factor Cos
Sin2 Sin2
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
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
111
311
220
200
331
422
420
222
400
Zone axis: [u v w]
Zone planes (h k l)
uh +vk + wl = 0
Real Lattice
Reciprocal Lattice
Real Lattice
Reciprocal Lattice
Reciprocal Lattice (1D)
Reciprocal Lattice (1D)
I f2
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)
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