X-ray Diffraction

Success Story of X-ray

1665: Diffraction effects observed by Italian
mathematician Francesco Maria Grimaldi
1868: X-rays Discovered by German Scientist
Rntgen
1912: Discovery of X-ray Diffraction by Crystals:
von Laue
1912: Braggs Discovery
Vacuum
Energy
levels
K
E
1
L
E
2
L
E
3
L
E
Nucleus
K
1
L
2
L
3
L
Characteristic x-rays
(Fluorescent X-rays)
(10
16
s later seems like scattering!)
Knocked out electron
from inner shell
Mechanism of X-ray Generation
Conduction Band
Valence Band
Incident electron
beam energy
Heat
Incident X-rays
SPECIMEN
Transmitted beam
Fluorescent X-rays
Electrons
Compton recoil Photoelectrons
Scattered X-rays
Coherent
From bound charges
Incoherent (Compton modified)
From loosely bound charges
X-rays can also be refracted (refractive index slightly less than 1) and reflected (at very small angles)
Refraction of X-rays is neglected for now.
For electromagnetic radiation to be diffracted the spacing
in the grating should be of the same order as the wavelength
In crystals the typical interatomic spacing ~ 2-3 so the
suitable radiation is X-rays
Hence, X-rays can be used for the study of crystal structures
Beam of electrons
Target
X-rays
An accelerating (/decelerating) charge radiates electromagnetic radiation
I
n
t
e
n
s
i
t
y

Wavelength ()
Mo Target impacted by electrons accelerated by a 35 kV potential
0.2
0.6
1.0
1.4
White
radiation
Characteristic radiation
due to energy transitions
in the atom
K
|
K
o
Target Metal of K
o
radiation ()
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
If Braggs eq. is NOT satisfied NO reflection can occur
If Braggs eq. is satisfied reflection MAY occur
Diffraction = Reinforced Coherent Scattering
Reflection versus Scattering
Reflection Diffraction
Occurs from surface Occurs throughout the bulk
Takes place at any angle Takes place only at Bragg angles
~100 % of the intensity may be reflected Small fraction of intensity is diffracted
X-rays can be reflected at very small angles of incidence
Braggs equation : n = 2d
hkl
Sin
n = 2d Sinu
n is an integer and is the order of the reflection
For Cu K
o
radiation ( = 1.54 ) and d
110
= 2.22
n Sinu u
1 0.34 20.7 First order reflection from (110)
2 0.69 43.92
Second order reflection from (110)
Also written as (220)
2 2 2
l k h
a
d
hkl
+ +
=
8
220
a
d =
2
110
a
d =
2
1
110
220
=
d
d
u sin 2
hkl
d n =
In XRD n
th
order reflection from (h k l) is considered as 1
st
order reflection
from (nh nk nl)
u sin 2
n
d
hkl
=
u sin 2
n n n l k h
d =
Crystal structure determination
Monochromatic X-rays
Panchromatic X-rays
Monochromatic X-rays
Many us (orientations)
Powder specimen
POWDER
METHOD
Single u
LAUE
TECHNIQUE
u Varied by rotation
ROTATING
CRYSTAL
METHOD
THE POWDER METHOD
u
u

u
2 2 2 2
2
2
2
2 2 2
2 2 2
2 2
2
2 2 2
sin ) (
sin
4
) (
sin 4
2
+ +
= + +
+ +
=
+ +
=
=
l k h
a
l k h
l k h
a
l k h
a
d
dSin
Note that in the Braggs equation:
- The interatomic spacing (a) along the plane does not appear
- Only the interplanar spacing (d) appears
Change in position or spacing of atoms along the plane should not affect
Braggs condition !!
d
Note: shift (systematic) is
actually not a problem!
Laues equations
S
0
incoming X-ray beam
S Scattered X-ray beam
h S S a = ) (
0

k S S b = ) (
0

l S S c = ) (
0

( ) ( ) | | u u h Cos Cos a =
2 1
Generalizing into 3D
( ) ( ) | | u u k Cos Cos b =
4 3
( ) ( ) | | u u l Cos Cos c =
6 5
This is looking at diffraction from atomic arrays and not planes
Intensity of the Scattered electrons
Electron
Atom
Unit cell (uc)
Scattering by a crystal
A
B
C
Polarization factor
Atomic scattering factor (f)
Structure factor (F)
B Scattering by an Atom
BRUSH-UP
The conventional UC has lattice points as the vertices
There may or may not be atoms located at the lattice points
The shape of the UC is a parallelepiped (Greek paralllepipedon) in 3D
There may be additional atoms in the UC due to two reasons:
The chosen UC is non-primitive
The additional atoms may be part of the motif
C
Scattering by the Unit cell (uc)
Coherent Scattering
Unit Cell (UC) is 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
d
(h00)

u
B

u
Ray 1 = R
1

Ray 2 = R
2

Ray 3 = R
3

Unit Cell
x
M
C
N
R
B
S
A
'
1
R
'
2
R
'
3
R
(h00) plane
a
h
a
d AC
h
= =
00
:: :: AC MCN
x AB RBS :: ::
h
a
x x
AC
AB
= =

u o = = = ) ( 2
00
2 1
Sin d MCN
h R R
o
h
a
x
AC
AB
RBS
R R
= = =
3 1
o

2
=
a
x
h
h
a
x
R R
t

t
2
2
3 1
= =
x coordinate fractional
a
x
'
x h
R R
' = t 2
3 1
Extending to 3D
2 ( ) h x k y l z t
' ' '
= + + Independent of the shape of UC
Note: R
1
is from corner atoms and R
3
is from atoms in additional positions in UC
o
t

=
2
If atom B is different from atom A the amplitudes must be weighed by the respective
atomic scattering factors (f)
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)
Scattering by an unit cell = f(position of the atoms, atomic scattering factors)
electron an by scattered wave of Amplitude
uc in atoms all by scattered wave of Amplitude
Factor Structure F = =
[2 ( )] i i h x k y l z
E Ae fe
t ' ' ' + +
= =
2 ( ) h x k y l z t
' ' '
= + +
In complex notation
2
F I
[2 ( )]
1 1
j j j j
n n
i i h x k y l z
hkl
n j j
j j
F f e f e
t ' ' ' + +
= =
= =

Structure factor is independent of the shape and size of the unit cell
For n atoms in the UC
If the UC distorts so do the planes in it!!
http://www.matter.org.uk/diffraction/x-ray/powder_method.htm
Diffraction cones and the Debye-Scherrer geometry
Film may be replaced with detector
Powder diffraction pattern from Al
4
2
0

1
1
1

2
0
0

2
2
0

3
1
1

2
2
2

4
0
0

3
3
1

4
2
2

o
1
& o
2
peaks resolved
Radiation: Cu Ko, = 1.54
Note:
Peaks or not idealized o peaks broadend
Increasing splitting of peaks with |g u
Peaks are all not of same intensity
n 2u u Sinu Sin
2
u 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
Determination of Crystal Structure from 2u versus Intensity Data
Structure factor calculation
Consider a general unit cell for this type of structure. It can be reduced to 4 atoms of
type A at 000, 0 , 0 , 0 i.e. in the fcc position and 4 atoms of type B at the
sites from the A sites. This can be expressed as:

The structure factors for this structure are:
F = 0 if h, k, l mixed (just like fcc)
F = 4(f
A
if
B
) if h, k, l all odd
F = 4(f
A
- f
B
) if h, k, l all even and h+ k+ l = 2n where n=odd (e.g. 200)
F = 4(f
A
+ f
B
) if h, k, l all even and h+ k+ l = 2n where n=even (e.g. 400)
Consider the compound ZnS (sphalerite). Sulphur atoms occupy fcc sites with zinc atoms
displaced by from these sites. Click on the animation opposite to show this structure.
The unit cell can be reduced to four atoms of sulphur and 4 atoms of zinc.
Many important compounds adopt this structure. Examples include ZnS, GaAs, InSb, InP
and (AlGa)As. Diamond also has this structure, with C atoms replacing all the Zn and S
atoms. Important semiconductor materials silicon and germanium have the same structure
as diamond.
Bravais lattice determination
Lattice parameter determination
Determination of solvus line in phase diagrams
Long range order
Applications of XRD
Crystallite size and Strain
Temperature factor
Scattering from uc
Number of equivalent scattering planes
Effect of wave polarization
Combination of 3 geometric factors
Specimen absorption
Thermal diffuse scattering
( )
|
.
|

\
|
|
.
|

\
|
=
u
u
u 2
1
2
1

Sin
Cos
Sin
factor Lorentz
( ) ( ) u 2 1
2
Cos I
P
+ =
Diffraction angle (2u)
I
n
t
e
n
s
i
t
y

90 180
0
Crystal

90 180
0
Diffraction angle (2u)
I
n
t
e
n
s
i
t
y

Liquid / Amorphous solid

90
180
0
Diffraction angle (2u)
I
n
t
e
n
s
i
t
y

Monoatomic gas

Schematic of difference between
the diffraction patterns of various phases