X-RAY DIFFRACTION

 X- Ray Sources
 Diffraction: Bragg’s Law
 Crystal Structure Determination

Elements of X-Ray Diffraction

B.D. Cullity & S.R. Stock
Prentice Hall, Upper Saddle River (2001)
 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 Å so the
suitable radiation is X-rays
 Hence, X-rays can be used for the study of crystal structures

Beam of electrons X-rays

Target

A accelerating charge radiates electromagnetic radiation

Mo Target impacted by electrons accelerated by a 35 kV potential

K

Characteristic radiation →
White K due to energy transitions
Intensity

radiation in the atom

0.2 0.6 1.0 1.4

Wavelength ()
Target Metal  Of K radiation (Å)

Mo 0.71

Cu 1.54

Co 1.79

Fe 1.94

Cr 2.29
 Incident X-rays

SPECIMEN Heat

Fluorescent X-rays
Electrons

Scattered X-rays
Compton recoil Photoelectrons

Coherent Incoherent (Compton modified)

From bound charges From loosely bound charges

Transmitted beam

X-rays can also be refracted (refractive index slightly less than 1) and reflected (at very small angles)
Incoherent Scattering (Compton modified) From loosely bound charges
 Here the particle picture of the electron & photon comes handy

E1  h1 (1 , 1 ) Electron knocked aside

2

E2  h 2 (2 , 2 )
  2  1  0.0243(1  Cos2 )

No fixed phase relation between the incident and scattered waves

Incoherent  does not contribute to diffraction
(Darkens the background of the diffraction patterns)
Fluorescent X-rays
Knocked out electron
Vacuum from inner shell

Energy
E L3
levels L 3

E L2 L2

E L1 L1
Characteristic x-rays
EK K (Fluorescent X-rays)
(10−16s later  seems like scattering!)
Nucleus
 A beam of X-rays directed at a crystal interacts with the
electrons of the atoms in the crystal
 The electrons oscillate under the influence of the incoming
X-Rays and become secondary sources of EM radiation
 The secondary radiation is in all directions
 The waves emitted by the electrons have the same frequency
as the incoming X-rays  coherent
 The emission will undergo constructive or destructive
interference

Secondary
Incoming X-rays emission
Sets Electron cloud into oscillation Sets nucleus into oscillation
Small effect  neglected
Oscillating charge re-radiates  In phase with the incoming x-rays
 BRAGG’s EQUATION

Deviation = 2

Ray 1

Ray 2  

 d

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

 For constructive interference: n = 2d Sin
 In plane scattering is in phase
Incident and scattered
waves are in phase if

Scattering from across planes is in phase

 A B

X Y
Atomic Planes

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
But this is still reinforced scattering
and NOT reflection
X Y
  Bragg’s equation is a negative law
 If Bragg’s eq. is NOT satisfied  NO reflection can occur
 If Bragg’s 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

  n = 2d Sin
 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 
a d 220  d 220 1
8 
h2  k 2  l 2 d110 2
a
d110 
2
In XRD nth order reflection from (h k l) is considered as 1st order reflection
from (nh nk nl)

n  2d hkl sin 

d hkl
2 sin 
n

  2d nh nk nl sin 
 Crystal structure determination

Many s (orientations) POWDER

Monochromatic X-rays Powder specimen METHOD

Single 
LAUE
Panchromatic X-rays
TECHNIQUE

ROTATING
Monochromatic X-rays  Varied by rotation CRYSTAL
METHOD
 THE POWDER METHOD

  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
Intensity of the Scattered electrons
A B C
Scattering by a crystal Electron Atom Unit cell (uc)
A Scattering by an Electron

(0 , 0 )
Sets electron into oscillation

Coherent
(definite phase relationship) (0 , 0 ) Scattered beams
For an 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 
For an unpolarized wave E is the measure of the amplitude of the wave
E2 = Intensityc

E E E
2 2
y
2
z

I0
 I0 y  I0z
2

IPy = Intensity at point P due to Ey

I Py  I 0 y
4
e   Sin    I
2 
2 e4  1 
2 4  2 
m 2c 4   0y
r2 m c r 
 

IPz = Intensity at point P due to Ez

I Pz
e 
 I0z 2 4

4 Sin 2 
2

 2   I e 4  Cos 2 2  
 
2 4 
mc   0z
r2 mc  r 2

 
 4
I 
e  0 y 0zI Cos 2
2  
I P  I Py  I Pz  2 4
mc   r 2 


I 0 e 4  1  Cos 2 2  
IP  
2 4  2
  Scattered beam is not unpolarized
2 mc  r 
Very small number
 Rotational symmetry about x axis + mirror symmetry about yz plane
 Forward and backward scattered intensity higher than at 90
 Scattered intensity minute fraction of the incident intensity

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
 B Scattering by an Atom
Scattering by an atom  [Atomic number, (path difference suffered by scattering from each e−, )]

Scattering by an atom  [Z, (, )]  Angle of scattering leads to path differences
 In the forward direction all scattered waves are in phase
Sin ( )


f  Atomic Scattering Factor 30

Amplitude of wave scattered by an atom

Amplitude of wave scattered by an electron
20 Schematic

f → 10

0.2 0.4 0.6 0.8 1.0

Sin ( )
(Å−1) →

 Coherent scattering Incoherent (Compton) scattering
Z  
Sin() /    
C Scattering 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'
B A 
x
R S
Ray 2 = R2 B R2'
d(h00)
M N a
(h00) plane
C
Unit Cell
 a
AC  d h 00 
h
MCN :: AC :: 
RBS :: AB :: x

AB x x
 
AC  a
h

 R R  MCN  2d h 00 Sin ( )  
2
1 2

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

Extending to 3D   2 (h x  k y  h z) Independent of the shape of uc

Note: R1 is from corner atoms and R3 is from atoms in additional positions in uc

 In complex notation
  2 (h x  k y  h z) E  Aei  fei[ 2 ( h x k yh z)]
 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)

I  F2
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  h zj )]
F n
j 1 j 1

Structure factor is independent of the shape and size of the unit cell
 ni
Structure factor calculations e  (1) n
Simple Cubic
A Atom at (0,0,0) and equivalent positions e ( odd n ) i  1
e ( even n ) i  1
e ni  e  ni
ei  e i
 Cos( )
2

i j i[ 2 ( h xj  k yj  h zj )]

F  fj e  fj e

i[ 2 ( h0 k 0 h0)]

F f e  fe  f 0

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- centred Orthorhombic

i j i[ 2 ( h xj  k yj  h zj )]

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

h k
i [ 2 ( )]
 f e0  f e 2
 f [1  ei ( 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), (033)

 F is independent of the ‘l’ index

 Body centred
C Atom at (0,0,0) & (½, ½, ½) and equivalent positions Orthorhombic

i j i[ 2 ( h xj  k yj  h zj )]

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

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

F 2f 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)
 D Atom at (0,0,0) & (½, ½, 0) and equivalent positions Face Centred Cubic

(½, ½, 0), (½, 0, ½), (0, ½, ½)

i j i[ 2 ( h xj  k yj  h zj )]
F  fj e  fj e
 i[ 2 ( 0)] i[ 2 ( h 2 k )] i[ 2 ( k 2l )] i[ 2 ( l 2h )] 
F  f e e e e 
 
 f [1  ei ( h  k )  ei ( k l )  ei (l  h ) ] Real

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

(h, k, l) unmixed F 4f F 2  16 f 2

e.g. (111), (200), (220), (333), (420)

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

Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
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) NaCl:
 i[ 2 ( 0)] i[ 2 ( h 2 k )] i[ 2 ( k 2l )] i[ 2 ( l 2h )]  Face Centred Cubic
F  f Na  e e e e 
 
 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) ]
Zero for mixed indices
(h, k, l) mixed F 0 F2  0 e.g. (100), (211); (210), (032), (033)

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

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

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

 Presence of additional atoms/ions/molecules in the uc (as a part of the motif ) can alter the
intensities of some of the reflections
Relative Intensity of diffraction lines in a powder pattern

Structure Factor (F) Scattering from uc

Multiplicity factor (p) Number of equivalent scattering planes

Polarization factor Effect of wave polarization


I P  1  Cos 2 2 
Lorentz factor Combination of 3 geometric factors

 1   1 
Lorentz factor   Cos  
 Sin 2   Sin 2 

Absorption factor Specimen absorption

Temperature factor Thermal diffuse scattering

Multiplicity factor
Lattice Index Multiplicity Planes
Cubic (100) 6 [(100) (010) (001)] ( 2 for negatives)
[(110) (101) (011), (110) (101) (011)] ( 2 for
(110) 12
negatives)
(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)
(210) = 3! Ways, (210) = 3! Ways,
(210) 24
(210) = 3! Ways, (210) = 3! Ways,
(211) 21
(321) 48
Tetragonal (100) 4 [(100) (010)]
(110) 4 [(110) (110)]
(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)
(210) 6
(211) 21
(321) 48
Polarization factor Lorentz factor


I P  1  Cos 2 2    1 
Lorentz factor  
 1 
Cos  
 Sin 2   Sin 2 

 1  Cos 2 30
2  
Lorentz Polarizati on factor   
 Sin  Cos 
2

25

Lorentz-Polarization factor
20

15

10

0
0 20 40 60 80
Bragg Angle (, degrees)
Intensity of powder pattern lines (ignoring Temperature & Absorption factors)

 Valid for Debye-Scherrer geometry

 1  Cos 2  2
I  F p 
2
 I → Relative Integrated “Intensity”
 Sin  Cos 
2
 F → Structure factor
 p → Multiplicity factor

 POINTS
 As one is interested in relative (integrated) intensities of the lines constant factors
are omitted
 Volume of specimen  me , e  (1/dectector radius)
 Random orientation of crystals  in a with Texture intensities are modified
 I is really diffracted energy (as Intensity is Energy/area/time)
 Ignoring Temperature & Absorption factors  valid for lines close-by in pattern
 Crystal = Lattice + Motif

 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  MOTIF
Reciprocal Lattice Properties are reciprocal to the crystal lattice

* 1   * 1   * 1  
b1  a2  a3  b2  a3  a1  b3  a1  a2 
V V V
* *

bi usuall written as ai a3
*
b3
* 1  
b  b3  a1  a2 
* C
3
V P 
Area(OXMB ) 1 a2
 
Area(OXMB )  Height of Cell OP

1 B
b  *
3
M
d 001 
O A
a1
The reciprocal lattice is created by interplanar spacings
 A reciprocal lattice vector is  to the corresponding real lattice plane

* * * *
g hkl  h b1  k b2  l b3
 The length of a reciprocal lattice vector is the reciprocal of the spacing of the
corresponding real lattice plane

* 1
g *
hkl  g hkl 
d hkl
 Planes in the crystal become lattice points in the reciprocal lattice
 ALTERNATE CONSTRUCTION OF THE REAL LATTICE
 Reciprocal lattice point represents the orientation and spacing of a set of planes
Reciprocal Lattice
02 12 22
(01)

 (11) 01 11
a2 (10) 21
(21) * * *
b2 g 11 g 21

a1
a1 * 10 20
00 1
b1 a1

The reciprocal lattice has an origin!

 22
(01) 12
02

(11) 21
 (10) 11
a2
(21) 01
 * 20
a1 b2
a1 10
*
22
b1
12
00
02
(01)
21
11
01 (11)
(10)
20
(21) 10 Note perpendicularity of various vectors
00
 Reciprocal lattice is the reciprocal of a primitive lattice and is purely
geometrical  does not deal with the intensities of the points
Physics comes in from the following:
 For non-primitive cells ( lattices with additional points) and for crystals
decorated with motifs ( crystal = lattice + motif) the Reciprocal lattice
points have to be weighed in with the corresponding scattering power
(|Fhkl|2)
 Some of the Reciprocal lattice points go missing (or may be scaled up
or down in intensity)
 Making of Reciprocal Crystal (Reciprocal lattice decorated with a
motif of scattering power)
 The Ewald sphere construction further can select those points which are
actually observed in a diffraction experiment
Examples of 3D Reciprocal Lattices weighed in with scattering power (|F|2)

SC
001
011

101 111

Lattice = SC 000
010

100
110
No missing reflections
Reciprocal Lattice = SC

Figures NOT to Scale

 002
022
BCC
202 222

011
101

020
000
Lattice = BCC 110
200
100 missing reflection (F = 0) 220

Weighing factor for each point “motif” Reciprocal Lattice = FCC

F2  4 f 2
Figures NOT to Scale
 002
022
FCC
202
222

111

020
000
Lattice = FCC
200
220
100 missing reflection (F = 0)
110 missing reflection (F = 0)
Weighing factor for each point “motif”
Reciprocal Lattice = BCC
F 2  16 f 2
Figures NOT to Scale
 The Ewald* Sphere

 The reciprocal lattice points are the values of momentum transfer for
which the Bragg’s equation is satisfied
 For diffraction to occur the scattering vector must be equal to a
reciprocal lattice vector
 Geometrically  if the origin of reciprocal space is placed at the tip of ki
then diffraction will occur only for those reciprocal lattice points that lie
on the surface of the Ewald sphere

* Paul Peter Ewald (German physicist and crystallographer; 1888-1985) See Cullity’s book: A15-4
Ewald Sphere

Reciprocal Space

2
KD
Ki The Ewald Sphere touches the
02 reciprocal lattice (for point 41)
01  Bragg’s equation is satisfied
K (41) for 41
00 10 20
K = K =g = Diffraction Vector
Diffraction cones and the Debye-Scherrer geometry

Film may be replaced with detector

http://www.matter.org.uk/diffraction/x-ray/powder_method.htm
Powder diffraction pattern from Al Radiation: Cu K,  = 1.54 Å

111
Note:
 Peaks or not idealized  peaks  broadend
 Increasing splitting of peaks with g 
 Peaks are all not of same intensity

311
220
200

331

422
420
222

400

1 & 2 peaks resolved

 Determination of Crystal Structure from 2 versus Intensity Data

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
 Extinction Rules

Structure Factor (F): The resultant wave scattered by all atoms of

the unit cell

The Structure Factor is independent of the shape and size of

the unit cell; but is dependent on the position of the atoms
within the cell
 Extinction Rules
Reflections which Reflections
Bravais Lattice
may be present necessarily absent
Simple all None
Body centred (h + k + l) even (h + k + l) odd
Face centred h, k and l unmixed h, k and l mixed
h and k unmixed h and k mixed
End centred
C centred C centred
Bravais Lattice Allowed Reflections
SC All
BCC (h + k + l) even
FCC h, k and l unmixed
h, k and l are all odd
Or
DC
all are even
(h + k + l) divisible by 4
Determination of Crystal Structure from 2 versus Intensity Data

n 2→  Intensity Sin Sin2  ratio

The ratio of (h2 + K2 + l2) derived from extinction rules

SC 1 2 3 4 5 6 8 …

BCC 1 2 3 4 5 6 7 …
FCC 3 4 8 11 12 …
DC 3 8 11 16 …
 2→  Intensity Sin Sin2  ratio
1 21.5 0.366 0.134 3
2 25 0.422 0.178 4
3 37 0.60 0.362 8
4 45 0.707 0.500 11
5 47 0.731 0.535 12
6 58 0.848 0.719 16
7 68 0.927 0.859 19

FCC
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
Consider the compound ZnS (sphalerite). Sulphur atoms occupy fcc sites with zinc atoms
displaced by ¼ ¼ ¼ 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.
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 ½ ½, ½ 0 ½, ½ ½ 0 i.e. in the fcc position and 4 atoms of type B at the sites ¼
¼ ¼ 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(fA ± ifB) if h, k, l all odd

F = 4(fA - fB) if h, k, l all even and h+ k+ l = 2n where n=odd (e.g. 200)

F = 4(fA + fB) if h, k, l all even and h+ k+ l = 2n where n=even (e.g. 400)

Applications of XRD

Bravais lattice determination

Scattering from uc

Lattice parameter determination

Number of equivalent scattering planes

Determination of solvus line in phase

Effect diagrams
of wave polarization


I P  1  Cos 2 2 
Long range order Combination of 3 geometric factors

 1   1 
Lorentz factor   Cos  
 Sin 2   Sin 2 

Crystallite size and StrainSpecimen absorption

Temperature factor Thermal diffuse scattering

Intensity → Crystal
Schematic of difference between
the diffraction patterns of various phases

0 90 180
Diffraction angle (2) →
Monoatomic gas

Intensity →
Diffraction angle (2) → Diffraction angle (2) →
Liquid300 310
Intensity →

/ Amorphous solid

0 90 1

0 90 180