X-RAY DIFFRACTION

X- Ray Sources
Diffraction: Braggs Law
Crystal Structure Determination
Elements of X-Ray Diffraction
B.D. Cullity & S.R. Stock
Prentice Hall, Upper Saddle River (2001)

X-Ray Diffraction: A Practical Approach
C. Suryanarayana & M. Grant Norton
Plenum Press, New York (1998)
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
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.
Incoherent Scattering (Compton modified) From loosely bound charges
Here the particle picture of the electron & photon comes in handy
) , (
1 1
v
Electron knocked aside
) , (
2 2
v
1 1
v h E =
2 2
v h E =
) 2 1 ( 0243 . 0
1 2
u Cos = = A
2u
No fixed phase relation between the incident and scattered waves
Incoherent does not contribute to diffraction
(Darkens the background of the diffraction patterns)
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!)
Fluorescent X-rays
Knocked out electron
from inner shell
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 with waves scattered from other atoms
Incoming X-rays
Secondary
emission
Sets Electron cloud into oscillation
Sets nucleus (with protons) into oscillation
Small effect neglected
Oscillating charge re-radiates In phase with the incoming x-rays
BRAGGs EQUATION
d
u
u
u
u
The path difference between ray 1 and ray 2 = 2d Sinu
For constructive interference: n = 2d Sinu
Ray 1
Ray 2
u
Deviation = 2u
Incident and scattered
waves are in phase if
Scattering from across planes is in phase
In plane scattering is in phase
Extra path traveled by incoming waves AY
Extra path traveled by scattered waves XB
These can be in phase if and only if
u
incident
= u
scattered

But this is still reinforced scattering
and NOT reflection
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!
Note: shift is actually not a problem! Why is systematic shift not a problem?
n AY YB = + [180 ( )] ( ) AY XY Cos XY Cos o u o u = + = +
( ) YB XY Cos o u =
[ ( ) ( )] [2 ] n AY YB XY Cos Cos XY Sin Sin o u o u o u = + = + =
( )
d
Sin
XY
o =
[2 ] 2
d
n Sin Sin d Sin
Sin
o u u
o
= = 2 n d Sin u =
Consider the case for which u
1
= u
2

Constructive interference can still occur if the difference in the path length
traversed by R
1
and R
2
before and after scattering are an integral multiple of the
wavelength
(AY XC) = h (h is an integer)
( )
1
u Cos
a
AY
= ( )
2
u Cos
a
XC
=
( ) ( ) u u h Cos a Cos a =
2 1
( ) ( ) | | u u h Cos Cos a =
2 1
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
A physical picture of scattering leading to diffraction is embodied in Laues equations
Braggs method of visualizing diffraction as reflection from a set of planes is a different
way of understanding the phenomenon of diffraction from crystals
The plane picture (Braggs equations) are simpler and we usually stick to them
Hence, we should think twice before asking the question: if there are no atoms in the
scattering planes, how are they scattering waves?
Braggs equation is a negative law
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
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 =
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)
Scattering by an Electron
) , (
0 0
v
Sets electron into oscillation
Scattered beams
) , (
0 0
v
Coherent
(definite phase relationship)
A
The electric field (E) is the main cause for the acceleration of the electron
The moving particle radiates most strongly in a direction perpendicular to its
motion
The radiation will be polarized along the direction of its motion
x
z
r
P
o
Intensity of the scattered beam due to an electron (I) at a point P
such that r >>
|
|
.
|

\
|
=
2
2
4 2
4
0
r
Sin
c m
e
I I
o
For a wave oscillating in z direction
For an polarized wave
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
0 30 60 90 120 150 180 210 240 270 300 330 360
t
C
o
s
(
t
)
The reason we are able to
neglect scattering from the
protons in the nucleus
The scattered rays are also plane polarized
|
|
.
|

\
|
=
2
2
4 2
4
0
r
Sin
c m
e
I I
o
For an unpolarized wave
E is the measure of the amplitude of the wave
E
2
= Intensity
2 2 2
z y
E E E + =
z y
I I
I
0 0
0
2
= =
( )
2
4
0
2 4 2
y
Py y
Sin
e
I I
m c r
|
| |
| =
|
\ .
I
Py
= Intensity at point P due to E
y

I
Pz
= Intensity at point P due to E
z

( )
2
4
0
2 4 2
z
Pz z
Sin
e
I I
m c r
| | |
=
|
|
\ .
Total Intensity at point P due to E
y
& E
z
( ) ( )
2 2
4
0
2 4 2
y z
P
Sin Sin
e
I I
m c r
| |
| |
+
| =
|
\ .
( ) ( )
2 2
4
0
2 4 2
y z
P
Sin Sin
e
I I
m c r
| |
| |
+
| =
|
\ .
( ) ( ) ( ) ( ) ( ) ( )
2 2 2 2 2 2
1 1 2
y z y z y z
Sin Sin Cos Cos Cos Cos | | | | | |
( ( (
+ = + =

( ) ( ) ( )
2 2 2
1
x y z
Cos Cos Cos | | |
(
+ + =

Sum of the squares of the direction cosines =1

( ) ( )
( ) ( )
2 2 2 2
2 2 1 ( ) 1 ( )
y z x x
Cos Cos Cos Cos | | | |
( ( (
= = +

Hence

( )
2
4
0
2 4 2
1 ( )
x
P
Cos
e
I I
m c r
|
| |
+
|
=
|
\ .
( )
2
4
0
2 4 2
1 (2 )
P
Cos
e
I I
m c r
u
| |
+
|
=
|
\ .
In terms of 2u

0
0.2
0.4
0.6
0.8
1
0 30 60 90 120 150 180
2t
[
C
o
s
(
2
t
)
]
^
2
In general P could lie anywhere in 3D space
For the specific case of Bragg scattering:
The incident direction IO
The diffracted beam direction OP
The trace of the scattering plane BB
Are all coplanar
OP is constrained to be on the xz plane

x
z
r
P
o
2u
|
|
.
|

\
|
=
2
2
4 2
4
0
2
r
Cos
c m
e
I I
u
For an unpolarized wave
E is the measure of the amplitude of the wave
E
2
= Intensity
2 2 2
z y
E E E + =
z y
I I
I
0 0
0
2
= =
( )
|
.
|

\
|
=
|
|
.
|

\
|
=
2 4 2
4
0
2
2
4 2
4
0
1
2
r c m
e
I
r
Sin
c m
e
I I
y y Py
t
I
Py
= Intensity at point P due to E
y

I
Pz
= Intensity at point P due to E
z

( )
( )
|
|
.
|

\
|
=
|
|
.
|

\
|

=
2
2
4 2
4
0
2
2
4 2
4
0
2
2
2
r
Cos
c m
e
I
r
Sin
c m
e
I I
z z Pz
u
u
t
The zx plane is to the y direction: hence, o = 90
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
0 30 60 90 120 150 180 210 240 270 300 330 360
t
C
o
s
(
t
)
( )
|
|
.
|

\
|
+
= + =
2
2
0 0
4 2
4
2
r
Cos I I
c m
e
I I I
z y
Pz Py P
u
( )
|
|
.
|

\
|
+
=
2
2
4 2
4
0
2 1
2 r
Cos
c m
e I
I
P
u
Scattered beam is not unpolarized
Forward and backward scattered intensity higher than at 90
Scattered intensity minute fraction of the incident intensity
Very small number
Polarization factor
Comes into being as we used
unpolarized beam
( )
|
|
.
|

\
|
+
=
2
2 1
2
4 2
4
2
0
u Cos
c m
e
r
I
I
P
0
0.2
0.4
0.6
0.8
1
1.2
0 30 60 90 120 150 180 210 240 270 300 330 360
2t
(
1
+
C
o
s
(
2
t
)
^
2
)
/
2
B Scattering by an Atom
Scattering by an atom [Atomic number, (path difference suffered by scattering from each e

, )]
Scattering by an atom [Z, (u, )]
Angle of scattering leads to path differences
In the forward direction all scattered waves are in phase
electron an by scattered wave of Amplitude
atom an by scattered wave of Amplitude

Factor Scattering Atomic f
=
=
f

u) ( Sin
(
1
)
0.2 0.4 0.6 0.8 1.0
10
20
30
Schematic

u) ( Sin
Coherent scattering Incoherent (Compton) scattering
Z | | +
Sin(u) / + | +
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!!
n ni
e ) 1 ( =
t
) (
2
u
u u
Cos
e e
i i
=
+

Structure factor calculations
A Atom at (0,0,0) and equivalent positions
[2 ( )]
j j j j
i i h x k y l z
j j
F f e f e
t ' ' ' + +
= =
[2 ( 0 0 0)] 0 i h k l
F f e f e f
t + +
= = =
2 2
f F = F is independent of the scattering plane (h k l)
t t ni ni
e e

=
Simple Cubic
1
) (
=
t i n odd
e
1
) (
+ =
t i n even
e
B Atom at (0,0,0) & (, , 0) and equivalent positions
[2 ( )]
j j j j
i i h x k y l z
j j
F f e f e
t ' ' ' + +
= =
1 1
[2 ( 0)]
[2 ( 0 0 0)]
2 2
[ 2 ( )]
0 ( )
2
[1 ]
i h k l
i h k l
h k
i
i h k
F f e f e
f e f e f e
t
t
t
t
+ +
+ +
+
+
= +
= + = +
F is independent of the l index
C- centred Orthorhombic
Real
] 1 [
) ( k h i
e f F
+
+ =
t
f F 2 =
0 = F
2 2
4 f F =
0
2
= F
e.g. (001), (110), (112); (021), (022), (023)
e.g. (100), (101), (102); (031), (032), (033)
If the blue planes are scattering in phase then on C- centering the red planes will scatter out
of phase (with the blue planes- as they bisect them) and hence the (210) reflection will
become extinct
This analysis is consistent with the extinction rules: (h + k) odd is absent
In case of the (310) planes no new translationally equivalent planes are added on lattice
centering this reflection cannot go missing.
This analysis is consistent with the extinction rules: (h + k) even is present
C Atom at (0,0,0) & (, , ) and equivalent positions
[2 ( )]
j j j j
i i h x k y l z
j j
F f e f e
t ' ' ' + +
= =
1 1 1
[2 ( )]
[2 ( 0 0 0)]
2 2 2
[ 2 ( )]
0 ( )
2
[1 ]
i h k l
i h k l
h k l
i
i h k l
F f e f e
f e f e f e
t
t
t
t
+ +
+ +
+ +
+ +
= +
= + = +
Body centred
Orthorhombic
Real
] 1 [
) ( l k h i
e f F
+ +
+ =
t
f F 2 =
0 = F
2 2
4 f F =
0
2
= F
e.g. (110), (200), (211); (220), (022), (310)
e.g. (100), (001), (111); (210), (032), (133)
D Atom at (0,0,0) & (, , 0) and equivalent positions
[2 ( )]
j j j j
i i h x k y l z
j j
F f e f e
t ' ' ' + +
= =
] 1 [
) ( ) ( ) (
)]
2
( 2 [ )]
2
( 2 [ )]
2
( 2 [
)] 0 ( 2 [
h l i l k i k h i
h l
i
l k
i
k h
i
i
e e e f
e e e e f F
+ + +
+ + +
+ + + =
(

+ + + =
t t t
t t t
t
Face Centred Cubic
Real
f F 4 =
0 = F
2 2
16 f F =
0
2
= F
(h, k, l) unmixed
(h, k, l) mixed
e.g. (111), (200), (220), (333), (420)
e.g. (100), (211); (210), (032), (033)
(, , 0), (, 0, ), (0, , )
] 1 [
) ( ) ( ) ( h l i l k i k h i
e e e f F
+ + +
+ + + =
t t t
Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
Mixed indices CASE h k l
A o o e
B o e e
( ) ( ) ( )
CASE A: [1 ] [1 1 1 1] 0
i e i o i o
e e e
t t t
+ + + = + =
( ) ( ) ( )
CASE B: [1 ] [1 1 1 1] 0
i o i e i o
e e e
t t t
+ + + = + =
0 = F
0
2
= F
(h, k, l) mixed e.g. (100), (211); (210), (032), (033)
Mixed indices
Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
Unmixed indices CASE h k l
A o o o
B e e e
Unmixed indices
f F 4 =
2 2
16 f F =
(h, k, l) unmixed
e.g. (111), (200), (220), (333), (420)
All odd (e.g. 111); all even (e.g. 222)
( ) ( ) ( )
CASE A: [1 ] [1 1 1 1] 4
i e i e i e
e e e
t t t
+ + + = + + + =
( ) ( ) ( )
CASE B: [1 ] [1 1 1 1] 4
i e i e i e
e e e
t t t
+ + + = + + + =
E
Na
+
at (0,0,0) + Face Centering Translations (, , 0), (, 0, ), (0, , )
Cl

at (, 0, 0) + FCT (0, , 0), (0, 0, ), (, , )

(

+ + +
+
(

+ + + =
+ +
+ + +

+
)]
2
( 2 [ )]
2
( 2 [ )]
2
( 2 [ )]
2
( 2 [
)]
2
( 2 [ )]
2
( 2 [ )]
2
( 2 [
)] 0 ( 2 [

l k h
i
l
i
k
i
h
i
Cl
h l
i
l k
i
k h
i
i
Na
e e e e f
e e e e f F
t t t t
t t t
t
] [
] 1 [
) ( ) ( ) ( ) (
) ( ) ( ) (
l k h i l i k i h i
Cl
h l i l k i k h i
Na
e e e e f
e e e f F
+ +
+ + +
+ + +
+ + + + =

+
t t t t
t t t
] 1 [
] 1 [
) ( ) ( ) ( ) (
) ( ) ( ) (
+ + +
+ + + + =
+ +
+ + +

+
k h i h l i l k i l k h i
Cl
h l i l k i k h i
Na
e e e e f
e e e f F
t t t t
t t t
] 1 ][ [
) ( ) ( ) ( ) ( h l i l k i k h i l k h i
Cl Na
e e e e f f F
+ + + + +
+ + + + =
+
t t t t
NaCl:
Face Centred Cubic
] 1 ][ [
) ( ) ( ) ( ) ( h l i l k i k h i l k h i
Cl Na
e e e e f f F
+ + + + +
+ + + + =
+
t t t t
Zero for mixed indices
Mixed indices CASE h k l
A o o e
B o e e
] 2 ][ 1 [ = Term Term F
0 ] 1 1 1 1 [ ] 1 [ 2 : A CASE
) ( ) ( ) (
= + = + + + =
o i o i e i
e e e Term
t t t
0 ] 1 1 1 1 [ ] 1 [ 2 : B CASE
) ( ) ( ) (
= + = + + + =
o i e i o i
e e e Term
t t t
0 = F
0
2
= F
(h, k, l) mixed e.g. (100), (211); (210), (032), (033)
Mixed indices
(h, k, l) unmixed
] [ 4
) ( l k h i
Cl Na
e f f F
+ +
+
+ =
t
] [ 4
+
+ =
Cl Na
f f F
If (h + k + l) is even
2 2
] [ 16
+
+ =
Cl Na
f f F
] [ 4
+
=
Cl Na
f f F
If (h + k + l) is odd
2 2
] [ 16
+
=
Cl Na
f f F
e.g. (111), (222); (133), (244)
e.g. (222),(244)
e.g. (111), (133)
Unmixed indices CASE h k l
A o o o
B e e e
4 ] 1 1 1 1 [ ] 1 [ 2 : A CASE
) ( ) ( ) (
= + + + = + + + =
e i e i e i
e e e Term
t t t
4 ] 1 1 1 1 [ ] 1 [ 2 : B CASE
) ( ) ( ) (
= + + + = + + + =
e i e i e i
e e e Term
t t t
Unmixed indices
Presence of additional atoms/ions/molecules in the UC can alter
the intensities of some of the reflections
Bravais Lattice
Reflections which
may be present
Reflections
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
End centred
h and k unmixed
C centred
h and k mixed
C centred
Bravais Lattice Allowed Reflections
SC All
BCC (h + k + l) even
FCC h, k and l unmixed
DC
h, k and l are all odd
Or
all are even
& (h + k + l) divisible by 4
Selection / Extinction Rules
h
2
+ k
2
+ l
2
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
Reciprocal Lattice
Properties are reciprocal to the crystal lattice
( )
3 2
*
1
1
a a
V
b

=
( )
1 3
*
2
1
a a
V
b

= ( )
2 1
*
3
1
a a
V
b

=
B
O
P
M
A
C
B
O
P
M
A
C
O
P
M
A
C
O
P
M
A
C
O
P
M
A
C
*
b
3

2
a

1
a

3
a

( )
OP Cell Height of OAMB Area
OAMB Area
a a
V
b b
1
) (
) (
1
2 1
*
3
*
3
=

=
= =

001
*
3
1
d
b =
The reciprocal lattice is created by interplanar spacings
* *
as written usuall
i i
a b

B
BASIS
VECTORS
2 1
*
3
to is a and a b

A reciprocal lattice vector is to the corresponding real lattice plane

*
3
*
2
*
1
*
b l b k b h g
hkl

+ + =
hkl
hkl hkl
d
g g
1
* *
= =

The length of a reciprocal lattice vector is the reciprocal of the spacing of the
corresponding real lattice plane
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
(01)
(10)
(11)
(21)
10
20
11
22
12 02
01
21
00
The reciprocal lattice has an origin!
1
a

2
a

1
a
1
1
a
*
11
g
*
21
g
*
b
2

*
b
1

1
0
2
0
1
1
2
2
1
2
0
2
0
1
2
1
0
0
(01)
(10)
(11)
(21)
1
a

2
a

*
b
2

*
b
1

1
a
(01)
(10)
(11)
(21)
1
0
2
0
1
1
2
2
1
2
0
2
0
1
2
1
0
0
Note perpendicularity of various vectors
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
(|F
hkl
|
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
In crystals based on a particular lattice the intensities of particular
reflections are modified they may even go missing
Crystal = Lattice + Motif
Diffraction Pattern
Position of the Lattice points
LATTICE
Intensity of the diffraction spots
MOTIF
There are two ways of constructing the Reciprocal Crystal:
1) Construct the lattice and decorate each lattice point with appropriate intensity
2) Use the concept as that for the real crystal
Examples of 3D Reciprocal Lattices weighed in with scattering power (|F|
2
)
Figures NOT to Scale
000
100
111
001
101
011
010
110
SC
Lattice = SC
Reciprocal Crystal = SC
No missing reflections
Figures NOT to Scale
000
200
222
002
101
022
020
110
BCC
Lattice = BCC
Reciprocal Crystal = FCC
220
011
202
100 missing reflection (F = 0)
2 2
4 f F =
Weighing factor for each point motif
Figures NOT to Scale
000
200
222
002
022
020
FCC
Lattice = FCC
Reciprocal Crystal = BCC
220
111
202
100 missing reflection (F = 0)
110 missing reflection (F = 0)
2 2
16 f F =
Weighing factor for each point motif
Ordered Solid solution
G = H TS
High T disordered
Low T ordered
470C
Sublattice-1
Sublattice-2
BCC
SC
In a strict sense this is not a crystal !!
Disordered Ordered
o- NiAl, BCC B2 (CsCl type)
c- Ni
3
Al, FCC L1
2
(AuCu
3
-I type)
BCC
SC
BCC
FCC
FCC
SC
Ordered
Ordered
There are two ways of constructing the Reciprocal Crystal:
1) Construct the lattice and decorate each lattice point with appropriate intensity
2) Use the concept as that for the real crystal
1) SC + two kinds of Intensities decorating the lattice
2) (FCC) + (Motif = 1FR + 1SLR)
1) SC + two kinds of Intensities decorating the lattice
2) (BCC) + (Motif = 1FR + 3SLR)
FR Fundamental Reflection
SLR Superlattice Reflection
The Ewald Sphere
* Paul Peter Ewald (German physicist and crystallographer; 1888-1985)
organisiert von:
Max-Planck-Institut fr Metallforschung
Institut fr Theoretische und Angewandte Physik,
Institut fr Metallkunde,
Institut fr Nichtmetallische Anorganische
Materialien
der Universitt Stuttgart
Programm
13:30 Joachim Spatz (Max-Planck-Institut fr Metallforschung)
Begrung
13:45 Heribert Knorr (Ministerium fr Wissenschaft, Forschung und Kunst Baden-Wrttemberg
Begrung
14:00 Stefan Hell (Max-Planck-Institut fr Biophysikalische Chemie)
Nano-Auflsung mit fokussiertem Licht
14:30 Antoni Tomsia (Lawrence Berkeley National Laboratory)
Using Ice to Mimic Nacre: From Structural Materials to Artificial Bone
15:00 Pause
Kaffee und Getrnke
15:30 Frank Gieelmann(Universitt Stuttgart)
Von ferroelektrischen Fluiden zu geordneten Dispersionen von Nanorhren: Aktuelle Themen der
Flssigkristallforschung
16:00 Verleihung des Gnter-Petzow-Preises 2008
16:15 Udo Welzel (Max-Planck-Institut fr Metallforschung)
Materialien unter Spannung: Ursachen, Messung und Auswirkungen- Freund und Feind
ab 17:00 Sommerfest des Max-Planck-Instituts fr Metallforschung
7. Paul-Peter-Ewald-Kolloquium

Freitag, 17. Juli 2008

The Ewald Sphere
The reciprocal lattice points are the values of momentum transfer for
which the Braggs 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 k
i

then diffraction will occur only for those reciprocal lattice points that lie
on the surface of the Ewald sphere
See Cullitys book: A15-4
hkl hkl
Sin d n u 2 =

u
2
1 2
hkl
hkl
hkl
d
d
Sin = =
Draw a circle with diameter 2/
Construct a triangle with the diameter as the hypotenuse and 1/d
hkl
as a side (any
triangle inscribed in a circle with the diameter as the hypotenuse is a right angle
triangle): AOP
The angle opposite the 1/d side is u
hkl
(from the rewritten Braggs equation)
Braggs equation revisited
hkl
hkl hkl
d
g g
1
* *
= =

u
2
1 2
hkl
hkl
hkl
d
d
Sin = =
Radiation related information is present in the Ewald Sphere
Crystal related information is present in the reciprocal crystal
The Ewald sphere construction generates the diffraction pattern
The Ewald Sphere construction
01
10
02
00 20
2u
(41)
K
i
K
D
AK
Reciprocal Space
AK = K =g = Diffraction Vector
Ewald Sphere
The Ewald Sphere touches the
reciprocal lattice (for point 41)
Braggs equation is satisfied
for 41
(Cu K
o
) = 1.54 , 1/ = 0.65
1
(2/ = 1.3
1
), a
Al
= 4.05 , d
111
= 2.34 , 1/d
111
= 0.43
1
Ewald sphere X-rays
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
Cone of diffracted rays
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 METHOD
Different cones for different reflections
The 440 reflection is not observed
The 331 reflection is not observed
THE POWDER METHOD
u
2 2 2 2
sin ) ( + + l k h
u

2
2
2
2 2 2
sin
4
) (
a
l k h = + +
) (
sin 4
2 2 2
2
2
2
l k h a + + =
u

2 2 2
l k h
a
d
Cubic
+ +
=
u dSin 2 =
2 2 2
2 2
2
sin 4
l k h
a
+ +
=
u

Cubic crystal
Structure Factor (F)
Multiplicity factor (p)
Polarization factor
Lorentz factor
Relative Intensity of diffraction lines in a powder pattern
Absorption factor
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
+ =
Multiplicity factor
Lattice Index Multiplicity Planes
Cubic
(with highest
symmetry)
(100) 6 [(100) (010) (001)] ( 2 for negatives)
(110) 12 [(110) (101) (011), (110) (101) (011)] ( 2 for negatives)
(111) 12 [(111) (111) (111) (111)] ( 2 for negatives)
(210) 24
*
(210) 3! Ways, (210) 3! Ways,
(210) 3! Ways, (210) 3! Ways
(211) 24
(211) 3 ways, (211) 3! ways,
(211) 3 ways
(321) 48
*

Tetragonal
(with highest
symmetry)
(100) 4 [(100) (010)] ( 2 for negatives)
(110) 4 [(110) (110)] ( 2 for negatives)
(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)
(210) 8
*

(210) = 2 Ways, (210) = 2 Ways,
(210) = 2 Ways, (210) = 2 Ways
(211) 16 [Same as for (210) = 8] 2 (as l can be +1 or 1)
(321) 16
*
Same as above (as last digit is anyhow not permuted)
* Altered in crystals with lower symmetry
Cubic
hkl hhl hk0 hh0 hhh h00
48
*
24 24
*
12 8 6
Hexagonal
hk.l hh.l h0.l hk.0 hh.0 h0.0 00.l
24
*
12
*
12
*
12
*
6 6 2
Tetragonal
hkl hhl h0l hk0 hh0 h00 00l
16
*
8 8 8
*
4 4 2
Orthorhombic
hkl hk0 h0l 0kl h00 0k0 00l
8 4 4 4 2 2 2
Monoclinic
hkl h0l 0k0
4 2 2
Triclinic
hkl
2
* Altered in crystals with lower symmetry (of the same crystal class)
Multiplicity factor
0
5
10
15
20
25
30
0 20 40 60 80
Bragg Angle (u, degrees)
L
o
r
e
n
t
z
-
P
o
l
a
r
i
z
a
t
i
o
n

f
a
c
t
o
r
Polarization factor
Lorentz factor
( )
|
.
|

\
|
|
.
|

\
|
=
u
u
u 2
1
2
1

Sin
Cos
Sin
factor Lorentz
( ) ( ) u 2 1
2
Cos I
P
+ =
( )
|
|
.
|

\
| +
=
u u
u
Cos Sin
Cos
f actor on Polarizati Lorentz
2
2
2 1

Intensity of powder pattern lines (ignoring Temperature & Absorption factors)
|
|
.
|

\
|
+
=
u u
u
Cos Sin
Cos
p F I
2
2
2 2 1
Valid for Debye-Scherrer geometry
I Relative Integrated Intensity
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 - m
e
, 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
THE POWDER METHOD
u
2 2 2 2
sin ) ( + + l k h
u

2
2
2
2 2 2
sin
4
) (
a
l k h = + +
) (
sin 4
2 2 2
2
2
2
l k h a + + =
u

2 2 2
l k h
a
d
Cubic
+ +
=
u dSin 2 =
2 2 2
2 2
2
sin 4
l k h
a
+ +
=
u

Cubic crystal
n 2u u Intensity Sinu Sin
2
u ratio
Determination of Crystal Structure from 2u versus Intensity Data
2u u Intensity Sinu Sin
2
u 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
h
2
+ k
2
+ l
2
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 (h
2
+ K
2
+ l
2
) 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
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, = 1.54056
Note:
Peaks or not idealized o peaks broadened
Increasing splitting of peaks with |g u
Peaks are all not of same intensity
X-Ray Diffraction: A Practical Approach, C. Suryanarayana & M. Grant Norton, Plenum Press, New York (1998)
0
2
4
6
8
10
12
14
0 30 60 90
t
1
/
C
o
s
(
t
)
2 n d Sin u =
2
d
d Cos
d

u
u
=
1
2
d
d d Cos
u
u
=
Actually, the variation in 2u is to be seen
n 2u u Sinu Sin
2
u ratio Index a (nm)
1 38.52 19.26 0.33 0.11 3 111 0.40448
2 44.76 22.38 0.38 0.14 4 200 0.40457
3 65.14 32.57 0.54 0.29 8 220 0.40471
4 78.26 39.13 0.63 0.40 11 311 0.40480
5* 82.47 41.235 0.66 0.43 12 222 0.40480
6* 99.11 49.555 0.76 0.58 16 400 0.40485
7* 112.03 56.015 0.83 0.69 19 331 0.40491
8* 116.60 58.3 0.85 0.72 20 420 0.40491
9* 137.47 68.735 0.93 0.87 24 422 0.40494
Determination of Crystal Structure from 2u versus Intensity Data
* o
1
, o
2
peaks are resolved (o
1
peaks are listed)

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 30 60 90
t
S
i
n
(
t
)
u

Sin
d
2
=
u
u
u
2
2
) (
Sin
Cos
d
d d
=
u
u
u
u
u
Tan
d
d
Sin
Cos
d
d d
=

=
) (
Error in d spacing
0
2
4
6
8
10
12
14
0 20 40 60 80 100
t
C
o
t
(
t
)
u
u
u
u
u
Tan
d
d
Sin
Cos
d
d d
=

=
) (
Error in d spacing
Error in d spacing decreases with u
Bravais lattice determination
Lattice parameter determination
Determination of solvus line in phase diagrams
Long range order
Applications of XRD
Crystallite size and Strain
More
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
Crystallite size and Strain
Braggs equation assumes:
Crystal is perfect and infinite
Incident beam is perfectly parallel and monochromatic
Actual experimental conditions are different from these leading various kinds of
deviations from Braggs condition
Peaks are not o curves Peaks are broadened
There are also deviations from the assumptions involved in the generating powder
patterns
Crystals may not be randomly oriented (textured sample) Peak intensities are
altered
In a powder sample if the crystallite size < 0.5 m
there are insufficient number of planes to build up a sharp diffraction pattern
peaks are broadened
XRD Line Broadening
Instrumental
Crystallite size
Strain
Stacking fault
XRD Line Broadening
Other defects
- Unresolved o
1
, o
2
peaks
- Non-monochromaticity of the source (finite width of o peak)
- Imperfect focusing
- In the vicinity of u
B
the ve of Braggs equation not being satisfied
- Residual Strain arising from dislocations, coherent precipitates
etc. leading to broadening
In principle every defect contributes to some broadening
B
i

B
c

B
s

... ) ( + + + + =
SF s c i
B B B B FWHM B
... ) ( + + + + =
SF s c i
B B B B FWHM B
Crystallite size
Size > 10 m Spotty ring
(no. of grains in the irradiated portion insufficient to produce a ring)
Size e (10, 0.5) Smooth continuous ring pattern
Size e (0.5, 0.1) Rings are broadened
Size < 0.1 No ring pattern
(irradiated volume too small to produce a diffraction ring pattern &
diffraction occurs only at low angles)
Spotty ring
Rings
Broadened Rings
Diffuse
Effect of crystallite size on SAD patterns
Single crystal
Spotty pattern
Few crystals in the selected region
Effect of crystallite size on SAD patterns
Ring pattern
Broadened Rings
Subtracting Instrumental Broadening
Instrumental broadening has to be subtracted to get the broadening effects due to
the sample
1
Mix specimen with known coarse-grained (~ 10m), well annealed (strain free)
does not give any broadening due to strain or crystallite size (the only
broadening is instrumental). A brittle material which can be
ground into powder form without leading to much stored strain is good.
If the pattern of the test sample (standard) is recorded separately then the
experimental conditions should be identical (it is preferable that one or more
peaks of the standard lies close to the specimens peaks)
2
Use the same material as the standard as the specimen to be X-rayed but with large
grain size and well annealed
r s c i
B B B B B = + ~
... ) ( + + + + =
SF s c i
B B B B FWHM B
For a peak with a Lorentzian profile
2 2 2
i r
B B B = For a peak with a Gaussian profile
2 2 2
) (
i i r
B B B B B =
A geometric mean can also used
Longer tail
Johann Carl Friedrich Gauss (1777-1855),
painted by Christian Albrecht Jensen
http://en.wikipedia.org/wiki/Carl_Friedrich_Gauss
Hendrik Antoon Lorentz
On the theory of reflection and refraction of light
University of Gttingen
Scherrers formula
( )
c
B
k
B
LCos

u
=
Wavelength
L Average crystallite size ( to surface of specimen)
k 0.94 [k e (0.89, 1.39)]
~ 1 (the accuracy of the method is only 10%)
For Gaussian line profiles and cubic crystals
0
2
4
6
8
10
12
14
0 30 60 90
t
1
/
C
o
s
(
t
)
Strain broadening
( )
s B
B Tan q u =
q Strain in the material
Smaller angle peaks
should be used to
separate B
s
and B
c

0
2
4
6
8
10
12
14
0 20 40 60 80 100
t
T
a
n
(
t
)
Separating crystallite size broadening and strain broadening
s c r
B B B + =
) (u

Cos L
k
B
c
= ) (u qTan B
s
=
) (
) (
u q
u

Tan
Cos L
k
B
r
+ =
) ( ) ( u q

u Sin
L
k
Cos B
r
+ =
Plot of [B
r
Cosu] vs [Sinu]
Example of a calculation
Sample: Annealed Al
Radiation: Cu ko ( = 1.54 )
Sample: Cold-worked Al
Radiation: Cu ko ( = 1.54 )
2u
I
n
t
e
n
s
i
t
y

2u
I
n
t
e
n
s
i
t
y

40 60
40 60
X-Ray Diffraction: A Practical Approach, C. Suryanarayana & M. Grant Norton, Plenum Press, New York (1998)
Annealed Al
Peak No. 2u () hkl B
i
= FWHM () B
i
= FWHM (rad)
1 38.52 111 0.103 1.8 10
3

2 44.76 200 0.066 1.2 10
3
3 65.13 220 0.089 1.6 10
3
Cold-worked Al
2u () Sin(u) hkl B

() B (rad) B
r
Cosu (rad)
1 38.51 0.3298 111 0.187 3.3 10
3
2.8 10
3
2.6 10
3

2 44.77 0.3808 200 0.206 3.6 10
3
3.4 10
3
3.1 10
3
3 65.15 0.5384 220 0.271 4.7 10
3
4.4 10
3
3.7 10
3
2 2 2
i r
B B B =
3
10 7 . 1

=
L
k
nm L Size Grain 90 ) ( =
end
Iso-intensity circle
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
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.
421 missing
Ewald sphere X-rays
(Cu K
o
) = 1.54 , 1/ = 0.65
1
, a
Cu
= 3.61 , 1/a
Cu
= 0.28
1
0.28
1
0.65
1
Multiplicity factor
Lattice Index Multiplicity Planes
Cubic
with highest
symmetry
(100) 6 [(100) (010) (001)] ( 2 for negatives)
(110) 12
[(110) (101) (011), (110) (101) (011)] ( 2 for
negatives)
(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)
(210) 24
(210) = 3! Ways, (210) = 3! Ways,
(210) = 3! Ways, (210) = 3! Ways,
(211) 24
(321) 48
Tetragonal (100) 4 [(100) (010)]
(110) 4 [(110) (110)]
(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)
(210) 6
(211) 24
(321) 48