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)
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 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

An accelerating (/decelerating) charge radiates electromagnetic radiation

Mo Target impacted by electrons accelerated by a 35 kV potential

Kα

Characteristic radiation →
White Kβ due to energy transitions
Intensity

radiation in the atom

0.2 0.6 1.0 1.4

Wavelength (λ )
Target Metal λ Of Kα 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)
 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

E1 = hν 1 (λ1 ,ν 1 ) Electron knocked aside

2θ

E2 = hν 2 (λ2 ,ν 2 )
∆λ = λ2 − λ1 = 0.0243(1 − Cos 2θ )

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)
(10−16 s 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 with waves scattered from other atoms

Secondary
Incoming X-rays 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
 BRAGG’s EQUATION

Deviation = 2θ

Ray 1

Ray 2 θ θ
θ
θθ d

dS
in θ

 The path difference between ray 1 and ray 2 = 2d Sinθ

 For constructive interference: nλ = 2d Sinθ
 In plane scattering is in phase
Incident and scattered
waves are in phase if

Scattering from across planes is in phase

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

But this is still reinforced scattering

and NOT reflection
Note that in the Bragg’s 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
Bragg’s condition !!

Note: shift (systematic) is

actually not a problem!

d
Note: shift is actually not a problem! → Why is ‘systematic’ shift not a problem?

n λ = AY + YB AY = XY Cos[180 − (α + θ )] = − XY Cos (α + θ )
YB = XY Cos (α − θ )
n λ = AY + YB = XY [Cos (α − θ ) − Cos (α + θ )] = XY [2 Sinα Sinθ ]
d d
nλ = [2 Sinα Sinθ ] = 2 d Sinθ n λ = 2 d Sinθ = Sin(α )
Sinα XY
onsider the case for which θ 1 ≠ θ 2

Constructive interference can still occur if the difference in the path length
traversed by R1 and R2 before and after scattering are an integral multiple of the
wavelength
⇒ (AY − XC) = h λ (h is an integer)

AY
= Cos (θ1 )
XC
= Cos (θ 2 ) a Cos (θ1 ) − a Cos (θ 2 ) = h λ
a a

a [ Cos (θ1 ) − Cos (θ 2 ) ] = h λ

 a [ Cos (θ1 ) − Cos (θ 2 ) ] = h λ
Generalizing into 3D
b [ Cos (θ 3 ) − Cos (θ 4 ) ] = k λ
c [ Cos (θ 5 ) − Cos (θ 6 ) ] = l λ

Laue’s equations  
a ⋅ (S − S0 ) = h λ
S0 → incoming X-ray beam  
b ⋅ (S − S0 ) = k λ
S → Scattered X-ray beam
 
c ⋅ (S − S0 ) = l λ

This is looking at diffraction from atomic arrays and not planes

 A physical picture of scattering leading to diffraction is embodied in Laue’s equations
 Bragg’s 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’ (Bragg’s 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?”
  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

  nλ = 2d Sinθ
 n is an integer and is the order of the reflection
 For Cu Kα radiation (λ = 1.54 Å) and d110 = 2.22 Å

n Sinθ θ

1 0.34 20.7º First order reflection from (110)

2 0.69 43.92º Second order reflection from (110)

Also written as (220)

a a
d hkl = 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)

nλ = 2d hkl sin θ

d hkl
λ=2 sin θ
n

λ = 2d nh nk nl sin θ
Intensity of the Scattered electrons
Scattering by a crystal

A
Electron Polarization factor

B
Atom Atomic scattering factor (f)

C
Unit cell (uc) Structure factor (F)
A Scattering by an Electron

Em
is sio
(λ0 ,ν 0 ) n in ‘
all’
dire
Sets electron into oscillation ctio
ns

Coherent
(definite phase relationship) (λ0 ,ν 0 ) Scattered beams

 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
For an polarized wave
z
P
For a wave oscillating in z direction α r

Intensity of the scattered beam due to an electron (I) at a point P

such that r >> λ
e 4  Sin 2α 
I = I 0 2 4  2 
mc  r 

The reason we are able to

1 neglect scattering from the
protons in the nucleus

The scattered rays are also plane polarized

0.8
 e 4  Sin 2α 
I = I 0 2 4  2 
mc  r 
For an unpolarized wave E is the measure of the amplitude of the wave
E2 = Intensity
I0
E =E +E
2 2
y
2
z
= I0 y = I0z
2

IPy = Intensity at point P due to Ey

e 4  Sin ( φ y ) 
2

I Py = I 0 y  
2 4
mc  r 2
 Total Intensity at point P due to Ey & Ez
 

e 4  Sin ( φ y ) + Sin ( φz ) 
2 2
IPz = Intensity at point P due to Ez
IP = I0 2 4  
mc  r 2

e 4  Sin ( φz )   
2

I Pz = I0z 2 4  

mc  r 2

 e 4  Sin ( φ y ) + Sin ( φz ) 
2 2

IP = I0 2 4  
mc  r 2

 
 Sin 2 ( φ y ) + Sin 2 ( φ z )  =  1− Cos 2 (φ y ) + 1− Cos 2 (φ z ) =  2− Cos 2 (φ y ) − Cos 2 (φ z )
     

Cos 2 ( φx ) + Cos 2 ( φ y ) + Cos 2 ( φ z ) = 1 Sum of the squares of the direction cosines =1

 

Hence    ( )
  (
 2 − Cos 2 ( φ y ) − Cos 2 ( φ z )  = 2 − 1− Cos 2 (φ x )  =  1+ Cos 2(φ x) 
 )
e  ( 1 +4Cos 2
(φx ) ) 
⇒ IP = I0 2 4  
mc  r 2

 
In terms of 2θ

e 4  ( 1 + Cos (2θ ) ) 
2

IP = I0 2 4  
mc  r 2

 
 z e 4  Cos 2 2θ 
I = I 0 2 4  
P m c  r 2 

α r
2θ

x 1

 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 0.8
The trace of the scattering plane → BB’
Are all coplanar
 ⇒ OP is constrained to be on the xz plane

s(2t)]^2
0.6
For an unpolarized wave E is the measure of the amplitude of the wave
E2 = Intensity

E 2 = E y2 + E z2

I0
= I0 y = I0z
2

IPy = Intensity at point P due to Ey

I Py = I 0 y
4
e   Sin ( )  = I
2 π
2 e4  1 
2 4  2 
m 2c 4   0y
r2 m c r 
 
The zx plane is ⊥ to the y direction: hence, α = 90°
IPz = Intensity at point P due to Ez

I Pz = I 0 z
4
e   Sin (
2 π
2
− 2θ )  = I e 4  Cos 2 ( 2θ ) 
 
2 4 
m 2c 4   0z
r2 mc  r 2

 
 4
I +
e  0 y 0zI Cos 2
( 2θ )  1
I P = I Py + I Pz = 2 4
m c  r2 

0.8
I 0 e 4  1 + Cos 2 ( 2θ ) 
IP = 
2 4  2
 ⇒ Scattered beam is not unpolarized
2 mc  r  0.6
Very small number

 Forward and backward scattered intensity higher than at 90°

0.4
 Scattered intensity minute fraction of the incident intensity

0.2

Cos(t)
0
0 30
-0.2
 I 0 e 4  1 + Cos 2 ( 2θ )  Polarization factor
I P = 2 2 4   Comes into being as we used
r mc  2  unpolarized beam

1.2

1
 B Scattering by an Atom
Scattering by an atom ∝ [Atomic number, (path difference suffered by scattering from each e−, λ )]

Scattering by an atom ∝ [Z, (θ , λ )]  Angle of scattering leads to path differences

 In the forward direction all scattered waves are in phase
Sin(θ )
λ

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(θ )
(Å−1 ) →
λ
 Coherent scattering Incoherent (Compton) scattering

Z↑ ↑ ↓
Sin(θ ) / λ ↓ ↑ ↓
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 parallēlepipedon) 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
 Ray 1 = R1 R1'

Ray 3 = R3 R3'
θ B A θ
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 :: λ
RBS :: AB :: x

AB x x
= =
AC λ a
h

δ R1R2 = MCN = 2d h 00 Sin(θ ) = λ

2π λ
AB x ϕ= δ ϕ =δ
δ R1R3 = RBS = λ= λ λ 2π
AC a
h
2π x x x
ϕ R1R3 = λ = 2π h → fractional coordinate → x′ ϕ R1R3 = 2π h x′
λ a a a
h

Extending to 3D ϕ = 2π ( h x′ + k y′ + l 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
ϕ = 2π ( h x′ + k y′ + l z′) E = Ae iϕ = fei [2π ( h x ′+k y ′+l 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)

Amplitude of wave scattered by all atoms in uc

F = Structure Factor =
Amplitude of wave scattered by an electron I ∝ F2
n n
= ∑ fj e = ∑ fj e
hkl iϕ j i [2π ( h x ′j +k y ′j +l z ′j )]
F n
For n atoms in the UC
j =1 j =1

Structure factor is independent of the shape and size of the unit cell
If the UC distorts so do the planes in it!!
 niπ
Structure factor calculations e = (−1) n
Simple Cubic
A Atom at (0,0,0) and equivalent positions e ( odd n ) iπ = −1
e ( even n ) iπ = +1
e niπ = e − niπ
e iθ + e − iθ
= Cos (θ )
2

iϕ j i [2π ( h x ′j +k y ′j +l z ′j )]
F = fj e = fj e

F=f e i[2π ( h ⋅0 +k ⋅ 0 +l ⋅ 0)] = f e 0 = f

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

iϕ j i [2π ( h x ′j +k y ′j +l z ′j )]
F = fj e = fj e
1 1
i[2π ( h ⋅ +k ⋅ +l ⋅ 0)]
F = f e i[2π ( h ⋅0 +k ⋅ 0 +l ⋅ 0)] + f e 2 2

h +k
i[ 2 π ( )]
= f e0 + f e 2
= f [1+ e iπ( h +k) ]
Real

(h + k) e
ve n
r b o t h odd F =2f F2 = 4 f 2
en o
Both ev
e.g. (001), (110), (112); (021), (022), (023)
F = f [1 + e iπ ( h + k ) ] Mixtu
r e of odd
a nd e ve n
( h + k)
odd F =0 F2 = 0
e.g. (100), (101), (102); (031), (032), (033)

⇒ F is independent of the ‘l’ index

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

iϕ j i [2π ( h x ′j +k y ′j +l z ′j )]
F = fj e = fj e
1 1 1
i [2π ( h ⋅ +k ⋅ +l ⋅ )]
F = f e i[2π ( h ⋅0 +k ⋅ 0 +l ⋅ 0)] + f e 2 2 2

h + k +l
i[ 2 π ( )]
= f e0 + f e 2
= f [1+ e iπ( h +k +l) ]
Real

l ) ev en F =2f F2 = 4 f 2
(h + k +
e.g. (110), (200), (211); (220), (022), (310)
F = f [1 + e iπ ( h + k +l ) ] (h + k +
l ) odd
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)

iϕ j i [2π ( h x ′j +k y ′j +l z ′j )]
F = fj e = fj e
 i[ 2π ( 0)] i[ 2π ( h +2 k )] i[ 2π ( k 2+l )] i[ 2π ( l +2h )] 
F = f e +e +e +e 
 
= f [1 + eiπ ( h + k ) + eiπ ( k +l ) + eiπ ( l + h ) ] Real

F = f [1 + e iπ ( h + k ) + e iπ ( k +l ) + e iπ ( 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)
Mixed indices 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 + eiπ ( e ) + eiπ (o ) + e iπ ( o )] = [1 + 1− 1− 1] = 0

CASE B : [1 + eiπ ( o ) + eiπ (e ) + eiπ (o )] = [1 − 1+ 1− 1] = 0

(h, k, l) mixed F =0 F =02 e.g. (100), (211); (210), (032), (033)

Unmixed indices All odd (e.g. 111); all even (e.g. 222)

Unmixed indices CASE h k l

A o o o
B e e e

CASE A : [1 + eiπ (e ) + eiπ (e ) + e iπ (e )] = [1 + 1+ 1+ 1] = 4

CASE B : [1 + eiπ (e ) + eiπ ( e ) + eiπ (e )] = [1 + 1+ 1+ 1] = 4

(h, k, l) unmixed F =4f F 2 = 16 f 2

e.g. (111), (200), (220), (333), (420)
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:
Face Centred Cubic
 i[ 2π ( 0 )] i[ 2π ( h +2 k )] i[ 2π ( k 2+l )] i[ 2π ( l +2h )] 
F = f Na + e +e +e +e +
 
 i[ 2π ( h2 )] i[ 2π ( k2 )] i[ 2π ( 2l )] i[ 2π ( h +2k +l )] 
f Cl −  e +e +e +e 
 
F = f Na + [1 + eiπ ( h + k ) + eiπ ( k +l ) + eiπ ( l + h ) ] +
f Cl − [eiπ ( h ) + eiπ ( k ) + eiπ ( l ) + eiπ ( h + k +l ) ]

F = f Na + [1 + eiπ ( h + k ) + eiπ ( k +l ) + eiπ ( l + h ) ] +

f Cl − e iπ ( h + k +l ) [eiπ ( − k −l ) + e iπ ( −l −h ) + eiπ ( − h −k ) + 1]
F = [ f Na + + f Cl − eiπ ( h + k +l ) ][1 + eiπ ( h + k ) + eiπ ( k +l ) + eiπ ( l + h ) ]
F = [ f Na + + f Cl − eiπ ( h + k +l ) ][1 + eiπ ( h + k ) + eiπ ( k +l ) + eiπ ( l + h ) ]
F = [Term − 1][Term − 2] Zero for mixed indices
Mixed indices CASE h k l
Mixed indices A o o e
B o e e

CASE A : Term − 2 = [1 + e iπ ( e ) + e iπ ( o ) + e iπ ( o ) ] = [1 + 1 − 1 − 1] = 0
CASE B : Term − 2 = [1 + e iπ ( o ) + e iπ ( e ) + e iπ ( o ) ] = [1 − 1 + 1 − 1] = 0

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

 Unmixed indices CASE h k l
Unmixed indices
A o o o
B e e e

CASE A : Term − 2 = [1 + e iπ ( e ) + e iπ ( e ) + e iπ ( e ) ] = [1 + 1 + 1 + 1] = 4
CASE B : Term − 2 = [1 + e iπ ( e ) + e iπ ( e ) + e iπ ( e ) ] = [1 + 1 + 1 + 1] = 4

(h, k, l) unmixed F = 4[ f Na + + f Cl − e iπ ( h + k +l ) ]
e.g. (111), (222); (133), (244)

F = 4[ f Na + + f Cl − ] If (h + k + l) is even F 2 = 16[ f Na + + f Cl − ]2
e.g. (222),(244)

F = 4[ f Na + − f Cl − ] If (h + k + l) is odd F 2 = 16[ f Na + − f Cl − ]2
e.g. (111), (133)
⇒ Presence of additional atoms/ions/molecules in the UC can alter
the intensities of some of the reflections
 Selection / Extinction Rules
Bravais Lattice Reflections which may Reflections necessarily
be present 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 h and k mixed
C centred 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
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
 Reciprocal Lattice Properties are reciprocal to the crystal lattice
* 1   * 1   * 1  
BASIS
VECTORS
b1 = ( a2 × a3 ) b2 = ( a3 × a1 ) b3 = ( a1 × a2 )
V V V
* 
*
bi usuall written as ai a3
*
b3
* 1  
b = b3 = ( a1 × a2 )
*
3
V C 
Area (OAMB ) 1 a2
= =
Area (OAMB ) ⋅ Height of Cell OP
P

1 *   B
b = *
3 b3 is ⊥ to a1 and a2
d 001 B 
a1 M
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

(01) 02 12 22


a2 (11)
(10) 01 11
* * * 21
b2 g11 g 21
(21) 
a1
a1 * 1
b1 a1
10 20
00 The reciprocal lattice has an origin!
 22
(01) 12
02

 (11) 21
a2 (10) 11
(21)  0 1*
a1 b2
a1 * 20
22
b1 10
12
02
(01)
00
21
11
01 (11)
(10)
Note perpendicularity of various vectors
(21) 20
10
 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
 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’

 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)

SC
001
011

101 111

Lattice = SC 000
010

100
110
No missing reflections
Reciprocal Crystal = 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 Crystal = 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 Crystal = BCC
F 2 = 16 f 2
Figures NOT to Scale
 In a strict sense this is not a crystal !!
Ordered Solid solution

High T disordered

BCC

470ºC
G = H − TS

Sublattice-1

Sublattice-2

Low T ordered SC
 Ordered

BCC SC
Disordered Ordered
FCC
δ - NiAl, BCC B2 (CsCl type)
ε - Ni3Al, FCC L12 (AuCu3-I type)

Ordered

FCC
SC BCC
 There are two ways of constructing the Reciprocal Crystal:
Construct the lattice and decorate each lattice point with appropriate intensity
Use the concept as that for the real crystal

) SC + two kinds of Intensities decorating the lattice

) (FCC) + (Motif = 1FR + 1SLR)

 FR → Fundamental Reflection
 SLR → Superlattice Reflection

) SC + two kinds of Intensities decorating the lattice

) (BCC) + (Motif = 1FR + 3SLR)
 The Ewald Sphere
* Paul Peter Ewald (German physicist and crystallographer; 1888-1985)
 7. Paul-Peter-Ewald-Kolloquium

Freitag, 17. Juli 2008 organisiert von:

Max-Planck-Institut für Metallforschung
Institut für Theoretische und Angewandte Physik,
Institut für Metallkunde,
Institut für Nichtmetallische Anorganische
Materialien
der Universität Stuttgart
Programm
13:30 Joachim Spatz (Max-Planck-Institut für Metallforschung)
Begrüßung
13:45 Heribert Knorr (Ministerium für Wissenschaft, Forschung und Kunst Baden-Württemberg
Begrüßung
14:00 Stefan Hell (Max-Planck-Institut für Biophysikalische Chemie)
Nano-Auflösung 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 Getränke
15:30 Frank Gießelmann(Universität Stuttgart)
Von ferroelektrischen Fluiden zu geordneten Dispersionen von Nanoröhren: Aktuelle Themen der
Flüssigkristallforschung
16:00 Verleihung des Günter-Petzow-Preises 2008
16:15 Udo Welzel (Max-Planck-Institut für Metallforschung)
Materialien unter Spannung: Ursachen, Messung und Auswirkungen- Freund und Feind
ab 17:00 Sommerfest des Max-Planck-Instituts für Metallforschung
 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

See Cullity’s book: A15-4

Bragg’s equation revisited λ 2 1 d hkl
n λ = 2 d hkl Sinθ hkl Sinθ hkl = =
d hkl 2λ
 Draw a circle with diameter 2/λ
 Construct a triangle with the diameter as the hypotenuse and 1/dhkl 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 θ hkl (from the rewritten Bragg’s equation)

* 1
*
g hkl = g hkl =
d hkl
 The Ewald Sphere construction

Crystal related information is present in the reciprocal crystal

λ 2 1 d hkl
Sinθ hkl = = The Ewald sphere construction generates the diffraction pattern
d hkl 2λ

Radiation related information is present in the Ewald Sphere

Ewald Sphere

Reciprocal Space

2θ The Ewald Sphere touches the

KD reciprocal lattice (for point 41)
Ki ⇒ Bragg’s equation is satisfied
02 for 41

01
∆ K(41)
= K =g = Diffraction Vector
Ewald sphere → X-rays

λ (Cu Kα ) = 1.54 Å, 1/λ = 0.65 Å−1 (2/λ = 1.3 Å−1 ), aAl = 4.05 Å, d111 = 2.34 Å, 1/d111 = 0.43 Å−1
 Crystal structure determination

Many θ s (orientations) POWDER

Monochromatic X-rays Powder specimen METHOD

Single θ
LAUE
Panchromatic X-rays
TECHNIQUE

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

Cone of diffracted rays

POWDER METHOD
Diffraction cones and the Debye-Scherrer geometry
Different cones for different reflections

Film may be replaced with detector

http://www.matter.org.uk/diffraction/x-ray/powder_method.htm
The 440 reflection is not observed
The 331 reflection is not observed
 THE POWDER METHOD

λ = 2dSinθ d Cubic = a
Cubic crystal
h2 + k 2 + l 2

4 a 2
sin 2
θ 4 a 2
λ = 2
2
(h 2 + k 2 + l 2 ) = 2 sin 2 θ
h + k2 + l2 λ

λ 2
a2 = ( h 2
+ k 2
+ l 2
) (h 2 + k 2 + l 2 ) ∝ sin 2 θ
4 sin θ2
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 ( 2θ ) )
Lorentz factor Combination of 3 geometric factors

 1   1 
Lorentz factor =  ( Cosθ )  
 Sin 2θ   Sin 2θ 

Absorption factor Specimen absorption

Temperature factor Thermal diffuse scattering

Multiplicity factor
Lattice Index Multiplicity Planes
Cubic (100) 6 [(100) (010) (001)] (× 2 for negatives)
(with highest
symmetry) (110) 12 [(110) (101) (011), (110) (101) (011)] (× 2 for negatives)
(111) 12 [(111) (111) (111) (111)] (× 2 for negatives)

(210) 24* (210) → 3! Ways, (210) → 3! Ways,

(210) → 3! Ways, (210) → 3! Ways
(211) 24 (211) → 3 ways, (211) → 3! ways,
(211) → 3 ways
(321) 48*
Tetragonal (100) 4 [(100) (010)] (× 2 for negatives)
(with highest
symmetry) (110) 4 [(110) (110)] (× 2 for negatives)

(111) 8 [(111) (111) (111) (111)] (× 2 for negatives)

(210) 8* (210) = 2 Ways, (210) = 2 Ways,

(210) = 2 Ways, (210) = 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

 Multiplicity factor

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)
Polarization factor Lorentz factor

(
I P = 1 + Cos 2 ( 2θ ) )  1 
Lorentz factor = 
 1 
( Cosθ )  
 Sin 2θ   Sin 2θ 

 1 + Cos 2 ( 230
θ) 
Lorentz Polarizati on factor =  
 Sin θ Cosθ 
2

25

Lorentz-Polarization factor
20

15

10

5
Intensity of powder pattern lines (ignoring Temperature & Absorption factors)
 Valid for Debye-Scherrer geometry
2  1 + Cos 2θ 
2
I = F p   I → Relative Integrated “Intensity”
 Sin θ Cosθ 
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
 THE POWDER METHOD

λ = 2dSinθ d Cubic = a
Cubic crystal
h2 + k 2 + l 2

4 a 2
sin 2
θ 4 a 2
λ = 2
2
(h 2 + k 2 + l 2 ) = 2 sin 2 θ
h + k2 + l2 λ

λ 2
a2 = ( h 2
+ k 2
+ l 2
) (h 2 + k 2 + l 2 ) ∝ sin 2 θ
4 sin θ2
Determination of Crystal Structure from 2θ versus Intensity Data

n 2θ → θ Intensity Sinθ Sin2 θ ratio

 2θ → θ Intensity Sinθ Sin2 θ 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
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 …
 Powder diffraction pattern from Al Radiation: Cu Kα , λ = 1.54056 Å

111
Note:
 Peaks or not idealized δ peaks → broadened
 Increasing splitting of peaks with ↑g θ
 Peaks are all not of same intensity

311
220
200

420
331

422
222

400

α 1 & α 2 peaks resolved

X-Ray Diffraction: A Practical Approach, C. Suryanarayana & M. Grant Norton, Plenum Press, New York (1998)
 14

12

10

1/Cos(t)
6

0
0 30 60

n λ = 2 d Sinθ
dλ
= 2 d Cosθ
dθ
dθ 1
=
d λ 2 d Cosθ

Actually, the variation in 2θ is to be seen

 Determination of Crystal Structure from 2θ versus Intensity Data

n 2θ θ Sinθ Sin2 θ 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

* → α 1 , α 2 peaks are resolved (α 1 peaks are listed)

 λ
d=
2 Sinθ
d (d ) − λCosθ
=
dθ 2 Sin 2θ
d (d ) − Cosθ − dθ
= dθ =
d Sinθ Tanθ

Error in d spacing

1
Fo
rt
he
sa
m e∆
θ
the
er r
or
i nS
inθ
↓w
ith
↑θ
d (d ) − Cosθ
d
=
Sinθ
dθ =
− dθ
Tanθ 14
Error in d spacing

Error in d spacing decreases with θ 12

Applications of XRD

Bravais lattice determination

Lattice parameter determination

Determination of solvus line in phase diagrams

Long range order

Crystallite size and Strain

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

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

Intensity →
Diffraction angle (2θ ) →
Diffraction angle (2θ ) →
Liquid / Amorphous solid
Intensity →

0 90 180

0 90 180
Crystallite size and Strain

 Bragg’s 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 Bragg’s condition
 Peaks are not ‘δ ’ 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 µ m

 there are insufficient number of planes to build up a sharp diffraction pattern
⇒ peaks are broadened
XRD Line Broadening
XRD Line Broadening

Instrumental • Unresolved α 1 , α 2 peaks

Bi • Non-monochromaticity of the source (finite width of α peak)
• Imperfect focusing

Crystallite size • In the vicinity of θ B the −ve of Bragg’s equation not being satisfied
Bc

Strain • ‘Residual Strain’ arising from dislocations, coherent precipitates

Bs etc. leading to broadening

Stacking fault
In principle every defect contributes to some broadening
Other defects

B ( FWHM ) = Bi + Bc + Bs + BSF + ...

B ( FWHM ) = Bi + Bc + Bs + BSF + ...
 Crystallite size

 Size > 10 µ m  Spotty ring

(no. of grains in the irradiated portion insufficient to produce a ring)

 Size ∈ (10, 0.5) µ  Smooth continuous ring pattern

 Size ∈ (0.5, 0.1) µ  Rings are broadened

 Size < 0.1 µ  No ring pattern

(irradiated volume too small to produce a diffraction ring pattern &
diffraction occurs only at low angles)
Spotty ring
Rings

Diffuse Broadened Rings

 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 (~ 10µ m), 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 specimen’s peaks)

2
 Use the same material as the standard as the specimen to be X-rayed but with
large grain size and well annealed
B ( FWHM ) = Bi + Bc + Bs + BSF + ...

For a peak with a Lorentzian B − Bi ≈ Bc + Bs = Br

profile

Hendrik Antoon Lorentz

Longer tail On the theory of reflection and refraction of light

For a peak with a Gaussian

profile
Br2 = B 2 − Bi2

A geometric mean can also

used Br2 = ( B − Bi ) B 2 − Bi2
Johann Carl Friedrich Gauss (1777-1855),
painted by Christian Albrecht Jensen
http://en.wikipedia.org/wiki/Carl_Friedrich_Gauss University of Göttingen
Scherrer’s formula For Gaussian line profiles and cubic crystals

λ → Wavelength
kλ
Bc =  L → Average crystallite size (⊥ to surface of specimen)
L Cos (θ B ) 
k → 0.94 [k ∈ (0.89, 1.39)]
~ 1 (the accuracy of the method is only 10%)

14

12

10

1/Cos(t)
6

0
0 30 60
Strain broadening
14
Bs = η Tan(θ B )
 η → Strain in the material

12

10
Smaller angle peaks
should be used to
separate Bs and Bc
Separating crystallite size broadening and strain broadening

Br = Bc + Bs kλ
Bc = Bs = η Tan(θ )
L Cos (θ )

kλ
Br = + η Tan(θ )
L Cos (θ ) Plot of [Br Cosθ ] vs [Sinθ ]

kλ
Br Cos (θ ) = + η Sin(θ )
L
 Example of a calculation

Sample: Annealed Al
Radiation: Cu kα (λ = 1.54 Å)

Intensity →
Sample: Cold-worked Al
Radiation: Cu kα (λ = 1.54 Å)
2θ →
40 60 Intensity →

2θ →
X-Ray Diffraction: A Practical Approach, C. Suryanarayana & M. Grant Norton, Plenum Press, New York (1998) 40 60
Annealed Al

Peak No. 2θ (°) hkl Bi = FWHM (°) Bi = 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
2θ (°) Sin(θ ) hkl B (°) B (rad) Br2 = B 2 − Bi2 Br Cosθ (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
kλ
= 1.7 ×10 −3 Grain Size ( L) = 90 nm
L
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
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)

421 missing
Ewald sphere → X-rays

−1
0.65 Å
0.2
λ (Cu Kα ) = 1.54 Å, 1/λ = 0.65 Å−1 , aCu = 3.61 Å, 1/aCu = 0.28 Å−1
Multiplicity factor
Lattice Index Multiplicity Planes
Cubic (100) 6 [(100) (010) (001)] (× 2 for negatives)
with highest (110) 12 [(110) (101) (011), (110) (101) (011)] (× 2 for
symmetry negatives)
(111) 8 [(111) (111) (111) (111)] (× 2 for negatives)
(210) 24 (210) = 3! Ways, (210) = 3! Ways,
(210) = 3! Ways, (210) = 3! Ways,
(211) 24
(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) 24
(321) 48