X-ray, electron and neutron diffraction:

Crystal structure determination

Outline
I. Scattering of x-rays from an array of atoms
II. Structure factor: Lattice with more than one atom
basis
III. Laue's condition
IV. Bragg's law
V. Examples
 X-ray, electron and neutron diffraction:
Crystal structure determination

Objectives
I. To understand the physics behind the diffraction
pattern of a solid
II. To understand Von Laue's and Bragg's approaches
for determining the structure of crystals
III. Structure determination from the given experimental
data
 X-ray diffraction from Solids: Two
Perspectives

Max von Laue William Henry Bragg William Lawrence Bragg

The Nobel Prize in Physics 1914 was awarded to Max von Laue "for his
discovery of the diffraction of X-rays by crystals".
The Nobel Prize in Physics 1915 was awarded jointly to Sir William
Henry Bragg and William Lawrence Bragg "for their services in the
analysis of crystal structure by means of X-rays"
 X-ray diffraction from Solids

A typical experimental setup for carrying out x-ray

diffraction from solids.
X-ray diffraction from Solids: Physics Aspects
 Diffraction from Solids: Requirements
For diffraction from solids the wavelength l of the incident wave
should be a few Angstroms.
For X-rays of energy E, =hc/ E
For matter waves (electrons and neutrons), =h/ 2mE

~2 Å

Energy of neutrons 20 meV

Energy of electrons 0.35 eV
Energy of x-rays 6 keV
 Diffraction : A Simple Example
Water waves in a ripple tank

A single large slit A single small slit

Diffraction : From Two Slits
 Scattering from Atoms: Assumptions

(i) For x-rays, electrons, and neutrons incident on a crystal,

diffraction occurs due to interference between waves
scattered elastically from the atoms in the crystal.
(ii) If we treat the incident waves as plane waves and the
atoms as ideal point scatterers, the scattered waves are
spherical waves.
(iii) We will assume that the scattering is isotropic.
Scattering from Atoms: Plane and Spherical Waves
Plane wave Spherical wave

B
r O

i k ∣r∣− t
i k⋅r− t  e
= A e = A
∣r∣
 D

Scattered wave
k

r'
Incident wave

B r O
d
P

i k ∣r '∣
 =Ae B i  k⋅r− t 
OD −i  t i k⋅r ' e
i  =Ae
s
[e f ]
 =Ae
O −i  t ∣r '∣ i k r ' −d
i
PD −i t i k⋅d i k⋅ r '−d e ∣ ∣
 =Ae i  k⋅d− t 
P
 s =A e e [e f ]
i
∣r '−d∣
 Scattering from Atoms: Theory
Waves at D from the atoms at O and P are
i k ∣r '∣
OD i k⋅r ' e
 =Ae
s
−i t
[e f ]
∣r '∣
i k ∣r '−d∣
PD −i  t i k⋅d i k⋅r '−d  e D
 =Ae
s
e [e f ]
∣r '−d∣
Consider the distance from the second scatterer to D
r'
∣r '−d∣≈r ' −r '⋅d
Multiplying it by the wave number k, we get O
d r ' ≫d
k ∣r '−d∣≈kr '− k '⋅d
where we have defined, k ' ≡k r ' P
 Scattering from Atoms: Theory
Defining the scattering vector  k ,
k− k '= k k' k
We get, ikr'
PD i k⋅r ' e i  k⋅d k
 = A[e
s
f e ]
r'
If we have n scatterers located at R then the sum of the
n
scattered wave at D can be written as
i k r'
D e i  k⋅R
 =A ∑
s fn e n

n r'
Let R be the translation vectors of a Bravais lattice such that
n

Rn=n 1 a1n 2 a2 n 3 a3 , n 1 , n 2 , n3 are integers

The scattering amplitude at D is
D i  k⋅R n
 = A∑ f ne
s
n
 Scattering from Atoms: Theory
Substituting for R and assuming that there are N 1 , N 2 and
n
N 3 scatterers along a1 , a2 and a3 respectively, we can write
the scattering amplitude at D as
D
 = A∑ f n e
i  k⋅R n
a3
s
n a2
N 1−1 N 2 −1 N 3−1

= Af ∑ ∑ ∑e
i n1 a1 n 2 a2 n 3 a3 ⋅ k a1
n 1=0 n 2 =0 n 3=0

N 1−1 N 2 −1 N 3−1
i n1 a1⋅ k i n 2 a 2⋅ k i n 3 a3⋅ k
=A f ∑e ∑e ∑e
n1 =0 n 2 =0 n 3=0
3 N j−1
i n j a j⋅ k
= Af ∏ ∑e
j=1 n j =0
 Scattering from Atoms: Theory
3 N j −1
D i a j⋅ k n j
 = Af ∏
s ∑ e 
j=1 n j =0
Simplifying,
3 i N j a j⋅ k
D 1−e
 = Af ∏
s i a j⋅ k
j=1 1−e
Since intensity I is related to the scattering amplitude as I ∝  D 2,
we get,
∣ ∣ s

3
1−cos  N j a j⋅ k
I =I atom ∏
j=1 1−cos a j⋅ k

Using 1−cos 2x=2 sin 2 x , the expression for intensity, as given

above, can be simplified.
 Scattering from Atoms: Theory
The intensity is given by

3
Y sin2(Njaj ¢ ¢k=2)
I = Iatom 2
j= 1
sin (aj ¢ ¢k=2)

The intensity is maximum whenever a j⋅ k=2 m j

Knowing that a reciprocal space lattice vector G hkl is given by
G hkl =h b1k b2 l b3 , h , k ,l are integers
and ai⋅b j =2   ij we get,

a j⋅ k=2 m j
 Scattering from Atoms: Theory
Thus
a1⋅G hkl =2  h
a2⋅G hkl =2  k
a3⋅G hkl =2  l
We get a peak whenever scattering vector is equal to one of the
reciprocal lattice vector,

 k=G hkl Laue' condition

 Scattering from Atoms: Numerical Check
Numerical check: Consider intensity in one dimension with finite
number of scatterers
2 1
sin  N a  k 
2
I∝ .
2 1
sin  a  k 
2
Scattering from Atoms: Numerical Check
 Scattering from Diffraction Grating

The bright fringes, which come from constructive interference of the

light waves from different slits, are found at the same angles they are
found if there are only two slits
 Scattering from Atoms: Ewald Sphere

Incident X-ray (white arrow) is getting diffracted (yellow arrow)

whenever Laue's condition is satisfied. The sphere, depicted in
green, is known as the Ewald sphere.
Scattering from lattice with basis : Structure factor
So far the sum over all Bravais lattice points, indicated by the sum
over n, yields the total scattering amplitude at D to be

D i  k⋅R n
 = A∑ f n e
s
n
However, for more than one atom basis, given by d , we must also
j
sum over the basis atoms at each lattice point,
D i K⋅ R n d j 
 = A∑ f j e
s
n, j
i K⋅R n i K⋅d j
= A∑ e ∑ f je
n j
Defining the second sum as the structure factor SK
i K⋅d j
S K =∑ f j e
j 2 2 2
i K⋅R n
Therefore, the intensity I =∣A∣ ∣∑ e ∣ ∣S ∣ K
Example: Simple cubic (sc) with one point basis
Consider a simple cubic lattice with a one point basis given by
d 1 =0
The corresponding reciprocal lattice vectors are
2
K= h x k y l z 
a
i K⋅d j
Evaluation of the structure factor S K = f j e
∑ leads to
j
S K = f 1

Thus, in simple cubic lattice, all (hkl) values will lead to maxima in
The intensity.
For example: (100), (110), (111), (200), (210), ...
 Example: bcc as sc with two point basis
Consider body-centered cubic lattice as a simple cubic lattice with a
two point basis given by
a
d 1 =0 and d 2=  x  y z 
2
The corresponding reciprocal lattice vectors are
2
K= h x k y l z 
a i K⋅d
Evaluation of the structure factor S K = f j e j leads to ∑
2 a j
i h x k y l z ⋅  x  y z 
a 2
S K = f 1e 
i  h kl
= f 1e 
Finally,

S K = 2 f when hkl is even

{
0 whenhklis odd }
 Example: bcc as sc with two point basis
For simple cubic lattice all (hkl) combinations will lead to
maxima in the intensity. For example, (100), (110), (111),
(200), (210), ...
However, for simple cubic lattice with a two point basis
some of the above will not be allowed. That is, if (h+k+l)
is odd then the intensity will be zero due to the structure
factor.

£ £ £
For example: (100), (110), (111), (200), (210), ...

What happens when we consider simple cubic lattice with a

two point basis as bcc lattice (with one point basis)?
 Reciprocal lattice vector and direct lattice planes
Denote parallel planes by {hkl}, and their separation by d hkl .
Show that (i) the reciprocal lattice vector K is perpendicular to {hkl}
(ii) it is the shortest reciprocal lattice vector.
Consider {hkl} planes with
unit vector n perpendicular to it

Construct K hkl =2  / d hkl  n n

The plane wave ei K⋅r is constant K
on {hkl} planes. The planes include (hkl)
all R and r=0. Hence,

ei K⋅R =1

K is a vector in the reciprocal

lattice to the direct lattice R
n

Reciprocal lattice vector and direct lattice planes
(ii) Show that K is the shortest reciprocal lattice vector.
2
Let K' < K, then d hkl
K'
i K '⋅r
The plane wave e will not be a constant on {hkl} planes.
Since the planes include all R and r=0 , we get

i K '⋅R
e ≠1

Therefore, K' is not a reciprocal space lattice vector

 Scattering from crystals: Bragg's law
k k'
The path length APB is the path
difference between the two reflected
O rays,
 

A B d hkl Path di®erence = 2dhkl sin µ

P
For constructive interference, we must have

2dhkl sin µ = n¸ Bragg's law

Bragg's law can also be written as,

µ ¶
dhkl
2 sin µ = ¸
n
 Equivalence of Laue's condition and Bragg's law
k k'
k'  k=G hkl
O
 
2 k ∣ k∣=2 k sin
A B d hkl 4
k = sin 
P 

A reciprocal lattice vector is G hkl =h b1k b2l b3 ,

with ∣Ghkl∣= 2 , using Laue's condition we get
dhkl
4 2
sin =
 d hkl

or, 2 d hkl sin = Bragg's law

 Crystal Structure Determination: Experimental
Techniques
There are primarily three experimental approaches for determining
the structure of crystals.
1. The Laue method (transmission or back-reflection)
2. The rotating crystal method
3. The powder method

In all the three methods, we essentially measure two quantities

(i) The scattering angle 2µ between the diffracted and the incident
beams
(ii) The diffracted intensity I.

We provide a sketch of the three methods used in the crystal

structure determination in the following.
 Crystal Structure Determination: The Laue Method
Features:
(i) Schematic diagrams for the Laue method are shown below.
(ii) In the transmission Laue method, the photographic plate (or the
detector) is placed behind the crystal (solid piece) as shown in (a).
(iii) However, in back-reflection Laue method the photographic plate
is placed between the incident beam and the crystal as shown
in (b).
(iv) Incident X-ray is white.

(a) Transmission and (b) back-reflection Laue method

Crystal Structure Determination: The Laue Method

(a) (b)

(a) Transmission and (b) back-reflection Laue method

Crystal Structure Determination: The Laue Method

(a) Transmission and (b) back-reflection Laue patterns of

an aluminum crystal (cubic)
 Crystal Structure Determination: The Rotating
Crystal Method
Features:
(i) A crystal mounted on a spindle which can be rotated.
(ii) Incident X-ray is monochromatic.
(iii) Photographic plate inside a cylinder.
(iv) Diffraction spots on the plate result whenever Bragg's law is
satisfied during the rotation of the crystal.

Experimental arrangement for the rotating-crystal method

 Crystal Structure Determination: The Rotating
Crystal Method

Rotating crystal pattern of a quartz crystal (hexagonal) rotated

about its c axis.
 Crystal Structure Determination: The Powder
Features: Method
(i) A polycrystalline or powder sample.
(ii) Incident X-ray is monochromatic.
(iii) Photographic plate is cylindrical surrounding the sample.
(iv) Due to symmetry along the incident beam direction, the
scattering angle sweeps a cone.

Debye-Scherrer powder method: (a) relation of film to specimen

and incident beam; (b) appearance of film when laid out flat.
 Crystal Structure Determination: The Powder
Method

Debye-Scherrer powder patterns of (a) copper (FCC), (b) tungsten

(BCC), and (c) zinc (HCP).
X-ray Diffractometer
Crystal Structure Determination from Experimental
Data

A sample diffraction pattern.

Crystal Structure Determination: Bragg's Law and
Miller Indices
For cubic lattices, we have
a
dhkl = 2 2 2 1/2
h k l 
Using Bragg's law

=2 dhkl sin 

Squaring and substituting for d hkl
2 2
2 4 a sin  sin 2 
 = 2 2 2
h k l
2
2  2 2 2 h2  k 2  l 2
sin = 2 h k l 
4a
Crystal Structure Determination: Allowed Reflections

Allowed reflections for cubic lattices

• Primitive h2 + k2 + l2 = 1,2,3,4,5,6,8,9,10,11,12,13,14,16…
• Body-centered h2 + k2 + l2 = 2,4,6,8,10,12,14,16…
• Face-centered h2 + k2 + l2 = 3,4,8,11,12,16,19,20,24,27,32…
Crystal Structure Determination from Experimental
Data of Intensity vs. Scattering Angle
Table of sin2 µ and h2 + k 2 + l2 for SC, BCC and FCC lattices.

h2 + ::: SC h2 + ::: FCC h2 + ::: BCC peak 2µ sin2 µ

1 100 3 111 2 110 1 38.43 0.1083
2 110 4 200 4 200 2 44.67 0.1444
3 111 8 220 6 211 3 65.02 0.2888
4 200 11 311 8 220 4 78.13 0.3972
5 210 12 222 10 310 5 82.33 0.4333
6 211 16 400 12 222 6 98.93 0.5776
8 220 19 331 14 321 7 111.83 0.6859
9 220 20 420 16 400 8 116.36 0.7220
Crystal Structure Determination from Experimental
Data
Plot of sin2 µ vs. h2 + k2 + l2
 X-ray, electron and neutron diffraction:
Crystal structure determination
Summary
I. Scattering of x-rays from atoms leads to diffraction.
II. The intensity of the diffracted beam is a maximum
whenever,
 k=G hkl Laue' condition

2dhkl sin µ = n¸ Bragg's law

III. By plotting sin2 µ vs: (h2 + k2 + l2) one can determine

the lattice constant.