TEQIP WORKSHOP ON HIGH RESOLUTION X-RAY

AND ELECTRON DIFFRACTION, FEB 01, 2016, IIT-K.

Introduction to x-ray diffraction

Peak Positions and Intensities

Rajesh Prasad
Department of Applied Mechanics
Indian Institute of Technology
New Delhi 110016
rajesh@am.iitd.ac.in
 Question 1:
Why crystal have
regular external
shapes?
Postulate of Kepler, Hooke et al.:
Because they have regular arrangement of
“building blocks” (“atoms” in modern
language)
 1895
Wilhelm Röntgen
Discovered x-
rays
First Nobel
Prize in
physics: 1901
 First x-ray picture
November 1895

Hand of Roentgen’s wife

 Question2:
Are x-rays waves
or particles?
X stands for the unknown
 Laue’s Postulate
If crystals are periodic arrangement
of atoms
And

If x-rays are waves

Then

Crystals should act as a 3D

diffraction grating for x-rays
Two GREAT results from a single
experiment:

1.  X-rays are waves

2.
Crystals are periodic arrangement
of atoms

One of the greatest scientific

discoveries of twentieth century
 X-Ray
Diffraction = Peak
Positions +
Peak
Intensities

Crystal
Structure = Lattice + Motif:
Atom
Positions
 X-Ray Diffraction

Sample
Incident Beam Transmitted Beam

Diffracted
Beam
X-Ray Diffraction
Sample ≡ Bragg Reflection

Incident Beam Transmitted

Beam

Braggs Law (Part 1): For every diffracted

beam there exists a set of crystal lattice
planes such that the diffracted beam
appears to be specularly reflected from this
set of planes.
 X-Ray Diffraction

Braggs’ recipe for Nobel prize?

Call the diffraction a reflection!!!

“The important thing in science is not so much to obtain new

facts as to discover new ways of thinking about them”.

W.L. Bragg
 A father-son team that
shared a Nobel Prize
Nobel Prize (1915)

William Lawrence Bragg William Henry Bragg

(1890–1971) (1862–1942
X-Ray Diffraction
Braggs Law (Part 1): the diffracted beam
appears to be specularly reflected from a set of
crystal lattice planes.
Specular reflection:
i r Angle of incidence
=Angle of reflection
θ θ (both measured from the
plane plane and not from
the normal)
The incident beam, the reflected beam and the
plane normal lie in one plane
X-Ray Diffraction

i r
θ θ
dhkl

Bragg’s law (Part 2):

nλ = 2d hkl sin θ
 i r

θ θ
θ θ
dhkl
P R

Q
Path Difference =PQ+QR= 2d hkl sin θ
i r
θ θ

P R
Q

Path Difference =PQ+QR= 2d hkl sin θ

Constructive inteference

nλ = 2d hkl sin θ
Bragg’s law
Two equivalent ways of stating Bragg’s Law

nλ = 2d hkl sin θ 1st Form

d hkl
⇒λ =2 sin θ
n
a d hkl
d nh,nk ,nl = =
2 2
(nh ) + (nk ) + (nl ) 2 n

⇒ λ = 2d nh nk nl sin θ 2nd Form

Two equivalent ways of stating Bragg’s Law

nλ = 2d hkl sin θ ⇒ λ = 2d nh nk nl sin θ

nth order 1st order
reflection from reflection from
(hkl) plane
≡ (nh nk nl) plane

e.g. a 2nd order reflection from (111)

plane can be described as 1st order
reflection from (222) plane
 X-rays
Characteristic Radiation, Kα
Target Wavelength, Å
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
 Experimental Diffraction
Settings

Laue method Variable λ Fixed θ

Rotating crystal method Fixed λ Variable θ

Powder method Fixed λ Variable θ

 Powder Method
λ  is fixed (Kα radiation)

θ  is variable –
millions of powder particles
randomly oriented in space
rotation of a crystal about all possible axes
 Powder Strong
diffractometer intensity
geometry
Zero
Diffracted Diffracted intensity
beam 2 beam 1 X-ray
detector
2θ1
Incident beam Transmitted
sample

Intensity
beam

i r
θ θ
plane θ
t
2θ1 2θ2 2θ
 Crystal
monochromator

detector

X-ray
tube

X-ray powder diffractometer

The diffraction pattern of austenite
Austenite = fcc Fe
 x
Bcc crystal λ

λ/2

d100 = a z
100 reflection= rays
reflected from
adjacent (100) planes
y
spaced at d100 have a
No 100 reflection for bcc path difference λ
No bcc reflection for h+k+l=odd
 Extinction Rules

Bravais Lattice Allowed Reflections

SC All

BCC (h + k + l) even
h, k and l all odd, or
FCC
h, k and l all even

h, k and l are all odd

Or
DC if all are even then
(h + k + l) divisible by 4
 X-Ray
Diffraction = Peak
Positions +
Peak
Intensities

Crystal
Structure = Lattice + Motif:
Atom
Positions
Intensity of Powder Diffraction Peaks

1. Scattering by an electron
2. Scattering by an atom
(Atomic scattering factor)
3. Scattering by a unit cell (Structure factor)
4. Polarization factor
5. Multiplicity factor
6. Lorentz factor
7. Absorption factor
8. Temperature factor
B.D. Cullity, Elements of X-Ray Diffraction, 2nd.
Edn., Addison Wesley, 1978, Ch. 4.
Intensity of Powder Diffraction Peaks
1. Scattering by an electron
Thompson’s equation

K ! 1+ cos2 2θ $
IP = I0 2 # & (4-2)
r " 2 %

Ip = Intensity of scattered beam at at P

I0 = Intensity of incident beam at O
P K = constant (7.94 x 10–30m2)
R = distance of P from O
2θ 2θ = scattering angle (angle between
O
Location transmitted and scattered beam)
of an
electron ! 1+ cos2 2θ $
Direction of
transmitted beam Polarization factor # &
" 2 %
Unpolarization factor!!
http://www-outreach.phy.cam.ac.uk/
 Polarization Factor
1

0.5

0 90 180

2θ
Intensity of Powder Diffraction Peaks
2. Scattering by an atom (Atomic scattering
factor)
Cu

Cullity Fig. 4-5

Cullity Fig. 4-6

amplitude of the wave scattered by an atom

f =
amplitude of the wave scattered by one electron
 3. Scattering by a unit cell (Structure factor)

Phase difference between waves scattered from

atom at the origin 000
k th atom at a fractional coordinate uiviwi
for waves reflected by (hkl) plane

ϕ k = 2π (huk + kvk + lwk )

Amplitude of this wave Ak = fk

where fk is the atomic scattering factor of the ith atom

In the complex exponential notation this wave is
represented by iϕ k
Ak e
 Summation of all such scattered waves from the
entire unit cell is called the STRUCTURE FACTOR, F

n
F = ∑ Ak e iϕ k

n
F = ∑ fn e 2 π i(huk +kvk +lwk )
1

* 2
Intensity I = FF = F
 Example: Structure factor of a
monatomic bcc unit cell
111
Coordinate of atoms in the unit cell = 000;
222
n
2πi ( hun + kv n + lwn )
F = ∑ f ne
1
1 1 1
2πi ( h + k +l )
2πi ( h 0+ k 0+l 0 )
=fe +fe 2 2 2

[
= f 1+ e πi ( h + k +l )
]
If, h + k + l = even then F =2f
h + k + l = odd then F =0
Intensity of Powder Diffraction Peaks
4. Multiplicity factor

{100}cubic = (100), (010), (001), {111}cubic = (111), ( 1 11), (1 1 1), (11 1 )

( 1 00), (0 1 0), (00 1 ) ( 1 1 1 ), (1 1 1 ), ( 1 1 1 ), ( 1 1 1)

p{100} = 6 p{111} = 8

The ratio of intensities of 100 reflection to the intensity of

111 reflection, other things being equal, is expected to be:

6 3
=
8 4
Intensity of Powder Diffraction Peaks
5. Polarization Factor

1 + cos 2 2θ
P=
2

Due to the fact that incident wave is

unpolarized
Intensity of Powder Diffraction Peaks
6. Lorentz Factor: (A) reflection at non Bragg angles
1
I max ∝

sin θ

1
B ∝

cos θ

1
Integrated intensity(A) ∝
sin 2θ
 Intensity of Powder Diffraction Peaks
4. Lorentz Factor: (B) Fraction of properly oriented crystals

ΔN rΔθ 2π r sin(90 − θ B )
=
N 4π r 2
Δθ cosθ B
=
2

Figure 4-15 of Cullity

Integrated intensity(B) ∝ cos θ

 Intensity of Powder Diffraction Peaks
6. Fraction of diffraction cone recorded

Figure 4-16 of Cullity

Full length of the diffracted line = 2π Rsin 2θ B
1
Integrated intensity(C) ∝
sin 2θ
 Intensity of Powder Diffraction Peaks
6. Lorentz Factor:
Integrated intensity(A)
1
reflection at non Bragg angles
sin 2θ

Fraction of properly oriented crystals

cos θ
1 Fraction of diffraction cone
sin 2θ recorded
Lorentz factor

⎛ 1 ⎞ ⎛ 1 ⎞ cosθ
L = ⎜ ⎟(cosθ )⎜ ⎟ = 2
⎝ sin 2θ ⎠ ⎝ sin 2θ ⎠ sin 2θ
Intensity of Powder Diffraction Peaks

5. Polarization Factor

1 + cos 2 2θ
P=
2
6. Lorentz Factor:
cosθ
L=
sin 2 2θ
Lorentz-Polarization Factor

1 + cos2 2θ ignoring the numerical

LP = constant
sin 2 θ cosθ
Figure 4-17 from Cullity
 7. Absorption Factor A
Absorption in the specimen

Independent of θ:

x x

d d

Low θ: High θ:
Low penetration depth, d High penetration depth, d
Large irradiated area, x Small irradiated area, x

Effective irradiated volume constant and

independent of θ.
Temperature factor
Gist of a Discussion in a Coffee House
in Munich before Laue’s famous
experiment

Atoms are continuously vibrating with random

amplitude

Thus there cannot be any periodicity of

instantaneous positions

Therefore no sharp diffraction

pattern will be observed.

Reference: Kittel, Solid state Physics

 Temperature factor

1. Lattice parameter increase -> Peaks shift to lower θ

2. Intensity of the diffraction lines decrease
3. Intensity of background scattering increases

Rather surprisingly, there is no significant

change in peak width.
Final Intensity expression for Diffractometer

2! 1+ cos2 2θ $ −2 M
I = F p# 2 &e
" sin θ cosθ %