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Chapter 3: Crystal Structures: X-Ray Diffraction (XRD)

X-ray diffraction is used to determine crystal structures by analyzing the diffraction patterns produced when X-rays interact with a crystal's periodic lattice. Wilhelm Röntgen discovered X-rays in 1895. Max von Laue realized in 1912 that crystals would produce diffraction patterns from X-rays due to their regularly spaced atoms, earning him a Nobel Prize. William and Lawrence Bragg developed a simple equation in 1913 relating the diffraction pattern angles to a crystal's lattice spacing, called Bragg's law. Bragg's law is used to determine crystal structures from their unique X-ray diffraction patterns.

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49 views

Chapter 3: Crystal Structures: X-Ray Diffraction (XRD)

X-ray diffraction is used to determine crystal structures by analyzing the diffraction patterns produced when X-rays interact with a crystal's periodic lattice. Wilhelm Röntgen discovered X-rays in 1895. Max von Laue realized in 1912 that crystals would produce diffraction patterns from X-rays due to their regularly spaced atoms, earning him a Nobel Prize. William and Lawrence Bragg developed a simple equation in 1913 relating the diffraction pattern angles to a crystal's lattice spacing, called Bragg's law. Bragg's law is used to determine crystal structures from their unique X-ray diffraction patterns.

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CHAPTER 3: CRYSTAL STRUCTURES

X-Ray Diffraction (XRD)


ISSUES TO ADDRESS...
Historical retrospective

Henry Bragg Equation


XRD-analysis
How to read XRD patterns?
Exclusions
What questions can be answered by XRD method?

Scale of Structure Organization

Crystal Structure

Practical questions to address:


How to define what crystal structure do we have?
Or in another words: what phases do we have?
Do we have defects or strain in our structure?

From art
to science
Materials science became a real science
due to the development of modern
analysis and imaging techniques.
Modern analysis and imaging techniques
become possible due to developments in
the materials science

Nature of light
Newton: particles (corpuscles)
Huygens: waves
Thomas Young double
slit experiment (1801)
Path difference phase difference
Light consists of waves !
Wave-particle duality

S1

S2

Schematic diagram of Youngs double slit experiment.


Slits S1 and S2 behave as coherent source of light waves
that produce interference pattern on the viewing screen
See additional file Interference of Light Waves on my website

Wilhelm Conrad Rntgen


Discovered the Rntgen rays in
1895.Named these X=rays.

Invisible
rays

X-radiation (composed of X-rays) is a form of electromagnetic radiation.


Most X-rays have a wavelength in the range of 0.01 to 10 nm, corresponding to frequencies
in the range 30 petahertz to 30 exahertz (31016 Hz to 31019 Hz) and energies in the range 100 eV to 100 kEV.

Radiation went straight through a closed,


black carton, hitting a fluorescent screen.

Nobel prize
1901

Max von Laue

The periodicity and interatomic spacing


of crystals had been deduced earlier (e.g.
Auguste Bravais).
von Laue realized that if X-rays were
waves with short wavelength,
interference phenomena should be
observed like in Youngs double slit
experiment.
Experiment in 1912, Nobel Prize in 1914

Sir William Henry Bragg:

Braggs law

William Henry and William Lawrence Bragg


(father and son) found a simple interpretation
of von Laues experiment.
They assume that each crystal plane reflects
radiation as a mirror and analyze this situation for
cases of constructive and destructive interference.

Noble
prize
1915!

2d sin n
Conditions for reflection:
The most important thing in science is not so much to obtain
new facts as to discover new ways of thinking about them.

Derivation of Braggs law


sin( )

x
d hkl

x d hkl sin( )

Path difference = 2x => phase shift


Constructive interference if =n
This gives the criterion for constructive interference:

2d hkl sin( ) n
Braggs law tells you at which angle B to expect maximum
diffracted intensity for a particular family of crystal planes.
For large crystals, all other angles give zero intensity.

dhkl

Conclusions:
DIFFRACTION AND THE BRAGG EQUATION
Max von Laue was the first to
suggest that crystals might
diffract X-rays and he also
provided the first explanation
for the diffraction observed.
However, it is the explanation
provided by Bragg that is simpler
and more popular.
In the Bragg view crystal
planes act a mirrors.
Constructive interference
is observed when the path
difference between the two
reflected beams in (a) = n.
The path difference in (a) is
2my. Since my/d = sin
2my = 2dsin n where d is
the interplanar spacing.

incident
beam

reflected
beam
B

o
x
oo

(1,0,0)
m

n
o

2d (1,0,0) sin (a)


incident
beam

UNIT
CELL

This is a first order reflection

reflected
beam
B

o
x
oo
d

(2,0,0)

n
o

o
y

UNIT
CELL

2d (1,0,0) sin 2(b)

This is a second order reflection

Fig. 11

Typical View of X-ray Diffractometer

The powder diffractometers typically use


the Bragg-Brentano geometry
Detector
X-ray
tube

The incident angle, w, is defined between the X-ray source and the sample.
The diffracted angle, 2, is defined between the incident beam and the detector angle.
The incident angle w is always of the detector angle 2 .
In a :2 instrument (e.g. Rigaku RU300), the tube is fixed, the sample rotates at /min
and the detector rotates at 2 /min.
In a : instrument (e.g. PANalytical XPert Pro), the sample is fixed and the tube rotates
at a rate - /min and the detector rotates at a rate of /min.

A single crystal specimen in a Bragg-Brentano diffractometer


would produce only one family of peaks in the diffraction
pattern.

At 20.6 2, Braggs law


fulfilled for the (100) planes,
producing a diffraction peak.

The (110) planes would diffract at 29.3


2; however, they are not properly
aligned to produce a diffraction peak
(the perpendicular to those planes does
not bisect the incident and diffracted
beams). Only background is observed.

The (200) planes are parallel to the (100)


planes. Therefore, they also diffract for this
crystal. Since d200 is d100, they appear at
42 2.

A polycrystalline sample should contain thousands of


crystallites. Therefore, all possible diffraction peaks should be
observed.

For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).
Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of
crystallites, not just one or two.

Example: Diffraction Patterns


Each peak represents the solution to Braggs law for known radiation
wavelength ( = 0.154nm)
The unique relationship between such patterns and crystal structures
provide a powerful tool for identification of the phase composition of
powders and polycrystalline materials.

Structure Factor
The general expression for :

F fn e2 i(hun kvn lwn )


n1

Now we apply this to various crystals. First, consider examples of crystals with a basis group of just one
atom per lattice point, with atomic scattering factor f. The results are valid for any crystal system.

Primitive Cells
This is really simple! N = 1, so

F fn e

2 i(hun kvn lwn )

fe

2 i(hukvlw)

n1

Define the position of the cell so that our atom is at uvw = 000; then (hu+kv+lw) = 0,
and we get just
2 i(0)

F fe

so

F f

Basis and Bravais Structure Factor Terms


Np

F e

2 igrn

n1

Nb

2 igrm
f
e
FBR FBA
m
m1

The following simple table giving the integer values of FBR for the different types of centering
translations. Keep in mind that these are valid for any crystal system.
Centering type

M issing Reflections
(FBR = 0)

Possible Reflections
(FBR 0)

P (primitive)

None

All

Bravais Term FBR for


possible reflections
1

I (body-centered)

(h + k + l) odd

(h + k + l) even

A (base-centered on A
face)
B (base-centered on B
face)
C (base-centered on C
face)
F (face-centered)

(k + l) odd

(k + l) even

(h + l) odd

(h + l) even

(h + k) odd

(h + k) even

hkl mixed

hkl unmixed

Summary

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