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
