Crystallography

and
Diffraction Techniques
 Characterization of Solids

How to characterize solid:

Diffraction, Microscopy, Spectroscopic techniques

X-ray diffraction, neutron diffraction and electron diffraction

Structure:
1. Single vs. Polycrystalline structure
2. Crystal structure (unit cell, dimensions)
3. Crystal defect (vs. molecular structure)
4. Impurities (concentration and distribution)
5. Surface structure (compositional inhomogeneities)
 Outline

Generation of X-ray
X-ray wavelength
Diffraction of X-ray
Diffraction methods
Qualitative identification of compounds
Scatterings of X-ray
Determination of X-ray Structure
Electron and neutron diffraction
 Generation of X-ray
X-ray are produced when high energy
charged particles (e.g. 30 kV) collide with
matter.
Only ~1% electron can produce x-ray,
the others lost as heat (anode need
efficient cooling)
Incident electron has sufficient
energy to remove 1s electron
The place will be refilled by outer
shell electron, and give X-ray
radiation
Fixed transition energy
 X-ray Wavelength

Fixed transition energy (Copper

White
radiation metal as target):
2p 1s Cu K 1.5418
3p 1s Cu K 1.3922

Moseleys Law
Cut off
= K/(Z-)2
Peak intensity rate of transition
 Monochromatic X-ray Radiation

Absorption of X-rays on passing through materials depends on

the atomic weight of the elements
Be is the best window, while Pb is a good shielding materials
White radiation and unwanted Kb lines can be filtered

How to choose X-ray filter?

 Diffraction of Light

Diffraction of light by an optical grating

AB = asin

Separation of lines should be slightly In phase: AB = , 2, 3,. n

larger than the wavelength of light
n = asin
 Diffraction of X-ray

Crystal with repeating structure Optical grating

Interatomic distance ~2-3, which is slightly larger than the wavelength

of X-ray e.g. Cu K

1D optical grating: n = a sin

3D crystal structure: n = a1 sin1

n = a2 sin2 Laue
equations
n = a3 sin3
 Braggs Law

Regard crystals as built up in layers or planes such that each

acts as a semi-transparent mirror

The angle of reflection is equal to the angle of incidence

X-ray Diffraction Method

1. Radiation: monochromatic or of
variable
2. Sample: single crystal, powder or a
solid piece
3. Detector: radiation counter or
photographic film
 X-ray Diffractometers

Single crystal X-ray diffractometer Powder XRD

 Debye-Scherrer Method
Sample: Powder Detector: Film

S/2R = 4/360

Each set of planes (unique d-spacing) gives its own cone of radiation.
d-spacing can be obtained.
 Focusing of X-rays
Intense X-ray beam improvement in resolution and reduced
exposure time

Theorem of a circle:

Crystal monochromator: Large single crystal, curved

Highly monochromatic radiation

Intense convergent X-ray beam
 Guinier Focusing Camera
The film is place in a cassette which is in the form of a short cylinder
and lies on the circle ABC

primary beam

sample
crystal
monochromator

Film (in the scale of 2):

Intensity : degree of Accurate d-spacing can

blackness are seen be obtained!

Undiffracted beam A
 Powder Diffractometer
1. Geiger counter scans a range of 2 value (10-80 degree) at constant
angular velocity
2. Intensities taken either peak heights or peak area
3. Most intense peak gives a intensity of 100 (rest are scaled according)
4. Internal standard with known d-spacing e.g. KCl
Qualitative Identification of Compounds
1. The existence of crystalline compounds or phases (not
chemical composition)
2. Peak position (d-spacing) and intensity (pattern)
3. Each crystalline phase has a characteristic powder pattern
which can be used as a fingerprint for identification process

Powder Diffraction File (International Centre for Diffraction Data, USA)

 Fingerprint Powder Pattern

What factors determine the powder pattern:

The size and shape of the unit cell

The atomic number and position of the atom in the cell

High symmetry (cubic) structure may have similar pattern

 Scattering of X-ray by Electrons
1. Elastic collision between the electromagnetic
wave and the electron
Coherent, without change of wavelength

Thomson equation:

Ip (1 + cos22)

2. Inelastic collision in that X-ray lose

some of their energy on impact
(Compton scattering)

Incoherent, longer wavelength

X-ray scattered by an atom are the

resultant of the waves scattered by
each electron in the atom
 Scattering of X-ray by a Crystal
Systematic absences
Arises if the lattice type is non-primitive or if elements of space symmetry
are present

Plane (100) no intensity (diffracted beam cancel completely)

Plane (200) strong intensity (all atom lie on the plane)

The diffracted beams must be out of phase and of the same amplitude
Rules for Systematic Absences
Phase Difference
Plane (100)

Phase difference between

A and B =
A and C = 2x

Plane (200)

Phase difference between

A and B = 2
A and C = 2*2x

Plane (h00)
= 2hx

Indices of reflection and fractional

coordinates
Phase Difference in 3D Crystal Structure
= 2 (hx + ky + lz)

For example: -Fe fcc structure

Fractional coordinates:
0,0,0 ,,0 ,0, 0,,

0, (h+k), (h+l), (k+l)

Reflection to be observed when h,k,l all even or all odd

For example: a-Fe bcc structure

0,0,0 , ,

0, (h+k+l)

Reflection to be observed when h+k+l = 2n

 Structure Factor (Fhkl)
Diffracted wave of each atom (j): Fj = fj sin(wt j)

Complex notation: Fj = fj(cosj + isinj)

Summation over the j atoms in the unit cell:

Structure factor: Fhkl = fj(cosj + isinj)

Intensity is obtained from the summation of the individual sine wave

I f j2

Intensity of diffracted beam Ihkl Fhkl 2

= [fj(cosj + isinj)] [fj(cosj + isinj)]

= (fjcosj)2 + (fjsinj)2

The structure factor and intensity of any (hkl) reflection may be calculated from a
knowledge of the atomic coordinates in the unit cell
 Calculation of Structure Factor

For example: CaF2 (fluorite structure)

Ca 0,0,0 , ,0 ,0, 0, ,
F ,, ,, ,, ,,
,, ,, ,, ,,

Fhkl = fj(cosj + isinj)

F202 = 4fCa + 8fF

d-spacing = 1.929 (a = 5.464 )

= 23.6, sin / =0.259, = 1.5418

Scattering factor fCa = 12.65, and fF = 5.8

Calculated structure factor Fcalhkl F202 = 97

 R-factors
Residual factor is used to measure the agreement between the individual,
scaled Fhklcalc and Fhklobs

Fhklobs is obtained from the experimental intensities (Fhklobs = Icorr)

Fobs - Fcalc
R=
Fobs

R should be less than 0.1 and 0.2 if the calculated structure is correct
 Structure Determination
Peak height is proportional
to the number of electrons
possessed by the atom
Difficult to locate light atom
e.g. hydrogen
Intensities of x-ray diffracted beam
Electron density map
Coordination variables
Structure refinement (position and
thermal vibration factors)
Common structure determination methods:
1. The Patterson method
2. Fourier methods
3. Direct methods
 Electron Diffraction
Wavelength is related to velocity, around 0.04 in conventional Electron Microscopy

Interact strongly with matter, intense diffraction pattern can be obtain

from small samples
Secondary diffraction occurs (extra reflections and unreliable intensity)
Unit cell and space group
Surface polarity
Small amount of impurity phases
Neutron Diffraction

Continuous spectrum of
radiation (need crystal
monochromator)
Neutrons that are used for
diffraction have wavelength of the
order 0.5 to 3 (depends on
velocity)
Low intensity, large sample size
Atomic nuclei (vs. extranuclear
electron) are responsible for
scattering

Crystal structure determination

Locate light atoms
Distinguish atoms that have similar X-
ray scattering
 Neutron Diffraction
Neutron (spin = ) posses magnetic dipole moment

Interact with unpaired electrons and diffracted by both atomic nuclei

and unpaired electrons

Magnetic structure analysis

NiO superstructure
MnO structure