02 Basic-Xrd
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sayyadmannan02 Basic-Xrd
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sayyadmannanOutline of the day
Introduction Basic X-ray diffraction
Powders, thin films, single crystals
Small-angle X-ray scattering X-ray absorption spectroscopy
Atomic structure Electronic structure (Ben Ruck)
Advanced X-ray diffraction
Anomalous diffraction Total X-ray scattering
Designing experiments
In situ measurements
Basic X-ray Diffraction
Peak positions Peak intensities Experiment setup Different types of samples
Single crystals Powders Thin films
Information that can be obtained
Phase analysis Crystallite size Full pattern analysis Preferred orientation
Properties of light
Wavelength = 1/frequency
Visible Colour
X-rays Energy
Amplitude = intensity Particle nature: photon
Two slit experiment
m=2 m=1 d m=0 m= -1 m= -2 dsin=m
Diffraction grating
m=2 m=1 m=0 m= -1 m= -2 dsin=m
A grating made of atoms
For constructive interference, reflected light must be in phase Path difference (2dsin) is a multiple of the wavelength
Braggs Law: n = 2dsin
The unit cell
c b a
= angle between b and c = angle between a and c = angle between a and b
Bravais lattices
Examples
Cubic Hexagonal Orthorhombic Triclinic
Diamond
WC YBCO
WO3 (distorted perovskite)
fcc
Graphite
NaCl Wurtzite
Supercells
lattice distortions ordering
atoms vacancies
Diffracting planes in a crystal
Peak positions
Peak position:
d = h+k+l a d = n/2sin
Diffraction intensity
Geometrical Electron scattering power
Structure factor Symmetry
Sample absorbance X-ray polarisation factor
X-ray diffraction experiment setup
Detector
Source Sample
Different sources
IRL laboratory instrument
Australian Synchrotron
Photon flux ratio 1:1,000,000
Advantages of using a synchrotron source for X-ray diffraction
Increased flux
Smaller samples Weakly scattering samples
Poorly crystalline, low Z
Faster measurement
Real-time experiments High throughput
Lower divergence
Better resolution
Question: Which would be suitable for X-ray diffraction: bend magnet, wiggler, or undulator?
Instrument resolution
Different detectors
Point detector
high resolution post-sample collimation: grazing incidence $ slow
Strip detector
collect entire pattern at once fast readout $$ no post-sample collimation
Area detector
collect entire pattern at once fast, direct observation of texture $$$ limited resolution no post-sample collimation
Different types of samples: single crystal
One large crystallite Diffraction condition is met at points in 3D reciprocal space Measure using 2D detector, rotate sample
Different types of samples: powder
Many small crystallites, randomly oriented Diffraction condition is met at spheres in 3D reciprocal space - isotropic Measure in one direction (point or strip detector ok)
Different types of samples: thin film
May be oriented out of plane (isotropic in plane) or epitaxial Normally use grazing incidence to reduce substrate diffraction
What can we find out?
Phases
Composition, ratio
Peak positions: lattice parameters Peak width: crystallite size, strain Full pattern analysis
Accurate lattice parameters, atomic positions
Texture (preferential orientation)
Direction and degree of texture
1. Phase analysis
2. Full pattern analysis
Using standard packages (e.g. GSAS, TOPAS) Obtain accurate lattice parameters, crystallite size, strain, atomic positions (Rietveld refinement)
Case study: Al-doped ZnO
T. Kemmitt et al., J. Phys. Chem. C (2011) DOI: 10.1021/jp204283k
Temperature/time series
Temperature/time series results
3. Peak width: crystallite size, deformations
Peaks are broadened by crystal defects: finite size, deformations Scherrer equation: Crystallite size = 0.9 . FWcos
Case study: Au nanoparticle coalescence
t=0
t = 15 min
t = 30 min
Observe: Peaks become sharper grain growth Peaks move apart release of strain (fault density decreases) Peak area constant no melting, transformation
B. Ingham et al., Chem. Mater. (2011) DOI: 10.1021/cm200354d
Analysis
For fcc metals, For the (111) peak, For the (200) peak,
(2 200 2111 ) =
1 Deff (111) 1 Deff ( 200) = =
90 3 tan 200 tan 111 + 4 2 2
1 3 (1.5 + ) + D 16 a 1 (1.5 + ) + D a
B. E. Warren, X-ray Diffraction, Dover Publishers (1969)
Therefore the deformation fault density , the twin fault density , and the true crystallite size D can be obtained by comparing the peak separation and peak widths together. A B C B C A
Deformation fault
A B C B A
Twin fault
Results
Combine with SAXS to compare the difference between particle size and crystallite size vs. time
1. Initial aggregation
Time (not to scale)
2. Final aggregation
3. Grain growth B. Ingham et al., Chem. Mater. (2011) DOI: 10.1021/cm200354d
4. Texture (preferential orientation)
Epitaxial
Fibre texture
Top view
Diffraction
Different XRD geometries
Q k k Q
Q k
k Q
Different XRD geometries
ZnO thin film with fibre texture
Q k k
Q k
Case study: ZnO electrochemical deposition
Electrochemical cell
Raw data
Au 111 ZnO 002 ZnO 101 ZnO 100
002 101
100
B. Ingham et al., J. Phys. Chem. C 112 (2008) 14863
Data reduction
102 102 Au 200 Au 111 002 110 101 101 002 101 110
Au 200
r
100
B. Ingham et al., J. Phys. Chem. C 112 (2008) 14863
Data analysis
ZnO (101)
102
102
101 110
002
101 110
B. Ingham et al., J. Phys. Chem. C 112 (2008) 14863
Time series results
5 mM ZnCl2, 0.1 M KCl electrolyte, -0.5V (SHE)
B. Ingham et al., J. Phys. Chem. C 112 (2008) 14863
Outline of the day
Introduction Basic X-ray diffraction
Powders, thin films, single crystals
Small-angle X-ray scattering X-ray absorption spectroscopy
Atomic structure Electronic structure (Ben Ruck)
Advanced X-ray diffraction
Anomalous diffraction Total X-ray scattering
Designing experiments
In situ measurements
