Methods of Analysis
References
Much of my material was drawn from the following
literature and web references
Instrumental Broadening
Extended Defects
Stacking Faults
Antiphase Boundaries
Lattice Strain (microstrain)
FWHM
0.12
0.1
0.08
0.06
Bragg Brentano
0.04
0.02
Debye-Scherrer
0
0
20
40
60
80
100
120
140
2-Theta
BET
Light (Laser) Scattering
Electron Microscopy (SEM)
Extended Defects
Lorentzian = (/2)
Gaussian = {/(4 ln2)}1/2
Voigt, Pseudo-Voigt See Delhez et al., in The Rietveld
Size Broadening
Dv = K/{ cos }
Strain Broadening
Lorentzian
obs = size + strain + inst
{obs inst} = size + strain
Gaussian
2obs = 2size + 2strain + 2inst
{2obs 2inst} = 2size + 2strain
Voigt, Pseudo-Voigt
Generally it is necessary to first deconvolute into
gaussian and lorentzian fractions before subtracting out
the instrumental effects.
Williamson-Hall Analysis
Simplified Integral Breadth Methods
Williamson-Hall Plot
1.8E-03
1.6E-03
odd-odd-odd
Reflections
<D>v = 88(8) nm
= 0.19(4)%
bcos(q) [radians]
1.4E-03
1.2E-03
1.0E-03
8.0E-04
even-even-even
Reflections
<D>v = 282(45) nm
= 0.24(2)%
6.0E-04
4.0E-04
2.0E-04
0.0E+00
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
sin(q)
A Williamson-Hall plot for Pb2ScTaO6. The size extracted from the eveneven-even reflections gives the volume weighted crystallite size, while
the size extracted from the odd-odd-odd reflections gives the volume
weighted size of the regions over which the Sc and Ta atoms are well
ordered. For more details see P.M. Woodward & K.Z. Baba Kishi, J. Appl.
Cryst. In press (2002).
Lorentzian
TCH Function
L = X/(cos) + Y tan
W-H Analysis
Dv = 36000 /{2 X}
str = 2 {Y-Yinst}/144000
Gaussian
TCH Function
Dv = 18000 /sqrt{23P}
str = sqrt{23(U-Uinst)}/72000
Fourier Methods
The most accurate way of extracting size and strain information is
to analyze the entire shape of several reflections in the pattern
(ideally higher order reflections of the same type I.e. 100, 200,
300, etc. or 111, 222, 333, etc.), by the method developed by
Warren and Averbach [J. Appl. Phys. 21, 596 (1950).] This is
done using the following steps:
Fit each reflection of interest with a Fourier series.
Repeat this procedure for a pattern of a sample which gives
no broadening, in order to determine the instrumental
contribution to broadening.
Use these results to deconvolute the sample broadening
from the instrumental broadening, via a Stokes Fourier
deconvolution.
Extract information regarding the size distribution and strain
profile by analyzing the theta dependence of the cosine
Fourier coefficients (which describe the symmetric
broadening)
Conclusions
Fourier Methods are the most general method of extracting sizestrain information but they are susceptible to error due to peak
overlap. This limits their use for crystal structures of moderate
and higher complexity.