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Lesson 5 - Rietveld Refinement
Lesson 5 - Rietveld Refinement
λ 2
different, at 0° 30 Zr(4+)
O(2-)
Zr and Zr4+ are slightly different at 0° 25
fo
the variation with (sin θ)/λ 15
depends on size of atom
10
smaller atoms drop off quicker
5
at higher angles, the difference
between Y3+ and Zr4+ is more readily 0
discerned 0 0.5 1 1.5
(sin θ)/ λ
at higher angles, the difference
between different oxidation states
(eg Zr and Zr4+) is less prominent
TEMPERATURE FACTOR
the efficiency of scattering by an B sin 2 θ
f = f 0 exp −
atom is reduced because the atom λ2
and its electrons are not stationary
40
atom is vibrating about its equilibrium B=0
lattice site 35 B=1
B=10
amount of vibration is quantified by the 30
Debye-Waller temperature factor:
25
B=8π2U2
20
U2 is the mean-square amplitude of
f
the vibration 15
Counts
Counts
4000
2000
1000
1000
0
0
42 44 46 48 50
45.50 46
Position [°2Theta]
Position [°2Theta]
8
PEAK PROFILE FUNCTION (PSEUDO-VOIGT)
𝐹𝐹 Δ𝑇𝑇 = 𝜂𝜂𝜂𝜂 Δ𝑇𝑇, Γ + 1 − 𝜂𝜂 𝐺𝐺(Δ𝑇𝑇, Γ)
2 1
4𝑙𝑙𝑙𝑙𝑙 −4𝑙𝑙𝑙𝑙𝑙(Δ𝑇𝑇)2 𝐿𝐿 Δ𝑇𝑇, 𝛾𝛾𝐿𝐿 = 2
𝐺𝐺(Δ𝑇𝑇, Γ𝐺𝐺 ) = 2 𝑒𝑒𝑒𝑒𝑒𝑒 𝜋𝜋𝛾𝛾𝐿𝐿 2Δ𝑇𝑇
𝜋𝜋Γ𝐺𝐺 Γ𝐺𝐺2 1+
𝛾𝛾𝐿𝐿
180 𝑘𝑘𝜆𝜆 1 180
Γ𝐺𝐺2 = 𝑈𝑈 𝑡𝑡𝑡𝑡𝑡𝑡2 𝜃𝜃 + 𝑉𝑉 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 + 𝑊𝑊 + 𝑃𝑃/𝐶𝐶𝐶𝐶𝐶𝐶 2 𝜃𝜃 𝛾𝛾𝐿𝐿 = + 𝑆𝑆 𝑡𝑡𝑡𝑡𝑡𝑡𝜃𝜃
𝜋𝜋 𝐷𝐷 𝑐𝑐𝑐𝑐𝑐𝑐𝜃𝜃 𝜋𝜋
10
GAUSSIAN AND LORENTZIAN CONTRIBUTIONS
A functions to describe the Gaussian – Lorentzian contributions :
Gaussian
Cauchy (Lorentzian)
Modified Lorentzian (1 &2)
Voigt
Pseudo Voigt
Pseudo Voigt with FJC Asymmetry correction
Split Pseudo Voigt
Pearson VII
SOURCE OF PROFILE BROADENING
Peak Broadening B ( FWHM ) = Bi + Bc + Bs + BSF + ...
Crystallite size In the vicinity of θB the −ve of Bragg’s equation not being
satisfied
Bc
Residual Strain’ arising from dislocations, coherent
Strain
precipitates etc. leading to broadening
Bs
In the vicinity of θB the −ve of Bragg’s equation not being
Stacking fault satisfied
BSF
2. External Standard
Use the same material as the standard (NIST standard: Si, CeO2, LaB6) as
the specimen to be X-rayed but with large grain size and well annealed
PARAMETERS OF A PATTERN SIMULATION
Global parameters affect the entire sample
Background function
Zero Shift
Specimen Displacement
POL (Lorentz polarization factor)
Sample Geometry
selecting the Profile Function
Other parameters are set individually for each phase
scale factor
preferred orientation (March-Dollase function)
unit cell
atomic parameters are for each atom in the phase
position, SOF, thermal parameter
Peak Profile parameters
Cagliotti peak width function parameters U,V, and W
Profile shape parameters
peak asymmetry profile
15
anisotropic broadening function
R - INDICES
1/2 1/2
2
∑ 𝑤𝑤𝑖𝑖 (𝑦𝑦𝑜𝑜,𝑖𝑖 − 𝑦𝑦𝑐𝑐,𝑖𝑖 ) 𝑁𝑁 − 𝑃𝑃
𝑅𝑅𝑤𝑤𝑤𝑤 = 𝑅𝑅𝑒𝑒𝑒𝑒𝑒𝑒 =
∑ 𝑤𝑤𝑖𝑖 (𝑦𝑦𝑜𝑜,𝑖𝑖 )2 ∑ 𝑤𝑤𝑖𝑖 (𝑦𝑦𝑜𝑜,𝑖𝑖 )2
o Rwp factor is the more valuable. Its absolute value does not depend on
the absolute value of intensities, but depends on the background. With
a high background is more easy to reach very low values. Increasing the
number of peaks (sharp peaks) is more difficult to get a good value.
Rwp < 0.1 correspond to an acceptable refinement with a medium
complex phase
Rwp < 0.15 a is good value for complex phase (monoclinic to
triclinic)
Rwp < 0.08 is acceptable for a highly symmetric compound (cubic)
with few peaks
o For high background, better to look at the Rwp background subtracted.
o The Rexp is the minimum Rwp value reachable using a certain number 16
of refineable parameters.
WSS AND GOF (OR SIGMA)
o WSS (Weighted Sum of Squares) is only used for the minimization
routines. Its absolute value depends on the intensities and number of
points.
o GoF (Goodness of Fit) is the ratio between the Rwp and Rexp and
cannot be lower then 1 (unless the weighting scheme is not correctly
valuable: for example in the case of detectors not recording exactly
the number of photons or neutrons).
o A good refinement gives GoF < 2.
o GoF is not a very good index for a noisy pattern because is quite easy
to reach a value near 1.
o For very high intensities and low noise patterns is difficult to reach a
value of 2.
o GoF is sensible to model inaccuracies.
17
LIMIT OF DETECTION
Following the rules of the statistic of Poisson distribution, the absolute and relative standard
deviation σ and σrel of measured number of count N at a 2θ position are given by:
𝜎𝜎 = 𝑁𝑁
𝑁𝑁 1
𝜎𝜎𝑟𝑟𝑟𝑟𝑟𝑟 = =
𝑁𝑁 𝑁𝑁
A usual criterion for the limit of detection (LOD) of a particular reflection, is that
𝑁𝑁𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 > 𝑁𝑁𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 + 3𝜎𝜎𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏
Example: measuring an 𝑁𝑁𝑚𝑚𝑚𝑚𝑚𝑚 of 10,000 counts, the 𝜎𝜎𝑟𝑟𝑟𝑟𝑟𝑟 is 0.01, corresponding to relative
error of 1%, the counting statistic error.
Imagine for a background of 100 counts and a small hump of 120 counts. Clearly this cannot
be classified as reflection because 3𝜎𝜎𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 = 30 is obviously higher than 20. The only
solution is to increase the measurement time to improve the peak to background ratio
WHAT IS PHYSICALLY MEANINGFUL?
Wel (1975)
19
Scherrer (1918) noted that the line profile width is inversely proportional
to crystallite size, Laue (1926) realized that using the integral breadth (IB)
gives approximate independent effect of the distribution in size and shape,
Stokes & Wilson (1944) introduce strain broadening e0 represents the
"mean"deviation from the undistorted state, Bertaut (1949) proposed an
interpretation to consider size broadening without making assumptions on
crystallite size and shape distributions. Jenkins & Snyder (1996) discussed
about Bragg extinction; crystallites larger than 2mm typically have a
sufficient number of planes to display its Darwin width. Balzar (1999)
modeling of microstructure effects; crystallite size and microstrain
comprise Lorentzian and Gaussian component convolutions varying in
2theta, Scardi & Leoni (2001, 2004), Scardi et al. (2010) the WPPM
approach for microstructure analysis. And there's a lot more.
The interpretation of size values is also difficult, as different methods may
report different quantities such as volume weighted mean, area weighted
mean and number weighted mean.
For parallel planes of atoms, with a space d between the planes and for a
given wavelength λ, Bragg’s law defines the (Bragg) angle for constructive
interference. As discussed more in detail by Jenkins & Snyder (1996), if the
incident beam angle theta is away from the Bragg angle so that the phase
shift becomes 1.1λ between adjacent planes, then the phase shift
originating of the 6th plane down the surface will be 5.5 λ resulting in
destructive interference (so-called Bragg extinction). The same is true for
the 2nd and 7th planes etc., thus no net scattering will occur. If theta is set
closer to the Bragg angle so that the phase shift becomes 1.0001 λ between
adjacent planes, then the scattering of the 1st plane will be cancelled by
scattering of
the 5.001th plane, with a phase shift of 5000.5 λ . If the crystal is too small,
then planes needed to cancel such phase shifts are not present; this is the
source of size broadening. As a result intensities at lower and higher angles
than the Bragg angle are observed. Crystallites larger than 2mm typically
have a sufficient number of planes to allow the diffraction peak to display its
inherent Darwin width.