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Rietveld Refinement
Nicola Dbelin
RMS Foundation, Bettlach, Switzerland
1000
Generation of X-rays
Diffraction at crystal structures
800
200
0
10 20 30 40 50 60
2
3
Rietveld Refinement
- Phase quantities
- Crystallite sizes / shapes No phase identification!
- Atomic coordinates / Bond lengths Identify your phases first
(unknown phase no Rietveld refinement)
- Micro-strain in crystal lattice
- Texture effects No structure solution
(just structure refinement)
- Substitutions / Vacancies
Needs excellent data quality!
4
Rietveld Refinement
4000 4000
3000 3000
Intensity [counts]
Intensity [counts]
2000 2000
1000 1000
0 0
10 20 30 40 50 60 10 20 30 40 50 60
Diffraction Angle [2] Diffraction Angle [2]
5
Rietveld Refinement
5000
Beginning of the refinement: Measured Pattern (Iobs)
Calculated Pattern (Icalc)
- Phase was4000
identified correctly (peaks Difference (Iobs-Icalc)
2000
- Peak positions slightly shifted
- Intensities
1000
-1000
10 20 30 40 50 60
Diffraction Angle [2theta]
6
Rietveld Refinement
5000
After the refinement: Measured Pattern (Iobs)
Calculated Pattern (Icalc)
Difference (Iobs-Icalc)
- Straight difference curve (only noise)
4000
3000
Intensity [cts]
2000
1000
10 20 30 40 50 60
Diffraction Angle [2theta]
7
Modelling the Peak Profile
12000
CuK Satellites
Intensity
10000 (= CuK3)
8000
Absorption Edge
CuK
6000
4000
0
27 28 29 30 31 32
Diffraction Angle (2)
8
Modelling the Peak Profile
9
Pseudo-Voigt Curves
n = 0.25 = 0.5
= 0.25
n = 0.5
n = 0.75
n = 1.0
10
Pseudo-Voigt Curves
K1
Fitting n, to peaks
of a reference material
11
Pseudo-Voigt: Problems
10000
8000
Pseudo-Voigt curves
4000 are symmetric.
Asymmetry
2000
0
29.8 30.0 30.2 30.4 30.6 30.8 31.0
Diffraction Angle [2]
12
Alternative Pseudo-Voigt Functions
Alternatives to PV function:
- Pearson VII FWHM of all these functions
must be fitted to peaks
- Thompson-Cox-Hastings PV of a reference material.
- Split PV
- PV with axial divergence Common reference materials
(Finger-Cox-Jephcoat PV) do not have peaks < 20 2
10000 0.30
0.25
8000
Intensity [cts]
0.20
FWHM [2]
6000
0.15
4000
0.10
2000
0.05
0 0.00
0 20 40 60 80 100 120 140
13
Fundamental Parameters Approach FPA
www.bruker.com
Tube Device Configuration Sample
14
Fundamental Parameters Approach
www.bruker.com
15
Fundamental Parameters Approach
16
Fundamental Parameters Approach
FPA needs:
- Very detailed and complete description of
the instrument configuration
- Very well aligned instrument
17
Fundamental Parameters Approach
http://www.bgmn.de
18
Fundamental Parameters Approach
If done properly:
Intensity [a.u.]
21.0 21.2 21.4 21.6 21.8 63.0 63.2 63.4 63.6 120 121 122
2 2 2
19
Fundamental Parameters Approach
Good news:
We created and verified configurations for all
instruments involved in the course!
20
Summary: Rietveld Basics
21
Rietveld Software Packages
1) http://www.ccp14.ac.uk/solution/rietveld_software/index.html
22
BGMN
BGMN:
- Fundamental Parameters Approach
- Open source (GPL v2 since mid 2013, not officially announced yet)
- Device independent
- Very robust automatic refinement strategy
- Good usability (at least better than most other academic programs)
- Slightly less steep learning curve
- Powerful scripting language
- Multi-Platform
- Multi-threaded
23
Graphical User Interfaces for BGMN
24
Graphical User Interfaces for BGMN
- Open source
- Multi-Platform
- Device database
- Structure database
- Batch processing
- File conversion
-
25
Example Refinement
1.
3.
2.
26
Example Refinement
2.
1.
3.
4.
5.
27
Example Refinement
Start Refinement
28
Example Refinement
1.
3.
2.
29
Example Refinement
Good fit
Summary
30
Summary: BGMN and Profex
31
Refinement Strategies
5000
Measured Pattern (Iobs)
Calculated Pattern (Icalc)
Difference (Iobs-Icalc)
4000
3000
Relation
Mismatch Structural Feature
Intensity [cts]
2000
1000
-1000
10 20 30 40 50 60
Diffraction Angle [2theta]
32
Refinement Strategies
33
Refinement Strategies
34
Refinement Strategies
- Preferred orientation
- Graininess
- Atomic species
- Atomic coordinates
- Site occupancies
- Thermal displacement
parameters
35
Refinement Strategies
- Crystallite size
- Micro-strain in crystal structure
36
Summary: Refinement Strategy
37