Lesson 1
Rietveld Refinement
and Profex / BGMN
Nicola Döbelin
RMS Foundation, Bettlach, Switzerland
June 13 – 15, 2018, Bettlach, CH
Diffraction Pattern
1000
Diffraction Angle
800
Absolute Intensity
600
Intensity [counts]
400 Relative Intensity
200 Shape
0
10 20 30 40 50 60
Diffraction Angle [°2]
2
Diffraction Pattern
Diffraction Angle: Relative Intensity:
Phase Identification Crystal Structure Determination
Absolute Intensity: Shape:
Phase Quantification Crystallite Size and Shape, Lattice Strain
3
Phase Identification
«Pattern Features» originate from crystallographic properties
Usually sufficient for identification
Feature Origin
Peak positions - Symmetry of the unit
cell (space group)
- Dimensions of the
1000
unit cell
800 Relative peak intensities - Coordinates of atoms
in unit cell
600
Intensity [counts]
- Species of atoms
400
Absolute peak intensities - Abundance of phase
200 Peak width - Crystallite size
- Stress/Strain in crystal
0
10 20 30 40
Diffraction Angle [°2]
50 60
lattice
4
Search-Match for Phase Identification
5
Rietveld Refinement
For more than just identification:
Rietveld refinement
Extracts much more information from powder XRD data:
- Unit cell dimensions Prof. Hugo Rietveld
- 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!
6
Rietveld Refinement
Known structure Calculate theoretical Compare with
model diffraction pattern measured pattern
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]
Optimize structure model, repeat calculation
Minimize differences between calculated and observed
pattern by least-squares method
7
Rietveld Refinement
5000
Measured Pattern (Iobs)
Calculated Pattern (Icalc)
Difference (Iobs-Icalc)
4000
3000
Intensity [cts]
2000
1000
10 20 30 40 50 60
Diffraction Angle [°2theta]
8
Rietveld Software Packages
Academic Software: Commercial Software:
- Fullprof - HighScore+ (PANalytical)
- GSAS - Topas (Bruker)
- BGMN - Autoquan (GE)
- Maud - PDXL (Rigaku)
- Brass - Jade (MDI)
- … many more1) - WinXPOW (Stoe)
1) http://www.ccp14.ac.uk/solution/rietveld_software/index.html
9
BGMN: Based on Text Files
Geometric Refined
Instrument Data Parameters
(*.geq) (*.lst)
Wavelength Refined
Distribution Pattern
(*.lam) Refinement (*.dia)
Control File Run
BGMN
Diffraction (*.sav) Peak
Pattern Parameters
(*.xy) (*.par)
Structure Refined
Models 1…n Structures
(*.str, *.res, *.fcf, *.pdb…)
(*.str)
10
BGMN
11
Profex: A Graphical User Interface for BGMN
12
Profex: A Graphical User Interface for BGMN
Developer: Nicola Döbelin (private)
License: GPL v2 or later (open source)
Founded in: 2003
Platforms: Windows 7 / 8 / 8.1 / 10
Linux
Mac OS X 10.9 -10.13 (64bit)
Rietveld Backends: BGMN, Fullprof.2k
Website: http://profex.doebelin.org
Current stable version: 3.13.0
13
Profex Key Features
Create and manage refinement projects
Convert raw data files for BGMN
Export results and graphs
Batch refinements
Structure and Instrument
file repositories
+ many more…
14
Fitting Data
Fitting experimental data requires an adequate mathematical model
1 𝑥−𝜇 2 𝑥
− −
𝑓 𝑥 = ∙𝑒 2𝜎 2 𝑓 𝑥 =𝑎∙ 𝑒 𝑡 + 𝑦0
𝜎 2𝜋
15
Fitting Data
𝑥−𝜇1 2
𝐴1 − 2
𝑓 𝑥 = ∙ 𝑒 2𝜎1
𝜎1 2𝜋
𝑥−𝜇2 2
𝐴2 − 2
𝑔 𝑥 = ∙ 𝑒 2𝜎2
𝜎2 2𝜋
𝑥−𝜇3 2
𝐴3 −
2𝜎32
ℎ 𝑥 = ∙𝑒
𝜎3 2𝜋
16
Fitting Data
𝑓 𝑥 𝜎1 , 𝐴1 , 𝜇1 )
𝑔 𝑥 𝜎2 , 𝐴2 , 𝜇2 )
ℎ 𝑥 𝜎3 , 𝐴3 , 𝜇3 )
𝐹 𝑥 = 𝑓 𝑥 + 𝑔 𝑥 + ℎ(𝑥)
17
Fitting Data
𝐹 𝑥 | 𝜎1 , 𝐴1 , 𝜇1 , 𝜎2 , 𝐴2 , 𝜇2 , 𝜎3 , 𝐴3 , 𝜇3
If not all parameters are independent,
(for example constant σ):
𝐹 𝑥 | 𝜎, 𝐴1 , 𝜇1 , 𝐴2 , 𝜇2 , 𝐴3 , 𝜇3
18
Fitting Diffraction Patterns
Fit every single peak to determine:
- Position (diffraction angle 2θ)
- Integrated intensity (area)
- Width
19
Fitting Diffraction Patterns
- Diffraction angle lattice plane spacing d
- Lattice type
- Space group
- Unit cell dimensions
- Intensity Structure factor Fhkl
- Atomic species
- Fractional coordinates
- Site occupancies
- Thermal vibration
- Phase quantity
- Width
- Crystallite size
- Micro-strain
20
Fitting Diffraction Patterns
Mathematical model for peaks
in a XRD pattern needed
21
Fitting Diffraction Patterns
2θ = 11.65° 2θ = 35.15°
22
Modelling the Peak Profile
Two Gaussian functions
11.3 11.4 11.5 11.6 11.7 11.8 11.9 12.0 34.8 34.9 35.0 35.1 35.2 35.3 35.4 35.5
Diffraction Angle [°2] Diffraction Angle [°2]
23
Modelling the Peak Profile
Traditional («Rietveld») Approach:
Pseudo-Voigt curves for Kα1, Kα2 and Kβ
𝑉𝑃 𝑥 = 𝑛 ∙ 𝐿 𝑥 + (1 − 𝑛) ∙ 𝐺(𝑥)
Lorentzian Gaussian
LORENTZ GAUSS PVN05
PVN025
PVN075
PVN0
PVN10
Lorentzian (ω = 1.0) Gaussian (ω = 1.0) Pseudo-Voigt (n = 0.5)
24
Profile functions in FullProf.2k
25
Alternative: Fundamental Parameters Approach (FPA)
Origin of peak shape features: 2θ = 11.65° 2θ = 35.15°
- Wavelength distribution
(radiation spectrum)
- Instrument configuration
FPA: Simulate peak shape based on instrument
geometry and wavelength distribution
26
FPA: Wavelength Contribution
Origin of peak shape features: 2θ = 11.65° 2θ = 35.15°
- Wavelength distribution
(radiation spectrum)
- Instrument configuration
𝐾𝛼1
𝜆
𝐾𝛼2 2𝜃 = 2 ∙ asin
2𝑑
Wavelength
27
FPA: Wavelength Contribution
2θ = 11.65° 2θ = 35.15°
𝜆
2𝜃 = 2 ∙ asin
2𝑑
0.10
Spacing between CuKa1 and CuKa2 [°2theta]
Spacing between CuKa1 and CuKa2 [°2theta]
0.5
0.08
0.4
0.06
0.3
0.04
0.2
0.1 0.02
0.0 0.00
0 20 40 60 80 100 120 5 10 15 20 25 30 35 40
2Theta [°] 2Theta [°]
28
FPA: Instrument Contribution
Origin of peak shape features:
- Wavelength distribution
(radiation spectrum)
- Instrument configuration
Detector window:
29
FPA: Instrument Contribution
0 500 1000 1500 2000 2500
30
FPA: Instrument Contribution
0 500 1000 1500 2000 2500
31
FPA: Sample Contribution
The same crystalline phase, same instrument configuration
Why different peak shape?
Crystallite Size = 560 x 390 nm
Crystallite Size = 45 x 20 nm
32
Fundamental Parameters Approach FPA
Observed peak shape = convolution of:
- Source emission profile (X-ray wavelength distribution from Tube)
- Every optical element in the beam path (position, size, etc.)
- Sample contributions (peak broadening due to crystallite size & strain)
www.bruker.com
Tube Device Configuration Sample
33
Fundamental Parameters Approach
http://www.bgmn.de
34
Visualize Peak Profiles
35
Visualize Peak Profiles
36
