Lesson 4

Rietveld Refinement

Nicola Dbelin
RMS Foundation, Bettlach, Switzerland

October 16 17, 2013, Uppsala, Sweden

Repetition: Powder XRD Patterns

1000

Generation of X-rays
Diffraction at crystal structures
800

Powder samples (Debye rings)

Diffractometers (Types, optical elements)
600
Intensity [counts]

Sample preparation (errors to avoid)

Phase identification
400

200

0
10 20 30 40 50 60

Diffraction Angle [2]

2
3
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
- Atomic coordinates / Bond lengths
- Micro-strain in crystal lattice
- Texture effects
- Substitutions / Vacancies
No phase identification!
Identify your phases first
(unknown phase no Rietveld refinement)
No structure solution
(just structure refinement)
Needs excellent data quality!

4
 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

5
 Rietveld Refinement

5000
Beginning of the refinement: Measured Pattern (Iobs)
Calculated Pattern (Icalc)
- Phase was4000
identified correctly (peaks Difference (Iobs-Icalc)

at the right position)

- But differences
3000 exist:
- Peak width
Intensity [cts]

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

CuK1 & CuK2 duplet

All these signals
20000
are generated
by one d-spacing.
18000
Mathematical
16000
model to describe
the profile is needed.
14000

12000
CuK Satellites
Intensity

10000 (= CuK3)

8000
Absorption Edge
CuK
6000

4000

2000 Remaining Bremsstrahlung

0
27 28 29 30 31 32
Diffraction Angle (2)

8
 Modelling the Peak Profile

Traditional (Rietveld) Approach:

Pseudo Voigt curves for K1, K2 and K

VP(x) = n * L(x) + (1-n) * G(x)

Lorentzian curve Gaussian curve

1
L(x) = G(x) = exp[-ln(2)( x-x 0)2]
1+( x-x 0)2

Lorentzian ( = 1.0) Gaussian ( = 1.0) Pseudo-Voigt (n = 0.5)

9
Pseudo-Voigt Curves

n = 0.0 n = 0.5 = 1.0

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

2 = f() = U tan2() + V tan() + W

Actually fitting n, U, V, W
K2

11
Pseudo-Voigt: Problems

10000

8000

Peaks at low 2 angles

6000 are asymmetric.
Intensity [cts]

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

Diffraction Angle [2]

13
 Fundamental Parameters Approach FPA

Calculate the peak profile from the device configuration

Take into account the contributions 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

14
Fundamental Parameters Approach

www.bruker.com

15
Fundamental Parameters Approach

Calculated Peak Profiles

2=10 2=30 2=80

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

Very good description of the peak profile

19
 Fundamental Parameters Approach

- Some fundamental parameters are not documented

- Complete configuration can be hard to obtain

Good news:
We created and verified configurations for all
instruments involved in the course!

20
Summary: Rietveld Basics

- Calculate XRD pattern from model structure

- Minimize differences between calculated and measured pattern
- Accurate mathematical description of peak profile required:
- Classical Rietveld approach: Fit a peak shape function (PV
or similar) to reference pattern
- Fundamental Parameters Approach: Calculate peak
profile from device configuration

21
Rietveld Software Packages

Academic Software: Commercial Software:

- Fullprof - HighScore+ (PANalytical)
- GSAS - Topas (Bruker)
FPA
- BGMN - Autoquan (GE) Commercial UI
for BGMN

- Maud - PDXL (Rigaku)

- Brass - Jade (MDI)
- many more1) - WinXPOW (Stoe)

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

Visit: http://www.bgmn.de for tutorials and documentation

23
 Graphical User Interfaces for BGMN

BGMNwin (shipped with BGMN software package)

24
 Graphical User Interfaces for BGMN

Profex (developed by Nicola Dbelin)

- 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

- BGMN is the Rietveld kernel

- Fundamental Parameters Approach
- Profex is an editor / graphical user interface to BGMN
- Best-case scenario (example):
- Load scan file
- Specify instrument configuration from internal database
- Load structure files from internal database
- Start refinement
- done

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

Wrong peak positions:

- Unit cell dimensions

- Sample height displacement
- Zero-shift (instrument
misalignment)

33
Refinement Strategies

Wrong absolute intensities:

- Weight fraction (scaling)

34
Refinement Strategies

Wrong relative intensities:

- Preferred orientation
- Graininess
- Atomic species
- Atomic coordinates
- Site occupancies
- Thermal displacement
parameters

35
Refinement Strategies

Wrong peak width:

- Crystallite size
- Micro-strain in crystal structure

36
Summary: Refinement Strategy
Effect in diffraction pattern
Wrong peak positions
Wrong absolute intensities
Wrong relative intensities
Wrong peak width
37
Origin in crystal structure model
Unit cell dimensions
Sample height displacement
Zero-shift
Weight fraction (scaling)
Preferred orientation
Atomic species / Substitutions
Atomic coordinates
Site occupancies
Thermal displacement parameters
Crystallite size
Lattice strain