Basics of Rietveld Refinement

Scott A Speakman
13-4009A
x3-6887
speakman@mit.edu
Uses of the Rietveld Method

The Rietveld method refines user-selected parameters to

minimize the difference between an experimental pattern
(observed data) and a model based on the hypothesized crystal
structure and instrumental parameters (calculated pattern)
can refine information about a single crystal structure
confirm/disprove a hypothetical crystal structure
refine lattice parameters
refine atomic positions, fractional occupancy, and thermal parameter
refine information about a single sample
preferred orientation
refine information about a multiphase sample
determine the relative amounts of each phase

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Requirements of Rietveld Method

High quality experimental diffraction pattern

a structure model that makes physical and chemical sense
suitable peak and background functions

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Obtaining High Quality Data

issues to consider
aligned and calibrated instrument
beam overflow problems
thin specimen error
good counting statistics
appropriate step size
sample transparency
surface roughness
preferred orientation
particle size
go to XRD Basics pg 102

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Describing the Crystal Structure

space group
lattice parameters
atomic positions
atomic site occupancies
atomic thermal parameters
isotropic or anisotropic

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The Crystal Structure of LaB6

LaB6
Space Group Pm-3m (221)
Lattice Parameter a=4.1527 A

Atom Wyckoff x y z B occ.

Site
La 1a 0 0 0 0.00157 1

B 6f 0.1993 0.5 0.5 0.0027 1

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Where to get crystal structure information
check if the structure is already solved
websites
Inorganic Crystal Structure Database (ICSD) http://icsd.ill.fr/icsd/index.html
4% is available for free online as a demo
Crystallography Open Database http://www.crystallography.net/
Mincryst http://database.iem.ac.ru/mincryst/index.php
American Mineralogist
http://www.minsocam.org/MSA/Crystal_Database.html
WebMineral http://www.webmineral.com/
databases
PDF4 from the ICDD
Linus Pauling File from ASM International
Cambridge Structure Database
literature
use the PDF to search ICSD listings and follow the references
look for similar, hopefully isostructural, materials
index the cell, and then try direct methods or ab-initio solutions
beyond the scope of todays class

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Instrumental Parameters

background
peak profile parameters
cagliotti parameters u, v, w
pseudo-voigt or other profile parameters
asymmetry correction
anisotropic broadening
error correcting parameters
zero shift
specimen displacement
absorption
extinction
roughness
porosity

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How many parameters can we refine?

Each diffraction peak acts as an observation

theoretically, refine n-1 parameters
refining a tetragonal LaNi4.85Sn0.15 crystal structure, there might be:
scale factor
2nd order polynomial background: 3 parameters
2 lattice parameters
no atomic positions (all atoms are fixed)
3 or 5 thermal parameters
2 or 4 occupancy factors
zero shift and specimen displacement
5 profile shape parameters
22 parameters maximum with 43 peaks (20 to 120 deg 2theta)
does this mean we can refine all parameters?

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background functions

manually fit background

polynomial
chebyshev
shifte chebyshev
amorphous sinc function
many others for different programs

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profile functions

vary significantly with programs

almost all programs use Cagglioti U, V, and W

H 2 W V tan U tan 2
HSP uses pseudo-voigt, Pearson VII, Voigt, or pseudo-voigt 3 (FJC
asymmetry)
GSAS uses functions derived more from neutron and synchrotron
beamlines

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 go to parameters_calc_pattern.pdf

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How do you know if a fit is good?

difference pattern
Rwp wi Yio Yic
2
Residuals R
R is the quantity that is minimized
during least-squares or other
i
fitting procedures
Rwp is weighted to emphasize
intense peaks over background
Rexp estimates the best value R
for a data set
an evaluation of how good the
data are
RBragg tries to modify the R for a
specific phase
GOF (aka X2)

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Refinement Strategy

Rietveld methods fit a multivarialbe structure-background-

profile model to experimental data
lots of potential for false minima, diverging solutions, etc
need to refine the most important variables first, then add more
until an adequate solution is realized
a correct solution may not result

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Ray Youngs Refinement Strategy

scale factor
zero shift or specimen displacement (not both)
linear background
lattice parameters
more background
peak width, w
atom positions
preferred orientation
isotropic temperature factor B
u, v, and other profile parameters
anisotropic temperature factors

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HSP Automatic Refinement Strategy

Very similar to Prof Youngs recommendations

a good choice for beginners
you can set limits on any of these parameters

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Additional Files

XRD_Basics_HSP_2006.pdf
large collection of information about X-ray diffraction, instrumentation,
and different techniques
XPert HighScore Plus Tutorial.pdf
overview of the different functionality available in HighScore Plus
Introduction.pdf
overview of Rietveld
parameters_calc_patterns.pdf
overview of parameters involved in calculating a diffraction pattern

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further reading

Rietveld refinement guidelines, J. Appl.Cryst. 32 (1999) 36-50

R.A. Young (ed), The Rietveld Method, IUCr 1993
V.K. Pecharsky and P.Y. Zavalij, Fundamentals of Powder
Diffraction and Structural Characterization of Materials,
Kluwer Academic 2003.
DL Bish and JE Post (eds), Modern Powder Diffraction, Reviews
in Mineralogy vol 20, Min. Soc. Amer. 1989.
CCP14 website http://www.ccp14.ac.uk/tutorial/tutorial.htm

prism.mit.edu/xray/resources.htm

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Rietveld Programs

Free
GSAS + ExpGUI
Fullprof
Rietica
PSSP (polymers)
Maud (not very good)
PowderCell (mostly for calculating patterns and transforming crystal
structures, limited refinement)
Commercial
PANalytical HighScore Plus
Bruker TOPAS (also an academic)
MDI Jade or Ruby

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Examples

Silicon
LaB6
intermetallic LaNi4.85Sn0.15

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Silicon

Open the datafile in HSP

Add the structure model
insert the structure manually
import (insert) a struture file
usually use the CIF format the ubiquitous standard for crystal
structures
HSP can also import ICSD *.cry files and structures from other
refinement programs
GSAS can import CIF or PowderCell files
try the automatic refinement
manually improve the fit

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Silicon Crystal Structure

Fd3m
which setting? (2)
a=5.43 A
Si at 0.125, 0.125, 0.125

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Lanthanum hexaboride LaB6

Open the datafile

insert the crystal
structure CIF file
Note that boron
(z=5) makes little
difference in the
XRD pattern
compared to the
lanthanum (z=57)
what can we do to
improve the fit

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LaNi4.85Sn0.15

The data was taken from Chapter 6 of Fundamentals of Powder

Diffraction and Structural Characterization of Materials, by
Pecharsky and Zavalij
The structure is a bit more complex that our earlier example,
which allows us to explore more features of HighScore Plus
The data (Ch6_1.raw) is in GSAS format, which can be read into
HighScore Plus
I have also included a CIF file from the ICSD (#104685) with all
the main features of the structure described

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Issue to Consider

How can I work without knowledge of the structure?

Use LeBail or Pawley method to determine lattice parameters
Try indexing and solving the structure using the HighScore Plus tools
You will find that there are 16 possible space groups for this material, but
picking the most common (and simplest) choice, P6/mmm, is the right way to go

Where do I put the atoms?

You can use a Fourier map to find out wherein the structure the electron densities
are greatest. Put the heaviest atoms (La) at these sites, then work your way
through the chemistry

What variables do I refine and in what sequence?

Take a look at the automatic option in HSP - this is not a bad strategy to use.
We will go through these in detail

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