Frank Girgsdies Phase Analysis and Structure Refinement 131129

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting
Phase Analysis and Structure Renement A Tutorial

Powder X-ray Dirac8on: Phase Analysis and Pa;ern Fi=ng

Part 1: Phase Analysis
Phase iden8ca8on by search/match methods

Part 2: Pa;ern Fi=ng
Extrac8ng informa8on from powder pa;erns by various
t methods

Dr. Frank Girgsdies, Nanostructures Group, Dept. of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany
Informa8on obtainable from powder dirac8on:

Qualita8ve analysis (phase iden8ca8on) Part 1
Quan8ta8ve analysis (phase mixtures)
Parts 1 & 2
La=ce parameters
Part 2
Crystallite sizes & defects (microstructure) Part 2

Crystal structure)
Part 2

9000
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Intensity [counts]
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2theta []
Informa8on content of an idealized dirac8on pa;ern

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Intensity [counts]
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peak area (integral intensity): real measure for peak intensity

relative intensities...
a) ...within one phase
crystal structure (contents of the unit cell,
i.e. types and relative positions of atoms)
b) ...between different phases (in a mixture)
phase quantification
peak width:
a) full width at half maximum (FWHM, a.k.a. half width)
peak position: d-spacing
depends on peak profile
lattice parameters
b) integral breadth (= integral intensity / maximum intensity)
(size & shape of the unit cell)
less dependent on peak profile
crystallite size, defects (strain, disorder)
1000
peak height (maximum intensity):

approximation for peak intensity
peak shape (peak profile):

crystallite size, defects
(strain, disorder)

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n = 2 d sin()
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2theta []
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The ideal crystal structure

la=ce
basis
crystal structure
unit cell
la=ce
basis
unit cell parameters
unit cell contents
(unit cell size & shape) (atom types & posi8ons)
peak posi8ons
rela8ve peak intensi8es
The real (crystal) structure

Ideal crystals are innite, but real crystals are not:
crystallite/domain size eects
peak shape, peak broadening

In ideal crystals, all unit cells are iden8cal, but real crystals have defects:
missing/wrong/addi8onal atoms, thermal mo8on
rela8ve intensi8es
stacking faults, twin boundaries
peak shape, peak broadening, even peak shiYs
local la=ce distor8ons = varia8on of d-spacings = (micro)strain
peak shape, peak broadening
Phase Iden8ca8on (Search & Match)

In powder XRD, crystalline phases are iden8ed by the posi-ons and
intensi-es of the dirac8on peaks.
Note:
The dirac8on angle 2 ( = Bragg angle) is related to the d-spacing via the Bragg equa8on
n = 2 d sin(). Thus, the peak posi8ons on the angular scale are wavelength dependent!

To iden8fy phases from XRD, you need:
a) experimental dirac8on data,
b) one or more database(s) of reference pa;erns,
c) a search/match soYware.

Note:
The soYware performing the search acts as an interface to the database,
thus the soYware and database must be compa8ble with each other.

Depending on the search/match strategies supported by your soYware,
your dirac8on data may (or must) have one of the following formats:
a) raw (i.e. unprocessed) dirac8on data in binary or ASCII format,
b) processed dirac8on data (e.g. background subtrac8on, 2 stripping),
c) a peak list (posi8ons & intensi8es) derived from the measured data
by peak search (crude) or peak =ng (more precise).

Some so3ware examples:
WinXPow (STOE & CIE):
automa8c search on peak list,
or manual matching with raw data (or peak list)
DIFRAC EVA (Bruker AXS), older version:
automa8c search on background subtracted raw data,
automa8c search on peak list
DIFFRAC EVA (Bruker AXS), later version, and
HighScore / HighScore Plus (Panaly8cal):
automa8c search on raw data (background subtracted automa8cally),
automa8c search on peak list
Search & Match with WinXPow
10
Search & Match with EVA (older version)
11
Search & Match with EVA (later version)
12

General strategies:
For a peak list search, the user has to dene a 2 tolerance interval
within which an agreement between reference and data is considered
to be a match.
Raw data search algorithms use the digital intensity informa8on,
without any separate peak recogni8on.
Thus, the background intensity has to be subtracted (by the user or the
soYware) before the search is executed.
Note that 2-stripping is recommended in the older EVA manual, but
it's prac8cal impact is usually unimportant or even nega8ve!
13

Analysis of phase mixtures:
If a posi8ve match is found, but some experimental peaks remain
unexplained, another search has to be performed on the unexplained
peaks (residual).
In the older DIFFRAC EVA version, a scissors tool can be used to
manually exclude explained (or unwanted) regions of the experimental
pa;ern before a residual search is conducted.
This procedure can be tedious, but gives the user maximum control.
In later DIFFRAC EVA versions and HighScore, a residual scan can be
prepared by omission of user controlled intervals around explained
peaks.
This method is easier, but especially in EVA the "one threshold for all
peaks" approach does not work so well.
14

Databases:
We have to dis8nguish between reference pa;ern databases and
crystal structure databases.
Pa;ern databases are used for search/match phase iden8ca8on.
The entries contain informa8on about peak posi8ons and intensi8es,
but tradi8onally no detailed structure informa8on (e.g. atomic coordinates).
The crystal structures of the respec8ve phases may be known or unknown, the
pa;erns may be indexed or not, measured or calculated.
Crystal structure databases contain structural informa8on, including space
group, unit cell, and atomic coordinates, which is necessary for Rietveld based
pa;ern =ng. They usually do not contain dirac8on pa;ern informa8on.
Since dirac8on pa;erns can be calculated from crystal structures, pa;ern
databases may contain calculated pa;erns derived from crystal structure
database entries.
15

Pa@ern databases:
The most commonly used commercial pa;ern databases are the various versions
of the PDF (Powder Dirac8on File) maintained by the ICDD (Interna8onal
Centre for Dirac8on Data), formerly known as JCPDS (Joint Commi;ee on
Powder Dirac8on Standards).
Note that the JCPDS was renamed to ICDD in 1978, so the s8ll ongoing cita8on of
"JCPDS" in the literature is somewhat outdated.
The PDF-2 covers inorganic materials. Since 2003, calculated pa;erns based on
ICSD and NIST crystal structures are included on a larger scale.
The PDF-4/Organics and PDF-4/Minerals cover organics/organometallics and
minerals, respec8vely.
PDF-4+ covers inorganic materials.
All PDF-4 products include a high percentage of calculated pa;erns which are
accompanied by corresponding crystal structure data.
16

Pa@ern databases (con-nued):
As a recent development, calculated pa;erns derived from the non-commercial
COD (Crystallography Open Database) are supported by commercial search/
match soYware (e.g. EVA 3 and HighScore) as alterna8ve to the commercial PDF
products.
Note that a simultaneous search over both databases is not supported due to
license restric8ons from the ICDD.
17

PDF quality marks:
* (Star): high quality measured pa;ern; chemical composi8on well
characterized, intensi8es measured objec8vely, no serious systema8c errors,
average delta 2 < 0.03.
I (Indexed): pa;ern has been indexed (thus almost certainly single phase);
reasonable range and even spread in intensi8es, no serious systema8c errors,
average delta 2 < 0.06.
0 (Zero): dirac8on data of poorly characterized material, or data known (or
suspected) to be of low precision.
B (Blank): pa;erns which do not meet the "*", "I", or "0" criteria.
D (Deleted): pa;ern which was subsequently discredited, or was superseded
by a later, be;er pa;ern (check comments of the entry for details).
Remains available as part of the database for backward reference reasons.
18

PDF quality marks (con-nued):
R (Rietveld): pa;erns with d-values directly from Rietveld renement;
accepted only in unusual cases.
C (Calculated): pa;ern calculated from single crystal data; very precise
d-values, but intensi8es may dier somewhat from experimental pa;ern.
C pa;erns contain reference to crystal structure database entry used for
calcula8on; useful for later Rietveld renement.
A (Alterna8ve): used to mark alterna8ve C pa;erns if mul8ple entries for the
same phase exist; useful to limit the number of choices.

Note:
If you have the choice between several alterna8ve pa;erns for the same phase,
you should chose a "*" or "C" pa;ern.
19

Pa@ern matching FAQ:
Q: How many peaks must match between a reference and measured pa;ern?
A: All peaks of the reference pa;ern should be present in the measured data,
otherwise it is not a valid match.
obs
ref
obs
valid match
(single phase pa;ern)
ref
obs
valid match
(mul8 phase pa;ern)
ref
invalid or ques8onable match

(some reference peaks missing
in experimental pa;ern)
Possible excep8ons:
Small peaks are below detec8on limit (high noise level)
Missing peaks may result from extreme preferred orienta8on eects or
extreme anisotropic peak broadening check if eect is hkl dependent
Bad sta8s8cs (few, large crystallites) peaks would be very sharp; try grinding
the sample thoroughly and measure again
20

Q: All reference peaks occur in the measured pa;ern, but the measurement
contains addi8onal peaks. What does this mean?
obs

ref

A: The iden8ca8on is probably correct, but the measured pa;ern represents a
phase mixture.
Keep the reference pa;ern, then con8nue searching for references
to explain the addi8onal peaks. Proceed un8l all peaks are explained.
obs
obs
ref1
ref2
ref
21

Q: All measured peaks are explained with a reference, except for some very
small ones. I tried to iden8fy them as an impurity phase, but failed.
What could this mean?

obs

A: Possible reasons are:
ref
The peaks are ar8facts resul8ng from spectral impuri8es (other wavelengths,
e.g. K, W L), i.e. weak "duplicates" of very strong peaks.
The peaks are real and belong to the reference compound. Your experimental
pa;ern might be be;er (signal/noise ra8o) than the reference pa;ern.
AYer all, diractometer technology improves with 8me.
Try to check if the addi8onal peaks are compa8ble with the unit cell
parameters of the reference compound.
22

Q: There is a match between all measured and reference peak posi8ons,
but the rela8ve intensi8es disagree. What does this mean?
obs

A: Possible reasons are:
ref
The iden8ca8on is correct, but there are preferred orienta8on eects in the measured
data.
The intensity devia8ons should correlate systema8cally with hkl
Check with Rietveld t including a preferred orienta8on model
The iden8ca8on is correct, but the reference intensi8es have a low level of precision.
Check if the reference intensi8es have only discrete,
rounded values (e.g. 100%, 80%, 50% etc.).
obs
If so, the reference data originated from visual evalua8on
ref
of a photographic lm (i.e. "very strong", "strong", "medium"

etc. translated into percentage numbers).
The iden8ca8on is incorrect, the peak posi8ons coincide only by chance
(not very likely, but possible).
23

Q: The measured and reference pa;erns look very similar, but the peaks seem to
be shiYed. What does this mean?

A: Check if the individual peak shiYs are
(a) constant in direc8on and magnitude,
(b) constant in direc8on but with increasing magnitude at increasing angle, or
(c) variable in their direc8on.

(a) A constant peaks shiY is most probably a measurement ar8fact.
If the deni8on of the 2 scale of the diractometer is o, then the shiY
should be strictly constant (zero shi+, zero error).
If the posi8on of the sample deviates from the center of the goniometer,
then the shiY is not exactly, but close to constant (sample displacement,
height error).
24

(b) Increasing peak shiYs with increasing angle are caused by dierences in the
la=ce parameter(s).
(c) The same is true for shiYs with opposite signs (some la=ce parameters
increase, some decrease).

Dierences in la=ce parameters may be caused by:
Temperature dierences (thermal expansion; could be even nega8ve in some
cases!)
Chemical dierences: instead of e.g. AO2, you may have
A1-xBxO2 (doping/solid solu8on),
AO2-x (variable vacancies),
BO2 (isostructural compound), ...
Note:
ShiYs to lower angles mean expansion, shiYs to higher angles contrac8on of
d-spacings/la=ce parameters.
25

Q: I explained all dirac8on peaks of my measured pa;ern with the reference
pa;ern of my target compound. Both peak posi8ons and intensi8es agree
very well. May I say that my sample is phase pure?

A: No, not necessarily.
Strictly speaking, XRD will never be able to prove phase purity.
There may be impuri8es which are invisible to XRD, either because their
amount is below the detec8on limit, or because they are "XRD amorphous".
However, if your measured pa;ern has a very low noise level and no
unexplained features (e.g. broad bumps) in the background, then you have a
good chance that your sample is indeed phase pure.

26

Q: What do you mean by "XRD amorphous"?

A: With "XRD amorphous" I mean absence of proper Bragg dirac8on peaks.
The material might be truly amorphous, i.e. lack any long range ordering
(crystal la=ce).
However, the material could also be what I would call "nanocrystalline",
i.e. crystalline with very small crystallite sizes.
Remember that the intensity of dirac8on peaks is given by their area,
and that small crystallites lead to peak broadening. Hence, if the crystallite
size is reduced, the peaks will not only become broader, but also lower.
Furthermore, dirac8on peaks have no abrupt end, thus they tend to merge
smoothly with the background, becoming increasingly indis8nct.
S8ll, such a "nanocrystalline" sample without recognizable Bragg peaks will
show la=ce fringes in high resolu8on TEM.

27

Peak broadening:
no discrete border between crystalline and
"nanocrystalline XRD amorphous" materials
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2 []
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Phase quan-ca-on by the RIR (Reference Intensity Ra-o) method
In the PDF product family, many experimental and all calculated
reference pa;erns are accompanied by I/Ic values.
I/Ic is the ra8o between the intensi8es of the strongest peaks of the
respec8ve phase and corundum in a binary 50:50 wt.% phase mixture.
In ideal powder XRD, the intensi8es are approximately propor8onal to
the weight frac8ons of the corresponding phases.
Thus, if all components of a mul8phase mixture have been iden8ed
with suitable reference pa;erns (with I/Ic values) and the reference
pa;erns are scaled to match the intensi8es of the experimental pa;ern,
then the ra8os of the I/Ic values weighted by the individual scaling
factors yield the approximate weight frac8ons of the phases (Ic
contribu8ons cancel out).
29

Phase quan-ca-on by the RIR (Reference Intensity Ra-o) method

Note:
This method requires that all phases are accounted for (no amorphous
or uniden8ed phases, no missing I/Ic values).
Any distor8ons of rela8ve peak intensi8es, e.g. by preferred
orienta8on eects or microabsorp8on, will lead to erroneous results.
In the RIR method, the peak height (instead of area) is used to scale
the reference pa;erns to the measured data. Thus, stronger varia8ons
in the peak width will distort the results (no propor8onality between
peak height and area).
30
Pa;ern Fi=ng
Some general remarks on Mng:
A model (empirical or physically based) is used to calculate a theore8cal data
set.
The variable parameters of the model are op8mized (usually by least squares
algorithms) to obtain the best possible agreement (t) between calculated and
measured data.
The aim of =ng experimental data is oYen to extract physical parameters
from the data.
Only with a physically based, appropriately chosen model, the rened
parameters may be interpreted as physically meaningful quan88es.
However, even if a physical model is absent, =ng may s8ll be useful to
parameterize the measurement data (data reduc8on).
31
Pa;ern Fi=ng
Some general remarks on Mng:
An increase in the number of rened parameters usually improves the t
(agreement between measured and simulated data) because the model
becomes more exible.
If the number of rened parameters is increased too much, they become less
well dened (parameters start to correlate with each other).
In the worst case, you will have an excellent looking t with a set of
meaningless parameters ("over=ng").
The number of rened parameters must stay small compared to the
number of "observables".
The strategy for any t should be to obtain the best possible t with as few t
variables as possible (which is in most cases easier said than done).
The choice of a t model is always a compromise and should be based on
physical reasoning.
32
Pa;ern Fi=ng
Types of Mng in powder dirac-on:
WPPM vs. WPPF
In powder dirac8on, a dis8nc8on is usually made between Whole Powder
Pa;ern Fi=ng (WPPF) and Whole Powder Pa;ern Modelling (WPPM).
In WPPF, the peak shape func8ons used are empirical, with the focus on the
determina8on of crystal structure parameters (Rietveld method) and/or
microstructural parameters (size/strain analysis).
In WPPM, the peak shapes are modelled based on physical assump8ons in
order to analyze the microstructure and especially the defect structure (e.g.
stacking faults) of the material.
33
Pa;ern Fi=ng
Rietveld method (crystal structure renement)
The Rietveld method was originally invented to rene crystal structures from
(neutron) powder dirac8on data.
A Rietveld structure renement primarily aims at the determina8on of the
crystal structure geometry (atomic coordinates and la=ce parameters bond
distances).
Depending on the context and the data quality, site occupancies and thermal
displacement parameters ("temperature factors") may also be rened.
The renement of further parameters (peak proles, background func8on,
zero error and other correc8ons) only serves the purpose of determining the
peak intensi8es as accurately as possible.
Preference for analy8cal peak shape func8ons.

34
Pa;ern Fi=ng
Rietveld method
Later, it was realized that the Rietveld scale factors obtained from =ng phase
mixtures are related to the concentra8ons of the respec8ve phases
Rietveld based phase quan8ca8on.
For quan8ca8on and "advanced qualita8ve analysis", it is advisable to keep
the atomic parameters of the reference structures xed, thus reducing the
number of rened parameters.
If a reference structure seems doub~ul or inappropriate for the samples
inves8gated, one may a;empt to rene the structural parameters once on a
reference measurement (data quality and phase purity as good as possible) to
obtain a modied reference structure, then keep the structural parameters
xed again during further analysis.

35
Pa;ern Fi=ng
1,150
t-ZrO2_refined
4.63 %
m-ZrO2_ICSD-89426 95.37 %
1,100
1,050
1,000
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36
Pa;ern Fi=ng
1,150
t-ZrO2_refined 4.68 %
m-ZrO2_refined 95.32 %
1,100
1,050
1,000
950
900
850
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37
Pa;ern Fi=ng
Rietveld method
In a Rietveld t, the intensi8es of the peaks are calculated from the crystal
structure model (whether the model itself is rened or not).
Individual peak shapes of a phase are usually correlated via a peak shape
func8on with renable parameters.
May be used for microstructure (size/strain) analysis.
Individual peak posi8ons are correlated via the la=ce parameters.
If the crystal structure model itself is not rened, the Rietveld method thus
provides the lowest possible number of rened variables for WPPF.

Note: The correla8on of peak posi8ons and shape parameters reduces the
number of variables and improves the extrac8on of intensi8es for overlapping
peaks, which is of primary importance for a Rietveld structure renement.
38
Pa;ern Fi=ng
Pawley and Le Bail methods
The Pawley and Le Bail methods have been developed to extract the reec8on
intensi8es from powder dirac8on pa;erns for the purpose of structure
solu8on.
Both methods may also be conceived as (or used as) structure-less methods in
WPPF.
In the Pawley method, the individual peak intensi8es are rened t variables.
In the Le Bail method, the intensi8es are not rened directly. Instead, the
par88oning scheme of overlapping reec8ons is op8mized itera8vely in
analogy to the Rietveld algorithm, but without the structure informa8on.

39
Pa;ern Fi=ng
Pawley and Le Bail vs. Rietveld
The Pawley and Le Bail methods share with the Rietveld method that the peak
shapes and peak posi8ons of a phase are correlated.
The lack of a crystal structure model (which would determine the peak
intensi8es) leads to a higher number of renable parameters.
If a good Rietveld t is possible, it is preferable over Pawley/Le Bail because of
the lower number of t parameters and the extra informa8on obtained (phase
quan8ca8on).
If a Rietveld t doesn't work well, a Pawley/Le Bail t may be the be;er
choice, as the increased exibility usually leads to a be;er t.
More accurate extrac8on of peak proles (microstructure) and la=ce
parameters.
However, you should ask yourself why the Rietveld approach has failed to
produce the desired t...

40
Pa;ern Fi=ng
Single peak Mng
Single peak =ng usually means that every individual peak has its own rened
peak shape, posi8on and intensity parameters very high number of
variables in WPPF.
Note: If you would do exclusively single peak =ng, this could barely be called
WPPF at all. Never rene a peak shiY correc8on parameter in such a case!
The renement of la=ce parameters (including peak shiY correc8on),
microstructure etc. would have to be performed secondarily.
Single peak =ng is especially troublesome in case of peak overlap.
Thus, single peak =ng should only be used for specic reasons or if there is
no other alterna8ve.
Examples: extra peaks from uniden8ed impurity phases in a mixture, sample
holder signals or other ar8facts, ...

41
Pa;ern Fi=ng
Powder pa@ern Mng step by step: an overview
Before you can t a powder pa;ern, you need to iden8fy your phase(s)
see part 1 (phase iden8ca8on).
AYer iden8ca8on of the main protagonists, you should try to get
corresponding crystal structure models for Rietveld based =ng.
Retrieve crystal structure data from structure databases or literature.
If the phase iden8ca8on can be based on a calculated pa;ern, it should give
you a reference to the corresponding structure database entry (e.g. PDF-2
references to ICSD and NIST), or be accompanied by structural data (e.g. COD
or PDF-4+).
If you cannot get crystal structure informa8on, you should at least try to get
the la=ce parameters and space group (or at least crystal class) of that phase
for use in Pawley/Le Bail =ng.
If you have none of the above informa8on, you are leY with single peak =ng
for the corresponding phase.
42
Pa;ern Fi=ng
Some8mes, you will realize during the pa;ern =ng that there are previously
overlooked addi8onal phases in the samples (this is what I call "advanced
qualita8ve analysis").
Repeat the iden8ca8on and data retrieval procedure for the addi8onal
phase(s).
If you are sa8sed with the t (i.e. with the agreement between calculated
and measured data), you can proceed with extrac8ng physical data from the
t variables.
If all relevant phases were treated appropriately with Rietveld =ng, you will
obtain the corresponding quan8ta8ve informa8on (weight percentages).
Rened la=ce parameters result for all phases represented by either Rietveld
or Pawley/Le Bail =ng.
If a suitable peak shape func8on was chosen, Rietveld, Pawley and Le Bail
phases will provide microstructural (size and/or strain) parameters.
43
Pa;ern Fi=ng
In the case of single peak =ng, quan88es like la=ce and microstructure
parameters can only be obtained by secondary evalua8on, usually with much
lower precision than from correlated =ng.
44
Pa;ern Fi=ng
Crystal structure databases
ICSD (Inorganic Crystal Structure Database) by FIZ Karlsruhe is the world's
largest database for inorganic structures.
Original deni8on: crystal structures of elements (including metals) and
compounds containing at least one non-metal and no C-H bonds.
As a recent development, the ICSD also incorporates some simple C-H
containing compounds (especially formates, acetates etc.) and some
intermetallic compounds.
CSD (Cambridge Structural Database) by CCDC (Cambridge Crystallographic
Data Centre) covers small-molecule organic and metal-organic crystal
structures (compounds with C-H bonds).
CRYSTMET by Toth Informa8on Systems covers metals, alloys, intermetallic
compounds and minerals (cri8cally reviewed, physical metadata).
45
Pa;ern Fi=ng
Crystal structure databases
NIST Crystal Data Iden8ca8on File contains inorganic and organic structures
(hasn't been updated for several years).
Pearson's Crystal Data by ASM Interna8onal covers inorganic structures
(cri8cally reviewed).
Furthermore, there are several databases for large organic molecules (mainly
proteins).
46
Pa;ern Fi=ng
Crystal structure data
Depending on the database source and the Rietveld soYware you are using,
you may have to convert the crystal structure data format.
The most common format, however, is the CIF (Crystallographic Informa8on
File) format, which is supported by most contemporary crystallographic
soYware.
Note that the CIF is an "open format", i.e. it may always happen that some
keywords are not understood by your soYware. Depending on the soYware,
such keywords are simply ignored, or may lead to incorrect data import or
even program crashes.
In the worst case, you have to iden8fy the problem and edit the CIF le
accordingly.
47
Pa;ern Fi=ng
Crystal structure data: possible piWalls
Many space groups have alterna8ve se=ngs.
In some cases, this involves dierent choices of crystallographic axes.
In others, it is simply a dierence in the choice of the coordinate origin.
Some8mes, the se=ng informa8on is coded in the space group symbol
(dierent cell choices in monoclinic or orthorhombic space groups), but will be
absent if the space group is iden8ed only via the space group number.
Alterna8ve origin choices can op8onally be coded by extending the Hermann-
Mauguin symbol with the le;ers "Z" and "S".
Some space groups occur in dierent nota8ons. For example, space group
3 is usually wri;en as Fm-3m, but some soYware or databases
No. 225 (Fm3m)
may use the nota8on Fm3-m or Fm3m instead.
The safest way to unambiguously describe the space group se=ng is to
explicitly include the symmetry opera8ons in the CIF le, in addi8on to the
space group symbol or number.
48
Pa;ern Fi=ng
Crystal structure data: possible piWalls
Crystallographic soYware diers in how a space group is recognized from the
data given in a CIF le.
Always check your crystal structures for plausibility aYer import. Erroneous
interpreta8on of crystal structures by the soYware will lead to wrong intensity
distribu8ons.
In the worst case, you may have to nd out the correct se=ng by trial and
error.
Some8mes, soYware may be oended by some forma=ng of the CIF le (e.g.
non-integer oxida8on states). In this case, you may have to edit the CIF le
accordingly.
Another possible source of error can be the end-of-line character problem
between unix/linux and windows systems.
demonstra8on
49
Pa;ern Fi=ng
Some commonly used Rietveld so3ware (non-exhaus-ve list):
Fullprof: freely available
GSAS: freely available
RIETAN: freely available
TOPAS (Bruker AXS) and TOPAS Academic: commercial, dier in license fee
and user interface
HighScore Plus (Panaly8cal): commercial, contains func8onality of HighScore
with addi8onal Rietveld capabili8es
DDM: freely available, contains conven8onal Rietveld approach in addi8on to
the Dierence Deriva8ve Minimiza8on.
50
Pa;ern Fi=ng
Peak proles
The peak shapes of dirac8on pa;ern result from a convolu8on of
instrumental and sample contribu8ons.
For microstructural analysis, the instrument contribu8on must be separated
from the sample contribu8on (not trivial, various approaches).
Instrumental proles may be determined experimentally (using reference
samples with negligible sample related peak broadening), or be calculated
from known instrument geometries (e.g. Fundamental Parameters Approach,
ray tracing methods).
Note that peak asymmetries from the instrumental prole will cause shiYs in
the peak posi8ons. Thus, this eect needs to be accounted for to get reliable
la=ce parameters.
For Rietveld renement in the strict sense, empirical peak shape func8ons are
commonly used.
51
Pa;ern Fi=ng
Peak proles
Commonly used peak prole func8ons are:
Gaussian
Lorentzian
Voigt (a convolu8on of a Gaussian and a Lorentzian contribu8on)
pseudo-Voigt (a linear combina8on of a Gaussian and a Lorentzian func8on;
approaches the Voigt func8on very well)
Pearson VII (popular during the 1980s and 1990s, now superceded in
popularity by the pseudo-Voigt)

Note: All above listed func8ons are symmetric. Some8mes, asymmetric versions
(so-called "split" func8ons) are used to model peak asymmetry. Split func8ons
have separate width an shape parameters for the parts leY and right of the
maximum.
52
Pa;ern Fi=ng
Peak proles
Voigt func8ons with dierent Gaussian and Lorentzian contribu8ons:
black: pure Gaussian
red: pure Lorentzian

The Gaussian has a narrower base and more rounded 8p,
while the Lorentzian has a more pointed 8p and much more extending "feet".
53
Pa;ern Fi=ng
Correla-on of peak proles
In order to reduce the number of rened parameters and to be;er resolve
peak overlap, the width/shape parameters of peaks belonging to a phase are
usually correlated in WPPF via a func8on with renable coecients.
The most common way is to describe the peak shapes as func8ons of the
dirac8on angle .
Depending on the prole =ng approach implemented, the rened angular
dependence will be either that of the total prole, or the sample contribu8on
to the prole.
In X-ray dirac8on, the peaks usually get broader with increasing angle.
If the peak widths are more properly described as a func8on of the Miller
indices hkl rather than the angle (so-called anisotropic peak broadening),
then the microstructural parameters vary with the direc8on in the crystallites.
54
Pa;ern Fi=ng
Correla-on of peak proles
Commonly used correla8on func8ons are:
The Caglio= formula G2 = U tan2() + V tan() + W was introduced for =ng
neutron dirac8on data (pure Gaussian proles).
The Thompson-Cox-Has8ngs formula is an extension of the Caglio= formula
to account for the dierent prole behavior in synchrotron XRD with pseudo-
Voigt proles:
G2 = U tan2() + V tan() + W + P/cos()
L = X/cos() + Y tan()
In the Double-Voigt approach, a Voigt func8on with 1/cos() dependence
(represen8ng crystallite size broadening) is convoluted with a tan()
dependent Voigt func8on (strain broadening) for the sample related peak
broadening, while the instrumental contribu8on can be represented by the
Fundamental Parameters Approach (convolu8onal =ng).

55
Pa;ern Fi=ng
Peak posi-on correc-ons
Common correc8ons for peak posi8ons include
Zero error or zero shi+: oset in the deni8on of the 2 scale of the
diractometer; all peaks are shiYed by a constant value (i.e. independent).
Sample displacement or height error: sample is posi8oned o the
diractometer center; peak shiYs are a func8on of cos().
Specimen transparency: incident beam penetrates into deeper layers of the
sample (diracted beam, on average, will come from a lower height);
indis8nguishable from a real sample displacement, thus not handled
separately.
Correc8ons connected with instrumental peak asymmetry (usually handled by
the soYware).
56
Pa;ern Fi=ng
X-ray tube
detector
sample holder
with sample
sample displacement
specimen transparency
57
Pa;ern Fi=ng
Peak posi-on correc-ons
In WPPF, you usually need to rene a peak posi8on correc8on parameter.
However, the eects of zero shi+ and sample displacement are so similar that
you should never rene both parameters together!
You need to decide which of the two parameters you want to rene.
In reality, probably both will aect your peak posi8ons.
However, as both are very similar, the choice between one or the other will
have very li;le impact on your results.
Personally, I chose displacement for reec8on (Bragg-Brentano) and zero shi+
for transmission geometry.
58
Pa;ern Fi=ng
Intensity devia-ons
Some8mes, the calculated rela8ve intensi8es of a phase do not match the
observed intensi8es. Possible reasons can be:
Incorrect crystal structure model (se=ng and origin choice, handling of special
posi8ons) calculated intensi8es are wrong.
Bad sampling sta8s8cs due to very large (thus comparably few) crystallites
peaks are extremely sharp.
Preferred orienta:on eects crystallites have strongly anisotropic shape
(platelets, needles); intensity devia8ons are func8on of hkl; direc8on of eect
will be reversed for change between reec8on and transmission geometry.
59

Example for very bad sta8s8cs
(few, very
large crystallites)
Pa;ern
Fi=ng
5000
4500
4000
3500
Absolute Intensity
3000
2500
2000
1500
1000
500
0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
2Theta
60
Pa;ern Fi=ng
Preferred orienta-on eect
One of the basic assump8ons of powder dirac8on is that you have a very
large number of crystallites in random orienta8on.
Random orienta8on means that all possible orienta8ons of crystallites within
the sample occur with the same probability.
Thus, for any possible orienta8on of the sample rela8ve to the primary beam
and the detector, a suciently large and representa8ve frac8on of crystallites
would be in the correct orienta8on to fulll the Bragg equa8on.
[Note that this implies that every observed reec8on in a powder pa;ern
(except higher orders) results from a dierent sub-set of crystallites in your
sample!]
If anisotropic crystallite shapes are combined with a direc8ng mechanical
force (sample prepara8on), then some crystallite orienta8ons will occur more
oYen that others assump8on of random orienta8on of crystallites in the
powder is not valid anymore.
61
Pa;ern Fi=ng
Reec8on geometry:
Transmission geometry:
62
Pa;ern Fi=ng
In the case of a preferred orienta8on eect, some reec8ons will be stronger,
and some weaker than calculated.
OYen, you may no8ce that there is a trend with the Miller indices hkl:
try to check if the eect is most pronounced for certain families of low-index
reec8ons, like h00, 0k0, 00l, hk0 etc.
If you suspect preferred orienta8on, you may want to check this hypothesis
against independent evidence:
- Crystal morphology from electron microscopy
- Typical crystal habit or cleavage from literature, especially for minerals
- The crystal structure itself (maybe 2D structure, e.g. MoO3?)
- Second XRD measurement with alternate measurement geometry
- Second XRD measurement with dierent sample prepara8on
63
Pa;ern Fi=ng
Most Rietveld programs contain one or more op8ons for the modeling of
preferred orienta8on.
The most popular is the March-Dollase model.
It requires that you explicitly chose the crystal direc8on of the preferred
orienta8on and renes a parameter represen8ng the magnitude of this eect.
Chose a direc8on which either seems to be most enhanced or suppressed in
your pa;ern, or base your choice on independent evidence as listed above.
Note that higher order reec8ons (e.g. 001, 002, 003) represent the same
direc8on in the crystal. Thus, if e.g. the 002 reec8on is most pronounced and
your crystal structure does not allow the presence of a 001 reec8on due to
the systema8c absences of its space group, the direc-on is s8ll called 001.
64
Pa;ern Fi=ng
Another popular approach is the renement of a spherical harmonics func8on.
You may chose the "order" of the func8on, which is an even integer number.
The higher the order, the more exible the model (higher number of rened
parameters).
Note that the actual number of variables also depends on the crystal
symmetry (higher symmetry = fever variables).
Advantage and disadvantage in comparison to March-Dollase:
- higher number of renable parameters
- model free (you do not need to chose the preferred direc8on, but you also
will learn less about it).
Depending on how your Rietveld soYware handles it, you may run into
physically unreasonable results (nega8ve intensi8es)!
65
Pa;ern Fi=ng
The preferred orienta8on eect modulates the intensi-es (i.e. areas) of the
peaks as a func8on of hkl.
Thus, you may some8mes be mislead by anisotropic peak broadening, which
modulates the widths of the peaks as a func8on of hkl.
If the areas of the peaks stay constant but their widths vary, then their heights
will vary, too.
Thus, you should check if the observed mismatch is really caused by the peak
areas, or maybe by their widths.
Try switching from a Rietveld t to a structure-less (Pawley or Le Bail) t.
If there is s8ll a prole mismatch, although you allowed the intensi8es to be
rened, then you have a problem with the peak widths or proles.
66
Pa;ern Fi=ng
Other eects inuencing peak intensi-es
There are several other eects which may distort the rela8ve intensi8es,
usually as a func8on of 2:
- details of the instrument geometry
- beam spill (beam cross-sec8on at low angles is larger than sample area)
- surface roughness
etc.
These eects are to numerous to be detailed here, please refer to you
Rietveld soYware manual to see what op8onal correc8ons may be
implemented.
The corresponding correc8ons are usually global, i.e. the intensi8es of all
phases in a mixture will be aected the same way.
If you decide to use one of these intensity correc8on op8ons because it
improves the t, you should s8ll consider whether this choice is physically
reasonable: For example, a surface roughness correc8on may be reasonable if
your sample is coarse grained or highly absorbing, but not if your sample has a
low absorp8on, very ne grain size and was carefully prepared.
67
Pa;ern Fi=ng
Peak broadening
Peak broadening may be sample or instrument related, symmetric or
asymmetric.
68
Pa;ern Fi=ng
Asymmetric peak broadening
Peaks at lower angles are usually asymmetrically broadened towards the leY,
which is an instrumental eect caused by axial beam divergence.
Axial divergence can be reduced by using axial sollers (on the tube and/or
detector side).
Theore8cally, asymmetric broadening on the right ank would occur for peaks
at very high angles (approaching 180 2), while peaks around 90 2 should
be symmetric.
If the measurement was done with K1+2 radia8on, the peaks may look
increasingly asymmetric (shoulder on the right) for increasing angle
(depends on the rela8on between peak width and angle).
69
Pa;ern Fi=ng
Asymmetries which cannot be explained as above may be sample related.
If the asymmetry aects all peaks of a phase and increases with the dirac8on
angle, then it may be caused by inhomogeneity of that phase.
For example, the d-spacings/la=ce parameters may have a non-symmetric
distribu8on (in contrast to microstrain, which is symmetric) due to chemical
varia8on between dierent crystallites, or even within crystallites (chemical
gradient).
You should consider whether chemical varia8on is likely for your type of phase
(solid solu8on, doping, variable stoichiometry).
A plausibility test may be made by inser8ng the same phase a second 8me
into the (preferably Rietveld-) renement with slightly dierent star8ng
parameters. If the t looks signicantly be;er, this may be taken as evidence
suppor8ng the inhomogeneity hypothesis.
70
Pa;ern Fi=ng
If only some peaks are aected, maybe even in dierent direc8ons, the reason
could be a symmetry reduc8on of your crystal structure.
Try to t with structurally closely related, lower symmetry version of the
crystal structure you are currently using (i.e. t-ZrO2 instead of c-ZrO2, MoO2
type instead of ru8le type).
If only few peaks are aected, it might be that an unrecognized impurity
phase accidentally overlaps with the main phase peaks.
Try nd a reference phase which has its main peaks in the posi8ons of the
apparent "shoulders" of your main phase peaks.
71
Pa;ern Fi=ng
Symmetric peak broadening / microstructure
Symmetric, sample related peak broadening is usually caused by the
microstructural proper8es crystallite size and microstrain (short: size & strain).
Size broadening has been recognized and described by Paul Scherrer almost a
century ago (1918). Scherrer equa8on.
Smaller crystallites yield broader reec8ons.
XRD is a volume eect, hence crystallite sizes determined from XRD peak
broadening ale volume weighted averages.
Size broadening can be best analyzed in the range of roughly 10 - 1000 .
For larger sizes, the eect becomes comparable to instrumental broadening.
For smaller sizes, the peaks become so indis8nct that they merge with the
background.
72
Pa;ern Fi=ng
With XRD, you get either crystallite or domain sizes, but not par8cle sizes!
If you do not know the exact microstructure of your material, you will not
know whether it is crystallite or domain size. Hence, both terms are mostly
used synonymously.
A very precise term would be "size of the coherently dirac8ng domain".
73
Pa;ern Fi=ng
par8cle
crystal
crystallite
domain
[ illustra8on taken from TOPAS Users Manual, Bruker AXS ]
74
Pa;ern Fi=ng
Many people s8ll use the Scherrer formula to extract size informa8on from
the width of a single dirac8on peak.
This is not state of the art and not recommended!

My favorite quote from the Rietveld mailing list (rietveld_l@ill.fr)
Ma;eo Leoni (in reply to a newbie ques8on concerning how to chose a peak for
Scherrer analysis):
"I think you can use the same criterion you use to select numbers to play bingo.
As (I hope!) you are going to use Scherrer formula on one peak just to get a
number (and not to get any physically meaningful informa8on), just select the
most isolated, most intense one. At least you play with a be;er sta8s8cs..."
75
Pa;ern Fi=ng
Scherrer realized that the peak broadening from XRD yields only "apparent"
crystallite sizes, which need to be converted by means of a shape factor if
"true" crystallite sizes should be obtained:
D = K / {FWHM cos()}
D: crystallite/domain size
K: shape factor (close to unity, on average around 0.9)

Shape factors have been calculated for several regular geometries (sphere,
cube, octahedron, tetrahedron).
The dier even for dierent miller indices (except for spheres).
76
Pa;ern Fi=ng
Most people don't know (or care about?) their crystallite shapes, so they use
something like an "overall average" shape factor.
In most cases, the details of the Scherrer analysis are not reported.
Dierent people would get dierent results from the same data set!
What is the point of using a shape factor to convert an apparent into a "true"
size, if the true shape is not known???
Even if done correctly, the Scherrer approach will only result in reasonable
values if no other sources of peak broadening (instrumental, strain etc.) are
present.
You should be;er:
1) Use WPPF instead of single peak analysis
2) Use integral breadth instead of FWHM
3) Report apparent instead of "true" crystallite sizes (e.g. LVol-IB)
4) Consider instrumental broadening and the possibility of strain
77
Pa;ern Fi=ng
LVol-IB is a measure for crystallize size which can be calculated directly from
WPPF without using a shape factor:
LVol-IB = / {IB cos()}
IB: Integral Breadth
"L" stands for a length (or height) of a column of stacked unit cells, while the
index "Vol" points at the fact that the value represents a volume weighted
mean.

78
Pa;ern Fi=ng
Microstrain means that not all d-spacings in a crystallite are exactly equal, but
show a certain distribu8on.
This can be envisioned as local, sta8c displacements of atoms out of their ideal
average posi8on.
Both compression and expansion of la=ce planes from the op8mum distance
consume energy. As both forces need to be in balance, the distribu8on is
symmetric, i.e. the peak is broadened, but not shiYed.
Stokes and Wilson (1944) described strain broadening as follows:
0 = IB / {4 tan()}
The dierent angular dependence of the broadening can be used to separate
size and strain eects (size broadening propor8onal to 1/cos(), strain
broadening propor8onal to tan())
79
Pa;ern Fi=ng
In the Williamson-Hall analysis, the widths of all peaks of a phase (corrected
for instrumental broadening) are extracted separately (uncorrelated, i.e.
single peak t).
The term widthcorr. cos() (in radians) is plo;ed on the y-axis,
while 4 sin() is plo;ed on the x-axis for all reec8ons.
If size and strain are isotropic (independent of the direc8on in the crystallite),
then the data points should fall on a straight line.
The slope of the line represents the microstain, while the y-axis intercept at
4 sin() = 0 represents the crystallite size.
As the Williamson-Hall approach requires extrac8on of single peak widths, it
will work properly only in absence of signicant peak overlap.
80
Pa;ern Fi=ng
The Double-Voigt approach (Balzar, 1992) uses two convoluted Voigt func8ons
to describe the sample related peak broadening of a phase over the whole
angular range.
The width of one Voigt func8on is propor8onal to 1/cos(), while the other is
propor8onal to tan().
Thus, the peak width correla8on used in this WPPF approach can be
interpreted as implying that a perfect isotropic Williamson-Hall type
correla8on exists.
This way, the problems of separa8ng overlapping peaks is overcome.
If the t yielded by this method is good, we may assume a Williamson-Hall
type correla8on and thus directly extract size and strain from the t.
81
Pa;ern Fi=ng
If the Double-Voigt t is not good, then we have probably a case of anisotropic
peak broadening.
Anisotropic peak broadening means that the distribu8on of peak widths
follows not so much the dirac8on angle but depends more on the direc8on
in the crystallite.
As size and strain are separated based on their angular dependence, the
anisotropic case leaves us with a phenomenological t of the pa;ern (no
extrac8on of size and strain).
In reality, the peak widths will probably depend on both and hkl with varying
weight.
However, the simultaneous renement of a and hkl dependence is usually
not recommended because of the risk of over=ng.
In an intermediate case, you need to decide which model suits your case
be;er.
82
Pa;ern Fi=ng
If you t anisotropic peak broadening with an isotropic model, the mist will
usually leave characteris8c symmetric signatures in the residual (dierence
between measured and calculated data).
Because the mist is symmetric, you may s8ll extract reasonable la=ce
parameters (peak posi8ons not aected, only error bars slightly increased).
The physical reason for anisotropic size broadening lies in anisotropic
crystallite shapes with high aspect ra8os. Thus, it may occur together with
preferred orienta8on.
83
Pa;ern Fi=ng
26,000
m-TaON_ICSD-1032 100.00 %
25,000
24,000
23,000
22,000
21,000
20,000
19,000
18,000
17,000
16,000
15,000
14,000
13,000
12,000
11,000
10,000
9,000
8,000
7,000
6,000
5,000
4,000
3,000
2,000
1,000
0
-1,000
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
monoclinic TaON with isotropic peak broadening

84
Pa;ern Fi=ng
13,500
13,000
12,500
12,000
11,500
11,000
10,500
10,000
9,500
9,000
8,500
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000
-2,500
-3,000
-3,500
-4,000
-4,500
15
m-TaON_ICSD-1032 100.00 %
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
monoclinic TaON with anisotropic peak broadening, isotropic t

85
Pa;ern Fi=ng
13,500
m-TaON_ICSD-1032 100.00 %
13,000
12,500
12,000
11,500
11,000
10,500
10,000
9,500
9,000
8,500
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
monoclinic TaON with anisotropic peak broadening, anisotropic t

86
Pa;ern Fi=ng
Many people compare their XRD crystallite sizes with electron microscopy
results.
It should be emphasized that this is by no means straight forward!
XRD is an integral method, EM is local.
Even if the EM operator is measuring a large number of crystallites to obtain a
histogram (size distribu8on), you may see two dierent things (like e.g.
crystallite vs. domain sizes).
A size distribu8on from EM can be used to produce various mean values, while
XRD will always yield the volume weighted mean.
Request specically the volume weighted mean size from your electron
microscopist!
87
Pa;ern Fi=ng
88
Pa;ern Fi=ng
Structure renement (Rietveld renement in the original sense)
This topic is too complex to be covered here in detail.
Some brief general guidelines would be:
Renement of (individual) thermal displacement parameters ("temperature
factors") or hydrogen posi8ons from powder XRD is very tricky and should be
leY to the experts. Beware if you come across publica8ons in which this seems
rou8ne.
Temperature factors are something like a waste bin in which many kinds of
ar8facts may accumulate.
Thermal parameters and site occupancy factors correlate strongly with each
other. Don't rene them together without reasonable restrains.
Judge the quality of a t not by R values, but by the look of the t (e.g. the
shape of the residual) and the plausibility of the resul8ng structure
(reasonable bond distances, small e.s.d.s (es8mated standard devia8ons).
89
Pa;ern Fi=ng
R values in Rietveld renement
In single crystal structure renement R values provide a rela8vely sound basis
to judge the quality of a rened crystal structure model on an objec8ve scale.
In Rietveld renement, this is not the case.
Originally, R factors were dened for renements in which the background
had been subtracted previously.
Nowadays, the background is usually not subtracted, but rened with the
other parameters (less bias). Two kinds of R values, including or excluding
the contribu8on of the background.
If you have a measurement with a high background and small dirac8on peaks
on top, than you can get excellent R factors with a lousy structure model, as
long as you t your background properly.
On the other hand, a perfect structure model may give bad R values if you e.g.
cannot t the peak proles perfectly.
90
Pa;ern Fi=ng
R values in Rietveld renement
There are no good or bad R values in Rietveld renement on an absolute scale.
However, the R values have a meaning for a given measurement (be;er R
value, be;er t).
Many Rietveld programs will report an Rexp value. This is an es8mate by the
soYware how good an ideal t would be if only the experimental noise was
leY as residual.
Another op8on is to switch from a Rietveld to a Pawley or Le Bail t with
otherwise the same set of parameters. The R value you obtain then is the
op8mum you could theore8cally reach with a perfect Rietveld t.
Suggested reading:
Brian H. Toby: "R factors in Rietveld analysis: How good is good enough?"
Powder Dirac8on 21(1), 2006, 67-70.
91

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Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Informa8on content of an idealized dirac8on pa;ern

peak area (integral intensity): real measure for peak intensity

peak height (maximum intensity):

peak shape (peak profile):

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

The ideal crystal structure

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

The real (crystal) structure

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

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Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Search & Match with EVA (older version)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Search & Match with EVA (later version)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

invalid or ques8onable match

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

of a photographic lm (i.e. "very strong", "strong", "medium"

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)

Powder X-ray Diffraction: Phase Analysis and Pattern Fitting

Phase Iden8ca8on (Search & Match)