USERS MANUAL

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1 CONTENTS
1 CONTENTS.....................................................................................................................................................II
2 THE GUI...................................................................................................................................................... - 1 -
1.1 ELEMENTS OF THE USER INTERFACE .......................................................................................................- 1 -
1.2 PARAMETERS WINDOW...........................................................................................................................- 2 -
1.3 Y-AXIS LIMITS, ZOOMING, PANNING AND SELECTING..............................................................................- 3 -
1.4 SCAN WINDOW - SHORT CUT MENU.......................................................................................................- 3 -
1.5 CHART OPTIONS DIALOG........................................................................................................................- 4 -
1.6 FIT WINDOW...........................................................................................................................................- 4 -
1.7 OPENGL STRUCTURE VIEWER................................................................................................................- 6 -
1.8 RIGID BODY EDITOR WINDOW................................................................................................................- 6 -
1.9 OPTIONS DIALOG....................................................................................................................................- 7 -
1.10 PRINTING AND REPORTING......................................................................................................................- 8 -
1.11 PROGRAM DEFAULTS ..............................................................................................................................- 9 -
1.12 OPERATION.............................................................................................................................................- 9 -
3 PEAK SHAPE MODELLING................................................................................................................. - 10 -
3.1 SOURCE EMISSION PROFILES .................................................................................................................- 11 -
3.2 DIRECT CONVOLUTION APPROACH: EMPIRICAL PARAMETERISATION....................................................- 14 -
3.2.1 General considerations ............................................................................................................... - 14 -
3.2.2 Example....................................................................................................................................... - 16 -
3.2.3 Use of classic analytical functions .............................................................................................. - 19 -
3.3 DIRECT CONVOLUTION APPROACH: FUNDAMENTAL PARAMETERS........................................................- 19 -
3.3.1 General considerations to FPA................................................................................................... - 19 -
3.3.2 Applicability of the FPA.............................................................................................................. - 20 -
3.3.3 Diffractometer configurations and their geometrical aberrations.............................................. - 20 -
3.3.4 Examples ..................................................................................................................................... - 21 -
3.4 MICROSTRUCTURE ANALYSIS ...............................................................................................................- 26 -
3.4.1 Origins of specimen line broadening .......................................................................................... - 26 -
3.4.2 The Double-Voigt Approach for size - strain analysis ................................................................ - 29 -
3.4.3 Comparability of results.............................................................................................................. - 30 -
3.5 CONCLUDING REMARKS........................................................................................................................- 31 -
4 REFERENCES.......................................................................................................................................... - 33 -
- 1 -
2 THE GUI
TOPAS-Academic uses the GUI capabilities of BRUKER-AXS TOPAS operating in Launch mode
(2006, General profile and structure analysis software for powder diffraction data. - User's Manual,
BRUKER AXS, Karlsruhe, Germany) . Launch mode is controlled by an INP format text file. The INP
script is described in the Technical Reference.
TOPAS-Academic is by no means an incomplete program. On the contrary the full power of BRUKER-
AXS TOPAS is only realized through Launch mode.
This manual describes the Lunch mode GUI related features. The later sections describe peak shape
modelling via convolution.
Items marked with (GUI) apply either partly or wholly to BRUKER AXS TOPAS operating in GUI mode.
1.1.. Elements of the user interface
Fig. 2-1 shows the main elements of the GUI. The Scan Window is where scans are displayed, the Fit
Window controls refinement, the Parameters Window contains a tree view representation of loaded
data and the Structure Viewer displays structures.
The Scan Window, Fit Window and OpenGL windows can be docked at the left, right, top or bottom of
the main window; Fig. 2-1 shows them docked at the top. The Scan Window contains the Quick Zoom
Window.
Data can be displayed in a single Scan Window or in individual Scan Windows; these can be tiled
horizontally, vertically, cascaded and closed using the appropriate Window menu commands. If there
are no Scan Windows then a Scan Window is created when a scan in loaded. Closing a Scan Window
does not unload its data; the data can be redisplayed by clicking on the corresponding coloured square
of the Treeview.
Tables 2-1 describes the Menu commands, Toolbars and icons of the main window.
When moving the mouse onto a phase name, the intensity distribution of the phase is displayed with a
bold line. Additionally the hkl markers for the phase are highlighted using small triangles at the bottom
of the markers. When moving the mouse onto the hkl markers, the cursor will lock-on to the nearest hkl
marker. After lock-on the marker will be highlighted using a small triangle at the top of the marker and
some hkl information is displayed. hkl's for systematic overlaps are also shown.
The Quick Zoom Window displays the complete scan which is particularly useful if the Scan Window is
displaying a zoomed area. Inside the Quick Zoom Window a zoom rectangle is displayed which
represents the data range within the Scan Window. It allows a modification of the zoomed area by
grabbing one of the red lines with the mouse and moving it. A double click on the Quick Zoom Window
resets the Scan Window to full scale. Panning is also possible by clicking and dragging the zoomed
rectangle with the RMB or using the mouse wheel.
- 2 -
Parameters Window Main Window Fit Window

Quick Zoom Scan Window Phase names Structure Viewer

Fig. 2-1. Main windows of TOPAS-Academic.
1.2.. Parameters Window
Only the features applicable to Launch mode is of concern (GUI) to TOPAS-Academic; this includes the
display of loaded scans in the Treeview, the ability to change chart colors, and the retrieval of hkl
information from the kernel in order to display hkl tick marks and quantitative information.
Using the coloured square displayed next to the Scans tree node, scans can be turned on or off for
displaying in the Scan Window. The Global/Path Tree tab allows for the unloading of scans by clicking
on the left most column of the gird to select the scans to unload and then pressing the Delete key.
- 3 -
Most tree items have short cut menus via the RMB. Alternatively the contents of these menus are also
mirrored at the bottom of the Treeview.
1.3.. Y-axis limits, zooming, panning and selecting
The Y-axis minimum and maximum limits, Y1 and Y2, can be fixed or unfixed using the Fix Y1 and Fix
Y2 toolbar icons. Fixing options include fixing of Y1 to zero as well as to the minimum count value, and
Y2 to the maximum count value. Fixing Y1 and/or Y2 affects zooming and panning behaviour.
Zooming can be performed in both the Scan Window and the Quick Zoom Window. Zooming is
performed by pressing the LMB at the upper left position of the targeted zoom area and dragging the
mouse to define the zoom area. By doing the same backwards, the axes are reset to the full X and Y
scale. Alternatively pressing the mouse wheel and scrolling zooms/unzooms the scan window. For
zooming out the X-scale can be compressed using the Compress toolbar icon. The previously zoomed
region can be reset using the short cut menu command Reset Axes to Previous.
Alternatively the rectangle in the Quick Zoom Window allows a modification of the zoomed area by
grabbing one of the red lines with the mouse and moving it. A double click on the Quick Zoom Window
resets the Scan Window to full scale. Note, if Y1 or Y2 have been fixed to the minimum or maximum
count value respectively, the y-axis limits will be automatically adjusted to the lowest and highest count
value within the zoomed x-region.
X and Y limits can also be set directly to discrete values using either the short cut menu or the chart
options dialog.
Panning in both the Scan Window and the Quick Zoom Window is performed by pressing the RMB and
moving the mouse, the zoomed area is moved over the data range horizontally and vertically; vertical
panning requires Y1 and/or Y2 to be unfixed.
Horizontal panning is also possible using the horizontal scroll bar which is displayed if View - Horizontal
Scroll Bar has been selected.
When panning horizontally with fixed Y1 and Y2, the y-axis limits will automatically adjust whilst moving
the zoomed region along the x-axis.
1.4.. Scan Window - Short Cut Menu
Clicking the RMB within the Scan Window opens a short cut menu offering fast access to the following
features:
Set X1 / X2 / Y1 / Y2 to Mouse Position sets the x- and y-axis limits to the actual mouse position. Fixed
Y1 or Y2 axis limits will be automatically unfixed to allow the setting of Y1 and Y2.
Reset Axes to Previous resets to the previously zoomed region.
Unzoom resets axes to the full X and Y scale.
Edit / Print / Chart Options opens the Chart Options Dialog for defining various chart properties such as
labels, ticks and fonts, which can be saved as defaults. Charts can be printed directly or copied to the
clipboard.
- 4 -
1.5.. Chart Options Dialog
This Dialog, Fig. 2-2, is linked to the short cut menu of the Scan Window (RMB) and provides two
pages; one for copying to Clipboard and printing of the chart and the other for changing the display
properties of the Scan Window. Settings are saved in STARTUP.DEF with the exception of the x- and
y-axis limits, which cannot be kept as defaults. Note, changing the Y1/Y2 axis limits requires them to be
unfixed.
Fig. 2-2. Chart Options Dialog
1.6.. Fit Window
This is the central place for controlling a refinement process, Fig. 2-3. It consists of a text field and a
plot window, and is a normal top level window which can be docked at the left, right, top or bottom of
the Working Area.
- 5 -
Fig. 2-3. Fit Window.

The text field displays refinement information such as space group information, number of independent
parameters, and details about the refinement iterations including iteration number, elapsed time, Rwp as
well as Rwp difference, and the number of Marquardt cycles (MC).
The plot window shows an Rwp plot versus
refinement cycle; it is updated according to the
Graphics Response Time as described later. This
window offers the same zooming and panning
possibilities as the Scan Window; additionally,
similar toolbar icons as well as a short cut menu
(RMB) are available. When zooming into the Rwp
plot, updating stops in order to allow examination
of the zoomed region. Updating can be started
again using the Keep X2 at max X toolbar icon, an
unzoom operation will show the whole Rwp plot
again.
The Refinement Options Dialog Fig. 2-4 (GUI)
offers several options to control the refinement
mainly in GUI mode. Of concern to TOPAS-
Academic is the Graphics Response Time which
defines the update frequency of the Scan Window
and the Rwp plot window. Increasing the time
between updates will give more CPU time for
numerical calculations.
Fig. 2-4. Refinement Options Dialog.

- 6 -
1.7.. OpenGL Structure Viewer
Structures can be viewed in an OpenGL window using the View/Hide Structure short cut menu item
invoked with the RMB over the structure node of the Tree view of the Parameters window. Typically a
refinement is Step initiated using the Step icon of the Fit Window. Then the structure viewer is displayed
and the refinement continued using the Run icon of the Fit Window. As the refinement continues the
structure viewer is updated providing animated refinement in 3D.
Alternatively the structure viewer can be invoked from within an INP file using the structure dependent
keyword view_structure.
The LMB down and dragging in the OpenGL window performs rotation and the RMB down and
dragging performs zooming.
Additionally holding down the Shift key and using the LMB and dragging performs rotation around an
axis perpendicular to the computer screen. The sensitivity of rotation decreases as the mouse position
moves away from the center of the window. This is very important for precise positioning of objects.
Pressing the RMB without mouse
movement bring up the context sensitive
menu on the right whose options allow for
isolating atoms and displaying fragments of
connecting atoms.
1.8.. Rigid body Editor Window
Invoked by the Tools / New-Rigid-body Editor window menu option. Allows for the editing of rigid bodies
and structures Fig. 2-5. It can also load and display cloud *.CLD and *.INP files. The format of *.RGD,
*.STR and *.INP is is INP format as described in the Technical Reference. Rigid body and structure
examples are provided in the RIGID directory.
Existing rigid bodies can be loaded by traversing the directory tree or by entering the file name in the
second column from the top. Clicking on files displays the item in the top two right columns. The item
can then be placed into the main viewing area (bottom of window) using the Load from above menu
item.
Rigid bodies can be modified / created by writing the INP text in the text area at the left of the window.
Updates of the OpenGL graphics is achieved by pressing Alt+F1.
New rigid bodies can be created and saved using the Save As option.
- 7 -
Add torsion angle is performed by first selection two atoms (pressing the LMB over the atoms) and
then clicking on the Add torsion angle menu option. This inserts a Rotate_about_points macro
(defined in TOPAS.INC).
Fig. 2-5. Rigid body editor window.
1.9.. Options Dialog
Provides several mouse control
modes.
Fig. 2-6. Options Dialog
Arrow corresponds to normal mouse operation for zooming and panning.
Insert Peak (GUI) shows the Peak Details Dialog and switches the mouse to peak insertion mode.
Capture (GUI) captures observed, calculated and difference plots in the Scan Window. After clicking on
- 8 -
the diagram line a new Scan Window is opened which contains the captured data including all
associated parameters. This feature allows for the export of any calculated data in a separate data file.
Manipulate X allows the movement of a selected scan in the positive or negative x-direction. This
feature is useful for comparing different data sets or for visualisation of 2u errors. Note, the data set in
memory which constitute loaded data is directly manipulated; the original data file remains unchanged.
Manipulate Y is similar to Manipulate X but in the y-direction. Note, the data set in memory which
constitute loaded data is directly manipulated; the original data file remains unchanged.
Exclude Region (GUI) allows the exclusion of selected data regions from calculations. Excluded regions
are defined with the mouse by clicking and dragging. An unlimited number of excluded regions are
allowed including the case of overlap.
Select allows the selection of peaks and excluded regions in the Scan Window.
1.10 Printing and reporting
Data grid information can be copied to the clipboard or transferred to the TopasEditor or Microsoft Word
(if available) using the short cut menu of the data grid shown in Fig. 2-7 (GUI). Available options are:
Copy all/selection copies the full page or the selection to the clipboard.
Copy all/selection, create TopasEditor document launches the TopasEditor and transfers the full page
or the selection into a new document in RTF format.
Copy all/selection, create Word document launches Microsoft Word (if available) and transfers the full
page or the selection into a new document in DOC format based on the currently defined document
template (default is TOPAS.DOT).
DOT file: topas.dot is template file for Microsoft Word (if available). This feature allows for the creation
of customized reports with, for example, user-defined headers, footers, page numbering and etc... Note,
Topas.dot does not contain macros, however to use DOT files containing macros the security level of
Microsoft Word for opening files must be set to either "low" (not recommended) or "medium"; if set to
"high" macros are disabled.
Save to TXT file saves the full text field or the selection to an ASCII text file.
Print directly sends the full text field or the selection to the default printer.

a) b)
Fig. 2-7, Short cut menu of the data grid showing available options for (a) grid pages and (b) text fields.
- 9 -
1.11 Program defaults
Defaults are controlled using ".DEF" files stored in the main TOPAS-Academic directory (GUI); these
are as follows:
STARTUP.DEF is loaded when the GUI is started. Its contains the global display defaults which can all
be set from within TOPAS-Academic, theres no need to edit this file directly.
RANGE.DEF is loaded and attached to ranges as they are created. All range dependent
keywords/macros can be used in this DEF file.
STR.DEF is loaded and attached to structures as they are created. All structure dependent GUI
keywords/macros can be used in this DEF file.
HKLI.DEF is loaded and attached to hkl_Is phases as they are created in the GUI. All hkl_Is dependent
GUI keywords/macros can be used in this DEF file.
CIF.DEF is loaded when a CIF file is attached to structure phases. All structure dependent GUI
keywords/macros can be used in this DEF file.
1.12 Operation
INP files contain all information for controlling TOPAS-Academic in Launch Mode and can be modified
by a text editor. Notepad is set as the default editor. A user specified editor can be made permanently
active by selecting Launch - Editor. In Launch mode refinement results are written to an output file
(*.OUT) which has the same format as the INP file. The output file can be inspected by selecting
Launch - Edit OUT File. After a refinement the User is asked whether to update the INP file with the
OUT file.
Scans loaded from Launch mode are placed into the Parameters Window for graphical display
purposes. Editing of Grid entries has no bearing on the fitting process which is controlled entirely from
the INP file.
The file LAUNCH_FILE.TXT in the main TOPAS-Academic directory can contain the name of an INP
file name to which TOPAS-Academic with operate on. If the file exists then an INP file name is read
from it and Launch mode is set to operate on this file.
The file TOPAS.INC contains standard macros in INP format; it is useful to have loaded in your editor.
The Technical Reference describes the Test Examples provided in the TEST_EXAMPLES directory;
over 70 examples covering the functionality of TOPAS-Academic is provided.
In addition the INDEXING directory contains indexing examples.
- 10 -
3 PEAK SHAPE MODELLING
TOPAS-Academic provides a general convolution approach to X-ray and neutron powder data, which
an accurately convolute and refine a wide variety of profile shapes numerically, including user efined
profiles, without the need to convolute analytically. Generally any combination of appropriate unctions
may be used in this context for modeling profiles empirically, including "classic" analytical eak shape
functions (PSF). With functions representing both the aberration functions of the iffractometer as well as
the various specimen contributions, a fundamental parameters based ynthesis of line profile shapes is
achieved (fundamental parameters approach, FPA).
Pofile fitting methods can be divided into the following two broad categories:
1) Analytical Profile Fitting
This method is generally characterized by PSFs with an explicit and relatively simple mathematical orm
which can be differentiated analytically with respect to each of the refined parameters within the east
squares refinement procedure. The most common PSFs in analytical profile fitting are the aussian,
Lorentzian, sums of Gaussians or Lorentzians, Voigt, pseudo-Voigt and Pearson VII unctions where the
angular dependence of the peak shape is described by smoothly varying functions ith 2u (e.g. Howard
& Preston, 1989; Snyder, 1993; Young, 1993). Although these functions are onvenient to use they are
often unable to fit X-ray profiles well over the whole 2_ range without using large number of
parameters.
2) Direct Convolution Approach
In this method profiles are generated by convolution where various functions are convoluted to form the
observed profile shape. For a convolution of n functions this process is written as:
Y(2u) = W F
1
(2u) F
2
(2u) ... F
i
(2u) ... F
n
(2u) (3-1)
where
Y(2u) is the observed line profile shape,
W is the source emission profile, and
denotes the convolution process.
In powder diffractometry the functions F
i
(2u) can be interpreted as both the aberration functions of the
diffractometer (Wilson, 1963) as well as the various specimen contributions leading to the so-called
FPA. More generally any combination of appropriate functions Fi(2u) may be used in this context.
A wide variety of profile shapes can be accurately convoluted and refined, both numerically and
analytically, without the need for explicit analytical convolution. Of significance is the ability to construct
profile shapes with any shape dependence on angle and hkl direction out of a pool of aberration
functions (including all analytical PSFs mentioned above as well as user defined functions) using a
mixture of analytical and numerical convolutions and to fit the PSFs to the observed line profiles with all
parameters refineable.
The use of physically based instrument aberration functions as opposed to empirically based functions
leads directly to the special case of the fundamental parameters approach with all instrument
parameters refineable. This approach is used within all currently employed profile fit methods including
(i) single line fitting, (ii) whole powder pattern fitting, (iii) whole powder pattern decomposition according
- 11 -
to Pawley (1981) and Le Bail et al. (1988), (iv) Rietveld refinement (Rietveld, 1967, 1969) and (v) ab-
initio structure determination from step intensity data (Coelho, 2000).
3.1 Source emission profiles
The knowledge of the exact shape of the source emission profile is of central importance to the
development of an accurate powder profile description. In the absence of instrumental effects the
spectral shape represents the highest possible resolution of a diffractometer and above 90 2u the
emission profile is the dominant contribution to the line profile shape. In the region 2u R 40 the
contribution of the emission profile is swamped by the geometrical aberrations. At 2u > 60, the
emission profile tends to dominate over the geometrical aberrations and at 2u >100 the total breadth of
the geometrical aberrations are relatively small and the profile shape conforms closely to the emission
profile.
Unlike for laboratory X-ray diffraction (transition element anodes), the source emission profiles for
synchrotron and neutron diffraction needs to be determined individually for each instrument, which can
be achieved by scanning a suited standard and refining on the source emission profile parameters. It
may be necessary to include more than one emission profile line to accommodate line asymmetry.
Unlike synchrotron and neutron diffraction, the source emission profiles of the transition element
anodes used in laboratory X-ray diffraction do not have simple descriptions, but are well known from
literature (Hlzer et al. 1997; Berger, H. 1986).
Laboratory X-ray diffraction
The form of the Ko
1,2
emission profile from Cu is shown in
Fig. 3-1. For all of the transition element anodes used in X-ray diffraction neither the Ko
1
nor the Ko
2
lines are purely Lorentzian in shape and both lines are asymmetric with extended high angle tails.
Moreover the asymmetries and FWHM values of the Ko
1
and Ko
2
peaks are different.

Fig. 3-1: Phenomenological
representation of the Cu Ko
emission profile based on four
Lorentzians (from Cheary et
al., 2002).
1.538 1.540 1.542 1.544 1.546
Ko
2
Ko
1
Wavelength ()

The natural asymmetry of the emission lines arises from the multiplet structure of the transitions. In
addition to the main transitions involving the change in vacancy state 1s U2p, it has been recognised
that 3d spectator transitions also contribute up to 30% of the Ko
1
o
2
emissions (Hlzer et al., 1997). In
these transitions the atom is doubly ionised and the actual vacancy transition is still 1s U2p , but the
second vacancy in the 3d level is not directly involved in the transition. The notation for this transition is
1s3dU2p3d. A phenomenological representation for accurately describing the asymmetric Cu emission
profile was first used by Berger (1986). In this model the Ko
1
and Ko
2
lines are each represented as the
sum of two Lorentzian profiles as shown in Fig. 3-1.
- 12 -
For Cr, Mn, Fe, Co, Ni and Cu the phenomenological representations are used to accurately represent
the emission profiles from these elements with up to seven Lorentzians being used in some cases.
Another aspect of Ko emission lines required for accurate line profile analysis is the satellite multiplet
structure in the high energy tail as shown in
Fig. 3-2 and Fig. 3-3. For Cu these collectively have an intensity of ~ 0.6% of the Ko
1
emission line. In
X-ray diffraction studies it is sufficient to represent the Ko satellite group as a single broad Lorentzian;
thus, for the case of Cu Ko a total of five Lorentzians are used to accurately describe the spectrum.

Fig. 3-2. CuKo emission profile
showing the satellite group of
lines and the extent of the tails
from the Ko
1
and Ko
2
emission
lines. This profile was recorded
using the 400 line from a
silicon single crystal wafer
(from Cheary et al., 2002).

67 68 69 70 71
1k
10k
100k
FWHM Ko
1
= 0.045 2u
Ko
2
Ko
1
Range ~ 90 x FWHM(Ko
1
)
Ko Satellites
X
-
r
a
y
C
o
u
n
t
s
2u
Fig. 3-3. Fundamental
parameters fit to the 331 line of
CeO
2
(Balzar, 2001) at about
76.7 2u. Divergent beam data
have been taken with a D8
ADVANCE (BRUKER AXS).
The Ko satellites contribute
significant intensity to the total
profile, which is typically
neglegted in analytical profile
fitting approaches.
75.00 75.50 76.00 76.50 77.00 77.50 78.00 78.50
2u [2u]
Ko satellites
As the natural shape of emission profiles is Lorentzian, the tails can extend a considerable distance
from the central peak as shown in
Fig. 3-2. Most diffractometers, however, operate with K| filtering or some form of monochromatisation
and as such the tails are attenuated to varying degrees as illustrated in
Fig. 3-4. When a Ni K| filter is inserted in the beam of CuKo the attenuation appears to be more or less
uniform across the profile except for below the Ni K absorption edge. The inclusion of a curved graphite
monochromator in the diffracted beam greatly reduces the range of wavelengths entering the detector
resulting in profile tails that diminish more rapidly than the natural emission profile. These
monochromators can also affect the relative intensity I
Ko2
/I
Ko1
by up to 10% depending on the
alignment and setting of the crystal. For example, in the monochromated spectrum shown in
- 13 -
Fig. 3-4 the relative intensity of the Cu Ko
1
/Ko
2
is approximately 0.46 rather than 0.50 as in the
unfiltered spectrum.

Fig. 3-4. CuKo emission profile obtained
using the 400 line from a silicon single crystal
wafer. Each pattern was recorded
sequentially using the same sample, first with
no filter or monochromator in the beamline,
then with a Ni K| filter, and finally with a
standard curved graphite diffracted beam
monochromator (from Cheary et al., 2002).
66 67 68 69 70 71 72 73
10
0
10
1
10
2
10
3
10
4
10
5
Effect of
Graphite
Monochromator
Ni K
Absorption Edge
Effect of
Ni K| Filter
Cu Ko Unfiltered
X
-
r
a
y
C
o
u
n
t
s
2u
Ground and bent Johannson monochromators achieve perfect focusing when correctly aligned and
are able to select a very narrow band of wavelengths. Fig. 3-5 shows an example spectrum for
CuKo from an asymmetrically cut ground and bent Ge crystal used as an incident beam
monochromator. The wavelength band-pass is narrow enough to remove 99.98% of the Ko
2
component
and 100% of the Ko satellite group. Also seen is that the Lorentzian tails are effectively eradicated.
68.8 69.0 69.2 69.4 69.6
Original Cu Ko
Spectrum
Monochromated
Spectrum
2u
a)
68.8 69.0 69.2 69.4
100
1k
10k
100k
Ko
1
Residual Ko
2
X
-
r
a
y
C
o
u
n
t
s
2u
b)
Fig. 3-5: Wavelength spectrum emerging from an asymmetrically cut Ge111 ground and bent incident
beam monochromator presented linearly (a) and logarithmically (b). The Ko satellites are completely
removed, but the Ko
2
is still present at ~0.02% of Ko
1
even in a well aligned system (from Cheary et
al., 2002).
In Table 3-1 two example descriptions for the Cu Ko emission profile are shown. In this table "CuKa5"
represents the characteristics of the four main Ko lines and the Ko satellite group by 5 Lorentzians,
where the sattelite is described by a broad single Lorentzian. For comparison the simple two line model
"CuKa2_analyt" is given as well, in which same shape and same width for the Ko
1
and Ko
2
components
with an intensity ratio of 0.514 is defined. A list of all emission profiles supported by TOPAS is provided
in Table 3-2.
- 14 -
Table 3-1. Two examples of the Cu Ko emission profile. : wavelength; I
Rel
: relative intensity; lh:
Lorentzian halfwidth (parameters are described in the Technical Reference manual).
Emission profile Emission lines [] I
Rel
lh [ x 10
-3
]
CuKa5 Satellites 1,534753 1,59 3,69
Ko
1a
1,540596 57,91 0,44
Ko
1b
1,541058 7,62 0,60
Ko
2a
1,544410 24,17 0,52
Ko
2b
1,544721 8,71 0,62
CuKa2_analyt Ko
1
1,540596 66,05 0,50
Ko
2
1,544493 33,95 0,50
Table 3-2. Emission profiles provided in the LAM directory. The name components "Holzer" and
"Berger" denote source emission profiles taken from Hlzer et al. (1997) and Berger (1986)
respectively
Anode material Ko K|
Cu CuKa1
1)
CuKa2
CuKa2_analyt
CuKa4_Holzer CuKb4_Holzer
CuKa5
CuKa5_Berger
Co CoKa3
CoKa7_Holzer CoKb6_Holzer
Cr
CrKa7_Holzer CrKb5_Holzer
Fe
FeKa7_Holzer FeKb4_Holzer
Mn
MnKa7_Holzer MnKb5_Holzer
Ni
NiKa5_Holzer NiKb4_Holzer
Mo
MoKa2
1)
Monochromatic Cu emission profile for instruments equipped with Johannson-type Ge primary
monochromator
3.2 Direct convolution approach: Empirical parameterisation
3.2.1 General considerations
In the literature, convolution based profile fitting is typically associated with microstructure analysis
where the specimen contribution is separated from the instrument contribution (e.g. Howard & Preston,
1989; Snyder, 1993). It can however also be used in an empirical manner to provide a greater variety of
profile shapes resulting in better fits. The two general areas of application for convolution based profile
fitting are:
1) The purely empirical parameterization of line profile shapes by convolution of appropriate functions
F
i
(2u) according to Eq. (3-2); a schematic of which is shown in Fig. 3-6.
2) The explicit discrimination of instrument and specimen contributions (Jones, 1938):
- 15 -
Y(2u) = (W G) S, (3-2)
where G and S are instrument and sample contributions respectively which are modeled separately
using appropriate F
i
(2u) functions according to Eq. (3-1).
In general, a particular target system or instrumental setup (W G) is seen as an entity called the
instrument function I(2u), which can be either measured (conventional approach) or calculated from
first principles based on the known instrument geometry (fundamental parameters approach, which
is discussed in detail later).
In the conventional convolution approach an instrument function I(2u) is determined experimentally from
a standard material, which ideally should (but does not) meet the following requirements: (i) large
crystallite size to minimize size broadening, (ii) small crystallite size to give sufficient particle statistics,
(iii) no strain and (iv) possess the same linear absorption coefficient as the specimen. The instrument
function is then convoluted with specimen related functions to represent the "real" specimen properties.
Obviously the requirement to have both large and small crystallites simultaneously is a contradiction
and limits the accuracy of microstructure analysis at small levels of specimen broadening. In many
approaches such as the Double-Voigt Approach (e.g. Balzar, 1999), Lorentzian and Gaussian functions
are employed to describe both crystallite size and strain effects.
In principle any instrument function can be described using the conventional convolution approach.
However, the quality of the instrument function is directly related to the quality of the standard material
and thus additional broadening in the instrument function is unavoidable for reasons described above.
As a result specimen broadening is underestimated resulting in erroneous specimen characteristics
such as over-estimated crystallite size estimates.
A further drawback is that the instrument function needs re-determination when relevant instrument
settings, such as slit settings, change. In addition the effects of sample penetration by the incident
beam is often overlooked resulting in increased broadening in the instrument function. This is an
intrinsic error to the conventional convolution approach whereby the instrument function is linked to
sample preparation (packing density).

- 16 -
Emission Profile
-
0 +
W
Final Profile
-
0 +
Y(2 ) u
Hat
- 0 +
Gaussian
-
0 +
Lorentzian
-
0 +
Hyperbolas, Circles,
Exponentials
- 0 + - 0+
Split Functions
-
0 +
Hat + Hat
-
0 +
Hat Hat
-
0 +
F(2 )
i
u
Y(2u) = W F
1
(2u) F
2
(2u) ... F
i
(2u) ... F
n
(2u)
Fig. 3-6. Schematic representation of the convolution approach as given in Eq. (3-1). The final profile
Y(2u) is described by the selection of appropriate functions F
i
(2u) and convoluting them on top of the
emission profile W. Note the capabilities of this approach to add functions before convoluting them as
shown for the sum of two hat functions as well as to convolute split-type functions.
3.2.2 Example
The following illustration demonstrates the power of the empirical convolution approach by accurately
fitting all of the CeO
2
data made available as part of the size-strain round robin conducted by the IUCr
CPD
1
(Balzar, 2001):
laboratory X-ray data (D8 ADVANCE, BRUKER AXS)
synchrotron X-ray data (NSLS X3B1, ESRF BM16)
CW neutron data (ILL D1A, NCNR BT1)
TOF neutron data (ISIS HRPD)
Two datasets were collected from each instrument; one well crystallized specimen to determine the
instrument functions and one specimen exhibiting strong specimen broadening.
The functions used to fit the data were chosen from the "function pool" shown in Fig. 3-6. An attempt
was made to minimize the number of functions and the number of parameters used.
In Fig. 3-7 to Fig. 3-10 the refinement results are shown for the most asymmetric peaks for the lab X-ray
data (D8 ADVANCE, Fig. 3-7), synchrotron X-ray data (NSLS X3B1, Fig. 3-8), CW neutron data (ILL
D1A, Fig. 3-9), and TOF neutron data (ISIS HRPD, Fig. 3-10). The data representing the measured
instrument functions are shown in Fig. 3-7a to Fig. 3-10a, respectively (in the following referenced as
"sharp data"). The broadened data are shown in Fig. 3-7b to Fig. 3-10b, respectively, together with the
instrument functions determined from the measured standard data scaled to the maximum peak
intensity.

1
International Union of Crystallography, Commission on Powder Diffraction
- 17 -
A maximum of 5 refineable parameters were required to fit the sharp data including its dependence on
angle / d. To describe the broadened data across the whole angular range and to obtain microstructure
information two Voigt functions comprising 4 refinable parameters were convoluted on top of the
instrument function (Double-Voigt Approach, e.g. Balzar, 1999). The microstructure results together
with the round robin equivalents (Balzar, 2001) are shown in Table 3-3. The excellent agreement seen
for all datasets quantitatively demonstrate the superior performance of convolution based profile fitting
on a wide variety of profile shapes and diffraction instruments.

28.00 28.20 28.40 28.60 28.80 29.00
2u [2u]
CeO
2
(D8 ADVANCE)
Fig. 3-7a. Laboratory X-ray data, measured
instrument function (D8 ADVANCE, BRUKER
AXS).
27.50 28.00 28.50 29.00 29.50
2u [2u]
CeO
2
(D8 ADVANCE)
Fig. 3-7b. Laboratory X-ray data, broadened data
(D8 ADVANCE, BRUKER AXS).

12.70 12.75 12.80 12.85 12.90 12.95 13.00
2u [2u]
CeO
2
(NSLS X3B1)
Fig. 3-8a: Synchrotron data, measured
instrument function (NSLS X3B1).
12.55 12.65 12.75 12.85 12.95 13.05 13.15
2u [2u]
CeO
2
(NSLS X3B1)
Fig. 3-8b. Synchrotron data, broadened data
(NSLS X3B1).

- 18 -
33.50 35.50 37.50 39.50 41.50 43.50
2u [2u]
CeO
2
(ILL D1A)
Fig. 3-9a. CW neutron data, measured
instrument function (ILL D1A).
33.50 35.50 37.50 39.50 41.50 43.50
2u [2u]
CeO
2
(ILL D1A)
Fig. 3-9b. CW neutron data, broadened data (ILL
D1A).

1.89 1.90 1.91 1.92 1.93
d []
CeO
2
(ISIS HRPD)
Fig. 3-10a. TOF neutron data, measured
instrument function (ISIS HRPD).
1.87 1.89 1.91 1.93 1.95
d []
CeO
2
(ISIS HRPD)
Fig. 3-10b. TOF neutron data, broadened data
(ISIS HRPD).

Table 3-3. Microstructure results for the size-strain round robin data (Balzar, 2001). Results are also
given for the ESRF BM16 and NCNR BT1 data. The round robin results are provided in the last row.
L
Vol
represents the volume weighted column length.
LVol [nm] Strain
D8 ADVANCE 23.43 (0.08) 0.0149 (0.0014)
NSLS X3B1 23.72 (0.08) 0.0307 (0.0014)
ESRF BM16 22.59 (0.05) 0.0143 (0.0010)
ILL D1A 23.29 (0.18) 0.0273 (0.0034)
NCNR BT1 23.88 (0.34) 0.0259 (0.0052)
ISIS HRPD 22.93 (0.06) 0.0193 (0.0021)

Balzar (2001) 22.60 (0.90) "nearly strain free"
- 19 -
3.2.3 Use of classic analytical functions
Table 3-4: Analytical PSFs supported. If more than one emission line is used, information about
intensity and line width ratios are taken from the source emission profile; for generic unit area
expressions and definitions of the PSF dependent parameters refer to the Technical Reference
manual.
PSF: Name: PSF dependent parameters:
Single line fitting:
Gaussian
1)
G Ia, 2u
k
, fwhm
Lorentzian
2)
L Ia, 2u
k
, fwhm
PearsonVII PVII Ia, 2u
k
, fwhm, m
Pseudo-Voigt PV Ia, 2u
k
, fwhm, q
Split PearsonVII SPVII Ia, 2u
k
, fwhm1, fwhm2, m1, m2
Split PseudoVoigt SPV Ia, 2u
k
, fwhm1, fwhm2, q1, q2
Whole pattern fitting:
PearsonVII PVII Ia, ha, hb, hc, ma, mb, mc
Modified Pseudo-Voigt PV_MOD Ia, ha, hb, hc, lora, lorb, lorc
TCHZ Pseudo-Voigt PV_TCHZ Ia, U, V, W, X, Y, Z
1)
PV function with mixing factor q = 0
2)
PV function with mixing factor q =1

The split functions allow for peak asymmetry. For asymmetry correction in whole pattern fitting various
functions are available ("Finger Model", Finger et al., 1994; "Simple and Full Axial Models", Cheary &
Coelho, 1998a, b), which are to be convoluted on top of the choosen PSF.
3.3 Direct convolution approach: Fundamental parameters
3.3.1 General considerations to FPA
FPA line profile shapes are characterized in terms of the physical parameters describing the
diffractometer or the diffraction process (Cheary & Coelho, 1992, 1994, 1998a, 1998b; Cheary et al.,
2002). Similar to Eq. (3-2) observed line profile shapes Y(2u) are described by convoluting the source
emission profile with the instrument aberrations; sample broadening is also incorporated by convolution.
In other words FPA represents Y(2u) in terms of the dimensions of the diffractometer and the physical
properties of the sample according to
Y(2u) = (W G) P S, (3-3)
where P represents the sample contribution function
The instrument function I(2u)=(WG) in terms of the individual aberrations G
i
(2u) can be written as:
I(2u) = W G
1
(2u) G
2
(2u) ... G
i
(2u) ... G
n
(2u) (3-4)
Thus it is seen from Eq. (3-1) and Eq. (3-4) that FPA is a special case of convolution based profile
fitting. The important difference is that I(2u) for FPA is determined from prior knowledge of the emission
- 20 -
profile and diffractometer geometry resulting in far fewer refinable profile parameters. This results in
decreased correlations between the profile, background and in particular microstructural parameters
leading to an overall improvement of the refinement process within all profile fitting methods.
It is clear from Eq. (3-3) that FPA explicitly distinguishes between sample transparency and related
microstructure broadening . While sample contributions are unavoidable, FPA allows from profile shape
considerations the independent treatment of aberrations such as the refinement of the linear absorption
coefficient or the thickness of a non-infinitely thick sample (e.g. Kern & Coelho, 1998).
Diffraction broadening analysis is an intrinsic property of FPA. Even in well crystallized powders with
crystallite sizes up to 2m, crystallite size broadening is detectable in high angle lines and it is
necessary to include a physical broadening function in the refinement.
When more than one type of sample broadening is present, FPA affords a multiplicity of broadening
functions that can be convoluted together to form S(2u). For example when crystallite size (c_size) and
stacking fault (s_fault) broadening are present then
S(2u) = S
c_size
(2u) S
s_fault
(2u) (3-5)
Many types of component broadening functions are available including the standard Lorentzian and
Gaussian functions with a full width at half maximum that can be constrained to fit a particular 2u or hkl
dependence.
3.3.2 Applicability of the FPA
The basic objectives of the FPA technique is to fit powder diffraction profiles using physically based
models to describe both the instrument profile and diffraction broadening generated by the specimen. In
principle the technique can be applied to any powder diffractometer and profiles of widely differing
shapes can be accommodated by modifying the physical parameters of the diffractometer used to
describe the profiles.
In general instrument parameters are not refined as they are measurable and known. Second order
effects however often lead to slight variations in some of the instrument parameters and refinement of
one or two parameters is sometimes necessary. For example, strongly oriented thin films and powders
generally produce narrower than expected line profiles simply because the diffraction cone is
incomplete. During refinement, this type of problem can be accommodated by refining on one of the
axial divergence parameters, such as the diffracted-beam Soller angle, which typically refines to a value
that is slightly different from the measured value.
Because the instrument contribution to line profile shapes can be predicted, instrument optimization is
possible where an appropriate balance between intensity and resolution can be deduced. It is also
possible to assess instrument alignment by comparing expected and observed profile shapes.
3.3.3 Diffractometer configurations and their geometrical aberrations
3.3.3.1 Divergent Beam Laboratory Diffractometers
In the conventional divergent beam laboratory diffractometer, diffraction is symmetric and the principal
geometric aberrations contributing to a profile alongside the wavelength distribution are,
- 21 -
the finite width of the X-ray source
flat specimen error
finite angular acceptance of the receiving optics (receiving slit)
specimen transparency
axial divergence
As discussed above, both primary and secondary monochromators modify the source emission profile
significantly and also reduce axial divergence (Cheary & Coelho, 1998a, 1998b; Cheary et al., 2002).
Position sensitive detectors (PSDs) lead to additional contributions to the instrument function. PSDs
used in divergent beam laboratory diffractometers are of the linear, step-scanned type with a small
acceptance angle of up to 10 2u, which are mounted tangentially to the detector circle. For such a
detector the only position on the detector that is normally in focus is its centre. All beams diffracted from
planes angled relative to the specimen surface will enter the detector at off-centre positions
(asymmetric diffraction). Additional aberrations are
defocusing due to asymmetric diffraction
discharge resolution of the detector
parallax error
3.3.3.2 Parallel Beam Diffractometers
In parallel beam diffractometers with analyser foils and / or analyser crystals and / or channel cut
monochromators in the primary or diffracted beam there are only two active geometric aberrations
namely,
axial divergence
finite angular acceptance of the receiving optics
PSDs used in parallel beam diffractometers are either linear, step scanned detectors as described
above, or large curved stationary detectors with acceptance angles of up to 150 2u. In case of a PSD
there are additional aberrations dependent on its type; these are
discharge resolution for both detector types
parallax error for linear detectors
In laboratory diffractometers, the parallel beam is produced by a parabolic graded multilayer mirror (so-
called "Gbel mirror"; Schuster & Gbel, 1995) with the line X-ray source positioned at the focus of the
mirror. Although the beam may be parallel in the equatorial plane, it will not be parallel in the axial plane
and axial divergence is present in both the incident and diffracted beams. Low angle profiles will
therefore be asymmetric although not to the same extent as diverging beam instruments. Gbel mirrors
as well as analyzer crystals and / or channel cut monochromators will in addition significantly change
the source emission profile as discussed above.
3.3.4 Examples
3.3.4.1 Example FPA single line fitting
Fig. 3-11 demonstrates the FPA based convolution process for the (100) reflection of LaB
6
at 21.35 2u.
The CuKo emission profile scaled to the peak intensity maximum is shown in Fig. 3-11a. The emission
profile accounts for the asymmetric line shapes of Ko
1
and Ko
2
, and the "Ko
3
" satellite as well. Fig.
3-11b convolutes equatorial instrumental contributions with the emission profile, Fig. 3-11c further
- 22 -
convolutes the axial instrumental contributions. Further convolutions for microstructure contributions,
represented by crystallite size and strain, result in the excellent fit seen in Fig. 3-11d. Note that the
calculated peak maximum position is offset from the Bragg 2u position; this is expected and there are
two reasons for it. First the centroids of some of the aberration profiles are different to the Bragg 2u
position and secondly the manner in which Bragg 2u is calculated is based on the wavelength of Ko
1
and not the peak maximum of the emission profile. This reflects one of the benefits of FPA, it
intrinsically corrects for errors in 2u due to instrument and sample aberrations. Thus provided the
aberration models for the aberration functions are correct, FPA gives a Bragg 2u position matching that
determined as if the data were collected with a "perfect sample" on a "perfect instrument" with
monochromatic radiation. Therefore, especially at low angles, the calculated 2u positions do not
generally coincide with the peak maximum.
With FPA the excellent profile shape description as well as the improved determination of peak
positions lead to more accurate lattice parameters in the Pawley, Le Bail and Rietveld procedures. The
instrument function constraint, which improves the description of profile asymmetry, eliminates the need
to refine an asymmetry parameter, which is mandatory in the "analytical functions approach", and also
leads to the refinement of physically meaningful zero point or sample height errors. While the zero point
of modern diffractometers can be easily aligned to better than 0.005 2u, the "analytical functions
approach" typically refines zero point errors in the order of several hundreds of a degree 2u which is
due to poor asymmetry modelling. With FPA this is no longer the case.

- 23 -
21.10 21.20 21.30 21.40 21.50 21.60
2O [2O]
0
20
40
60
80
100
I
rel
W
LaB
6
(100)
SRM 660
a)
21.10 21.20 21.30 21.40 21.50 21.60
2O [2O]
0
20
40
60
80
100
I
rel
Wx G
Eq
LaB
6
(100)
SRM 660
b)
21.10 21.20 21.30 21.40 21.50 21.60
2O [2O]
0
20
40
60
80
100
I
rel
Wx G
Eq
x G
Ax
LaB
6
(100)
SRM 660
c)
21.10 21.20 21.30 21.40 21.50 21.60
2O [2O]
0
20
40
60
80
100
I
rel
Wx G
Eq
x G
Ax
x S
LaB
6
(100)
SRM 660
2u
d)
Fig. 3-11: Step-by-step synthesis of an observed line profile (LaB
6
, 100, SRM660) by convoluting the
source emission profile W (a) with equatorial G
Eq
(b) as well as axial instrument contributions G
Ax
(c)
and finally crystallite size and strain effects S (d). Relative intensities, all calculated intensities in a-c
scaled to the observed peak maximum intensity. From Kern & Coelho, 1998.
3.3.4.2 Treatment of satellite peaks and tube tails
An important advantage of FPA in practice is the ability to easily account for additional scattering
contributions coming from Ko satellite peaks and tube tails (Bergmann, 2000); these contributions are
typically ignored in present "analytical function approaches".
In
- 24 -
Fig. 3-12 an example is shown for the 211 line of LaB
6
, NIST SRM660a. Divergent beam data have
been taken with a D5000 (BRUKER AXS) equipped with an AEG long fine focus tube. The broad
impulse function of tube tails has a width of about 1 2u and an intensity that is approximately 2% of the
total line profile intensity. The R
WP
of the fit shown in
Fig. 3-12 is 3.6%, the Durbin-Watson parameter DW (Durbin & Watson, 1950; Hill & Flack, 1987), which
is a measure of serial correlation and therefore the quality of the fit model, is 1.57, which is close to the
ideal value of 2. Ignoring tube tails yields an R
WP
of 8.9% while DW drops to 0.27; when also ignoring
the Ko satellites R
WP
becomes 12.0% with a DW of 0.16.
Although tube tail effects as large as that shown in
Fig. 3-12 are rare, the Ko satellites are always present in diffraction data taken with sealed tubes and
rotating anodes and, for accurate work, should not be ignored particularly at low levels of specimen
broadening.

Fig. 3-12: Single line fundamental
parameters fit to the 211 line of LaB
6
(NIST SRM 660a) at about 54 2u with
tube tails (square root scale). The blue
line represents the calculated data
without background. Courtesy by Cline
(2001).
53.40 53.80 54.20 54.60
2u [2u]
Ko satellites
Tube tails
3.3.4.3 Quality of fit
One of the outstanding features of convolution based profile fitting is the quality of fit, which is directly
visible from the difference plot, but can also be quantified using agreement indices such as R-values or
the DW parameter. As an example for a single line fit, Fig. 3-13 compares a FPA fit to a split-Pearson
VII (SPVII) fit. The improvement of the various agreement indices provided in Table 3-5 is obvious.
- 25 -
21.10 21.20 21.30 21.40 21.50 21.60
2u [2u]
LaB
6
(SRM660a)
SPVII
a)
21.10 21.20 21.30 21.40 21.50 21.60
2u [2u]
LaB
6
(SRM660a)
FPA
b)
Fig. 3-13: Comparison of a single line fit to the 100 line of LaB
6
(SRM660a) with a SPVII function (a)
versus a FPA fit of the same data in (b).

Table 3-5: Agreement indices obtained by the split-PearsonVII (SPVII) and fundamental parameters
approach (FPA) in Fig. 3-13.
R
P
R
WP
R
Exp
GOF DW
SPVII 4.8 6.1 1.9 3.2 0.44
FPA 2.2 3.1 1.9 1.6 1.35
3.3.4.4 Number of fit parameters required
Convolution based profile fitting generally reduces the number of refinable profile parameters and thus
many problems related to over-parametrization such as refinement of redundant parameters and
parameter correlations are minimized. This is illustrated in Fig. 3-14 for a single line fit of the well known
"5 fingers" of quartz using 3 unconstrained Pearson VII functions in Fig. 3-14a and fundamental
parameters in Fig. 3-14b. The Pearson VII functions exhibit an almost perfect fit as indicated by the R
WP

of 2.2%; this however is at the expense of largely divergent half-width and shape parameters
particularly for the second and third peaks. Using fundamental parameters to introduce the instrument
function as a constraint (dotted line in Fig. 3-14b) and fitting independent crystallite size contributions to
each of the peaks results in a slightly worse R
WP
of 2.8%; however, the half-width and shape
divergence problems are removed thus realizing a more stable and meaningful determination of
integrated intensities and analysis of anisotropic peak broadening.
A comparison of the number of profile parameters required in i) single line fitting and ii) whole powder
pattern fitting techniques (where profile parameters are constrained by smoothly varying functions with
2u) such as the Pawley, Le Bail or Rietveld method, is shown in Table 3-6. As can be seen the use of
the instrument function concept within convolution based profile fitting, preferentially with the FPA,
drastically reduces the number of refineable profile parameters, resulting in
improved refinement stability,
increased refinement speed due to faster convergence, and
reduced parameter correlations and therefore more physically meaningful parameters.
- 26 -
67.00 67.50 68.00 68.50 69.00
2u [2u]
a)
67.00 67.50 68.00 68.50 69.00
2u [2u]
b)
Fig. 3-14: Comparison of an unconstrained single line fit to the Quartz "5 finger peak" with SPVII
functions (a) versus a FPA fit of the same data in (b).

Table 3-6: Minimum number of refineable profile parameters required in traditional Analytical Profile
Fitting (APF) and Direct Convolution Approaches (DCA). For definitions of the PSF dependent
parameters refer to the Technical Reference manual.
Single Line Fitting Rietveld, LeBail or Pawley method
APF (SPVII) DCA APF (PVII) DCA
2u
k
2u
k
U, V, W L, G
Ia Ia lora, lorb, lorc
fwhm1, fwhm2 L, G Asymmetry
m1, m2
6 4 7 2
3.4 Microstructure analysis
TOPAS-Academic supports the Double-Voigt Approach (e.g. Balzar, 1999), where crystallite size and
strain comprise Lorentzian and Gaussian component convolutions varying in 2u as a function of
1/cos(u) and tan(u) respectively.
3.4.1 Origins of specimen line broadening
Origins of specimen (= physical) line broadening are numerous. In general any lattice imperfections will
cause additional line broadening, which can be dependent and independent on the reflection order:
If a crystal is broken into smaller incoherently diffracting domains by dislocation arrays (small-angle
boundaries), stacking faults, twins, or other extended imperfections, then crystallite size broadening
occurs.
Dislocations, vacancies, interstitials, substitutionals, and similar defects lead to strain broadening.
- 27 -
From the nature of the lattice imperfections noted above follows, that both effects are interconnected.
For example dislocations cause lattice strain but also arrange into boundaries between incoherently
diffracting domains resulting in crystallite size broadening. This is one of the reasons why any
interpretation of the underlaying physics of broadening is difficult.
3.4.1.1 Crystallite size broadening
Crystallite size determination is one of the most important applications in powder diffractometry for
materials characterisation. Unfortunatly crystallite size is a quantity, which can not be measured directly
as explained below. In addition there is an enormous confusion in literature concerning the definition of
particle size, crystal size, crystallite size, and domain size.
In Fig. 3-15 a schematic representation of the terms mentioned above is given.
Fig. 3-15a represents a typical particle ("secondary grain"), which may consist of one or more crystals
("primary grains"). The different crystals may be separated e.g. by large angle boundaries, amorphous
or crystalline interfaces. It is important to realize, that particle size is not accessible by powder
diffraction! Typical methods used for particle size determination are light microscopy, laser size
analysis, sieving and others. Complications may arise due to the fact, that particles can agglomerate.
In Fig. 3-15b several crystals are shown. For crystal size the same principles are true as for particle
size: Crystal size is not accessible by powder diffraction as well! Methods for crystal size determination
are the same as for particle size determination, but agglomeration effects can hamper crystal size
analysis, too. The size of a crystal is in general equal or less than the partical size.
Each crystal may consist of one or more crystallites, as shown in Fig. 3-15c. The size of a crystallite is
in general equal or less than the crystal size. Crystallite size can be determined by means of powder
diffraction, but not directly as mentioned above and explained below.
Each crystallite may consist of one or more coherently reflecting domains, which need not to be
connected! In Fig. 3-15d a crystallite is shown, which is "broken" into two domains as a result of
stacking fault twinning ABCBA (dashed line) as may be found in fcc-structures. For a reflection hkl
represented by the diffraction vector a
r
there are two domains, but only one crystallite. In contrast to
this, for a reflection hkl represented by the diffraction vector b
r
there may be two domains and two
crystallites. It is important to realize, that line broadening is due to domain size, which can not be
determined by powder diffraction (although in rare cases a "domain structure" can be deduced). The
size of a domain is in general equal or less than the crystallite size.

A
B
C
B
A
a
r
b
r
a) b) c) d)
Fig. 3-15: Schematic representation of terms. a) particle or grain size, b) crystal size, c) crystallite size,
and d) domain size. For a detailed description refer to the text.
- 28 -
As mentioned above, crystallite size is a quantity, which can not be measured directly. Actually
measurable quantities are so-called column heights, as illustrated in Fig. 3-16. As the scattering power
of a column is dependent on its volume it makes sense to use volume weighted mean column heights
L
Vol
.
For example only for a cube and only for h00 reflections the column height L
Vol
is identical with the
edge-length L
0
of the cube (crystallite size for h00) as shown in Fig. 3-16a. For any other hkl a column
height distribution will be observed with a mean less than the crystallite size.
This is illustrated in Fig. 3-16b for a sphere, where for any given hkl a column height distribution is
observed. For any given hkl L
Vol
will be not identical with the diameter of the sphere, but can be derived
from the known crystallite shape: L
0
= 4 L
Vol
/ 3.

a) b)
Fig. 3-16: Schematic representation of a square and a circular cross-section of a crystallite built up of
columns perpendicular to the lattice planes (Haberkorn, 1999). d: d-spacing. L
0
: Edge length and
sphere diameter respectively.
From this follows, that any crystallite size terms are only to be used tentatively. With powder diffraction
only column heights can be determined. To obtain the true crystallite size, the true mean shape of the
crystallites must be known in order to derive and apply a correction to the column height of each hkl.
As long ago as 1918 Scherrer noted that the line breadth varies inversely as the size of crystallites in
the sample, leading to the Scherrer equation
u c | cos = (3-6)
where is the wavelength, u the Bragg angle and | the FWHM of the instrument corrected line profile. c
is an "apparent crystallite size" dependent on the "true crystallite size" and hkl and has no direct
physical interpretation; nevertheless it may be used as a measure for crystallite size.
The Scherrer constant k allows the relation of c with the volume weighted mean column height L
Vol
, e.g.
u | cos
Vol
L k = (3-7)
Employing integral breadths |
i
, Stokes & Wilson (1942) developed a more generalized treatment of
domain-size broadening which is independent on the crystallite shape.
u | cos
Vol i
L = (3-8)
- 29 -
Note that this conception directly leads to a formula identical with the Scherrer equation except that the
constant k assumes a value of unity.
3.4.1.2 Strain broadening
Lattice Strain (microstrain) represents variable displacements of atoms from their sites in the idealised
crystal structure as shown in Fig. 3-17 caused by any lattice imperfection (Dislocations, vacancies,
interstitials, substitutionals, and similar defects).
Strain e
0
is conceived by considering two extreme values of the lattice spacing d, namely d + Ad and d -
Ad, with e
0
= Ad/d. By equating the FWHM | with the angular range corresponding to d + Ad and d - Ad,
and by assuming that Bragg's law holds over this range (implying that parts of the specimen with
spacings d + Ad and d - Ad diffract independently, i.e. incoherently), it follows that
u c | tan 4
0
= (3-9)
Fig. 3-17: Schematic representation of lattice
strain (Haberkorn, 1999).

3.4.2 The Double-Voigt Approach for size - strain analysis
The Double-Voigt Approach as implemented in TOPAS-Academic can be used with both calculated
(FPA) and measured instrument functions. It allows the calculation of volume weighted mean crystallize
sizes (LVol-IB and LVol-FWHM) and a mean strain value (e0), based on individual crystallite size and
strain contributions to line profile shapes versus 2u in terms of Lorentzian and Gaussian type line
broadening.
The following parameters have been made available, for details about their definition refer to the
Technical Reference manual:
Crystallite size parameters
Cry Size L FWHM based measure for crystallite size (according to Eq. (3-6)) assuming purely
Lorentzian-type crystallite size broadening (which is not reasonable for real samples)
Cry Size G FWHM based measure for crystallite size (according to Eq. (3-6)) assuming purely
Gaussian-type crystallite size broadening (which is not reasonable for real samples)
LVol-FWHM FWHM based L
Vol
calculation (according to Eq. (3-7)) assuming intermediate crystallite
size broadening modelled by a Voigt function. The Scherrer constant k needs to be defined properly
dependent on crystallite shape.
- 30 -
Note: Use of LVol-FWHM is not recommended, but has been implemented to allow comparison of
results obtained with classic methods.
LVol-IB Integral breadth based L
Vol
calculation (according to Eq. (3-8)) assuming intermediate
crystallite size broadening modelled by a Voigt function.
Note: Use of LVol-IB is recommended.
Strain parameters
Strain L FWHM based strain calculation assuming purely Lorentzian-type strain broadening (which
is not reasonable for real samples)
Strain G FWHM based strain calculation assuming purely Gaussian-type strain broadening (which
is not reasonable for real samples)
e0 FWHM based strain calculation assuming intermediate strain broadening modelled by a Voigt
function. Describes a lattice distortion Ad/d with a 50% probability related to the undistorted lattice.
3.4.3 Comparability of results
There are literally dozens of different analysis methods that can yield much different or even physically
impossible results. These approaches can be broadly divided into two groups:
Model independent approaches
Mainly identified with the Fourier-deconvolution correction for instrumental broadening (Stokes method),
which is followed by the Warren-Averbach method for the separation of crystallite size and strain
effects.
Model dependent approaches
Mainly represented by integral breadth methods, e.g. the Double-Voigt approach. Integral-breadth
methods are to be preceded by an instrumental broadening correction, which depend on a particular
method and have to be defined accordingly. Profile fitting is usually carried out to model the physically
broadened line profile and instrumental profile followed by the application of some integral breadth
method.
Note: Results obtained from model dependent and independent approaches are usually not comparable
due to different parameter definitions (e.g. Klug & Alexander, 1974; Balzar, 1999) being an underlying
source of disagreement between the results obtained from both methods:
The integral breadth methods usually give volume weighted column heights and an upper limit
(maximum) of strain.
In contrast to this the Warren-Averbach analysis usually gives area weighted column heights and a
mean-square strain averaged over some distance perpendicular to the diffracting planes.
The disagreement between volume weighted and area weighted column heights as determined by both
methods is demonstrated in Fig. 3-18, where a typical column height distribution is shown. The
differences between volume weighted and area weighted column heights as determined by the different
methods can be highly significant.
Things become even more complicated when keeping in mind, that any direct imaging techniques for
crystallite size analysis (e.g. SEM, TEM, AFM) provide number weighted column heights!

- 31 -
0.00 10.00 20.00 30.00 40.00 50.00 60.00
L [nm]
g
(
c
h
)
L
Max
L
0
L
Num
L
Area
L
Vol
Fig. 3-18: Schematic representation
of a column height distribution g(ch)
showing the following characteristic
points:
L
Max
: most probable value
L
0
: median
L
Num
: number weighted mean
L
Area
: area weighted mean
L
Vol
: volume weighted mean

At this point it is interesting to remember, that the determination of crystallite size from column heights
always requires the knowledge of the true mean crystallite shape (section 3.4.1.1). Even if several
laboratories measure the same sample using the same evaluation method significantly different results
can be obtained, if there is no agreement concerning the mean crystallite shape.
The way out of this situation is the fact, that in most cases the imperfect crystalline structure need not to
be characterized on an absolute scale! In addition it makes sense to report column heights instead of
crystallite sizes. Very often it suffices to trace changes in the imperfect crystalline structure as induced
by some treatment or an alteration in the preparation conditions of the material. Then an analysis on a
relative scale, with reference to a defined starting condition of the specimen, should be preferred. This
avoids uncertainties about the quality of the "ideal" reference specimen and, even more important,
ambiguities in the interpretation of the line broadening may be reduced. Obviously any report of
microstructural results always requires information about the evaluation method and correction factors
employed.
3.5 Concluding remarks
The benefits that follow from synthesizing and fitting X-ray line profiles by means of convolution are
many and varied and are clearly evident from the accurate description of observed line profile shapes
across the whole 2u range for a wide range of instrument and sample conditions. Some of the most
important advantages of convolution based profile fitting are:
Peak shape and angle dependence can be described using minimal profile parameters in
laboratory and synchrotron X-ray data as well as CW and TOF neutron data. This is possible
because numerical convolution and numerical differentiation is used within the refinement
procedure so that a wide range of functions can be incorporated into the convolution equation.
The number of parameters required to describe a pattern is typically smaller than the analytical
function approach and thus parameter correlations are significantly reduced. In addition, increasing
profile complexity does not necessarily lead to an increase in the number of profile parameters.
The quality of fit by convolution is normally better than using other methods; the uncertainty in
derived parameters is therefore reduced.
Using physically based diffractometer models for the instrument aberration functions rather than
functions empirically selected directly leads to the Fundamental Parameters Approach. FPA has 34
- 32 -
already been implemented for most laboratory based X-ray powder diffractometer configurations
including conventional divergent beam instruments, parallel beam instruments and diffractometers used
for asymmetric diffraction. It can also accommodate various optical elements (e.g. multilayers and
monochromators) and detector systems (e.g. point and position sensitive detectors) and has already
been applied to neutron powder diffraction systems (e.g. Australian Nuclear Science and Technology
Organisation, ANSTO) as well as synchrotron based diffractometers (e.g. BM16 at the European
Synchrotron Radiation Facility, ESRF, and Station 2.3 at the Synchrotron Radiation Source, SRS,
Daresbury).
The FPA is a universal approach to profile fitting in which parameters fitted are physically
identifiable and measurable. The validity of the fitted terms is therefore self-evident.
The excellent profile shape description with FPA significantly improves the accuracy of derived
lattice parameters. As a result, refined zero point and sample height errors no longer serve as a
garbage can for misfits.
A small number of profile parameters are required to describe a pattern and therefore parameter
correlation is typically less than with purely empirical convolution based profile fitting.
Knowledge of the instrument contribution improves the discrimination between profile and
background intensity in complex peak overlaps, unless sample broadening becomes dominant.
It is possible to identify whether or not a diffractometer is operating at its optimum resolution and to
therefore determine unequivocally whether or not an observed line profile posses specimen
broadening. The FPA is the ideal tool for instrument verification particularly in regulated
laboratories.
Synthesised profiles rather than profiles from a reference material can be used as the basis for
deconvolution of instrumental effects from observed profiles.

- 33 -
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