Analysis of X-ray Powder Diffraction Data Using the

Maximum Likelihood Estimation Method

Yoed Tsur* and Clive A. Randall*
Center for Dielectric Studies, Materials Research Laboratory, The Pennsylvania State University,
University Park, Pennsylvania 16802
The details of substitutional chemistries can be deduced with
the associated relaxation of the crystal structure. This paper
demonstrates the use of the maximum likelihood estimation
method (MLE) for X-ray powder diffraction (XRD) analysis.
Detailed calculations are performed for cubic and tetragonal
systems. Analysis of yittrium-doped BaTiO
3
prepared under
different conditions is shown as an example. The methodology
outlined here gives rise to a correct evaluation of the standard
deviations of the lattice parameters. In addition, MLE ap-
proaches asymptotically the CramerRao lower bound
(CRLB) and, therefore, has an advantage over other estima-
tion methods. A link between the output of a commercial
software and the standard deviation in the peak position is also
suggested.
I. Introduction
O
NE of the most common applications of X-ray powder diffrac-
tion is the precise determination of lattice constants. For this
application, it is very important to have a reliable statistical tool
that allows the correct estimate of both the lattice constants and
their variances (or standard deviations).
For the most simple case, cubic crystals, it is sufficient to use
weighted least squares (WLS) for the estimation of the single
lattice constant (a) and its variance a.
1
Note, that it is important
to use WLS and not least squares, since with different peaks, the
determination of both a and a is a function of the peak position
and shape. However, when dealing with lower-symmetry crystal
systems, WLS is insufficient. This is primarily because the
variances of the different constants are in general correlated.
Therefore, for these cases, one has to use a more general method,
such as the maximum likelihood estimation (MLE) method.
24
This choice is superior to other options, because its variance
reaches asymptotically the CramerRao lower bound (CRLB).
4
The main goal of this paper is to show how to apply MLE for
the calculation of lattice parameters and their standard deviations.
The analysis requires as many peaks as possible in the form of (2
i
,

i
) where 2
i
is the position of the i-th peak and
i
is the standard
deviation in that position (which is not always so easy to evaluate).
It is first assumed that all the data are available, and we show how
to apply MLE for two different cases, cubic and tetragonal. A
formula for the
i
values, under the assumptions that diffraction
peaks are Pearson VII functions and the counts in each step of the
diffractometer are distributed according to the Poisson distribution
function, is then developed. It is also described how to use MLE
along with a simple model to correct systematical errors with a
standard material.
In the experimental part of this work, the above analysis is
applied to tetragonal BaTiO
3
with metal tungsten as the standard
material. Typical standard deviations of the lattice constants are
a 3 10
4
and c 5 10
4
. The protocol of finding
accurate lattice parameters for BaTiO
3
is described.
II. Data Analysis of XRD Measurements Using MLE
(1) General
Typical powder XRD data are a list of intensity (counts) versus
2. There are peaks and unknowns. The number of unknowns
ranges from one for a cubic system (the lattice constant, a) to six
for a triclinic system (a, b, c, , , ). Suppose one has good
estimations for p peak positions. The problem of how to find such
good estimations of the peak positions, and in particular, how to
evaluate the corresponding standard deviations, is addressed in
Section II (4). The i-th peak is at
i

i
. Let us assume that the
probability distribution of finding the measured peak
i
away from
its true value

i
is normal. This assumption is correct for diffrac-
tion intensities by the statistical law of large numbers. The
likelihood function
2,3
is, therefore,
u

i1
p
1
2
i

1/ 2
exp

i
u
2
2
i
2
(1)
where u is the vector of the unknowns. It is easier and, therefore,
is the common practice to deal with W ln ((u)). The best
estimation for the vector of unknowns is found by the set of
equations,
W
u
j

i1
p

i
u

i
2

i
u

u
j
0 (2)
Note that this is also exactly the solution of WLS. This similarity
is due to the assumption of normal distribution made for large
numbers. However, the MLE standard deviations are, in general,
different from the results of WLS.
The maximum likelihood standard deviations for this solution
are calculated using the covariance matrix, E H
1
, where
H

2
W
u

(3)
and then the standard deviations related to diagonal terms of the
covariance matrix, viz.,
u
j
E
jj

1/ 2
(4)
For the analytical treatment we use the following approximation:
R. L. Snydercontributing editor
Manuscript No. 189376. Received May 3, 1999; approved January 13, 2000.
Supported by the Center for Dielectric Studies and the National Science Founda-
tion I/VCRC program.
*Member, American Ceramic Society.
J. Am. Ceram. Soc., 83 [8] 206266 (2000)
2062
journal
H

i1
p
1

i
2

i
u

i
u

i
u

i
u

i1
p
1

i
2

i
u

i
u

(5)
since the neglected term should be close to zero near the solution,
u , of Eq. (2). It should be noted that there are specific cases where
this approximation does not hold. (As an example, consider a case
where

i
(u )
i
u
1
2
u
2
2
, where the neglected terms are required to
prevent det(H) 0). In the case of X-ray diffraction analysis these
specific cases do not occur.
(2) Cubic Systems
In the simple case of cubic systems, there is only one unknown,
the lattice constant a, and the peak positions are

i
a

arcsin

h
i
2
k
i
2
l
i
2

1/ 2

2a

(6)
The maximum likelihood solution, a, is found by solving the single
equation

i1
p

i
a

i
2
tan

i
a

0 (7)
The standard deviation can be evaluated using the approximation
of Eq. (5), by
a

i1
p
1

i
2
sin
2
2

i
a

1/ 2
(8)
(3) Tetragonal Systems
In tetragonal systems there are two unknowns, a and c, and the
peak positions are

i
u

arcsin

h
i
2
k
i
2

2a

2
l
i
2

2c

1/ 2
(9)
Equation (2) in explicit form for this system is

i1
p

i
u

i
2
h
i
2
k
i
2
sin 2

i
u

i1
p

i
u

i
2
l
i
2
sin 2

i
u

0
(10)
The actual procedure of finding the best solution can be done
numerically, by changing the parameters a and c and finding the
values (within the neighborhood defined by the maximum likeli-
hood standard deviations, see below) that give the best approxi-
mation to Eq. (10).
The standard deviation treatment is much more complicated,
because the standard deviations are correlated. This means that the
error matrix has nonzero off-diagonal elements. Therefore, one
should write explicitly the H matrix and find the covariance matrix
by matrix inversion. Using the approximation Eq. (5) one finds,

H
aa


4
4a
6
i1
p
1

i
2
h
i
2
k
i
2

2
sin
2
2

i
u

H
cc


4
4c
6
i1
p
1

i
2
l
i
4
sin
2
2

i
u

H
ac


4
4a
3
c
3
i1
p
1

i
2
l
i
2
h
i
2
k
i
2

sin
2
2

i
u

(11)
After inverting the H matrix and taking the square root of the
diagonal elements of the covariance matrix,

a

H
aa

H
ac
2
H
cc

1/ 2
c

H
cc

H
ac
2
H
aa

1/ 2
(12)
In addition, since the errors are correlated, care should be taken
while calculating errors in functions of the variables. The general
formula for this is,
2
y
2

j
y
u
i
y
u
j
E
ij
(13)
where y is a function of the variables. For instance, the error in the
cell volume V a
2
c is
V 4a
2
c
2
E
aa
a
4
E
cc
4a
3
cE
ac

1/ 2
(14)
Combining Eqs. (14) and (4) gives
V
V


2
a
a

2

c
c

2
4
E
ac
ac

1/ 2
(15)
(4) Evaluating the Standard Deviation in the Estimated
Position of a Single Peak
Normally every software package that comes with modern
diffractometers provides estimations for the peak positions. This is
usually done by least squares. Regarding the standard deviation of
these positions there are basically three options.
(i) The software may give this information and one might
count on it as is.
(ii) One can print each peak with significant zoom-in and try
to evaluate the accuracy of the peak position. This method usually
gives rise to over-estimated standard deviations, especially for the
bigger (high-intensity) peaks.
(iii) One can calculate the standard deviations of each peak, as
we do below for a special system.
In this study, a Scintag machine and software (models PAD V
and DMSNT ver. 1.34, respectively, Scintag, Cupertino, CA.)
were used. The aim of this section is to relate the parameters given
by the software to the accuracy of the peak position.
The software does a fit to Pearson VII function,
I2
I
0

1
2 2
0

2
mb
2
m
(16)
and returns the parameters: amplitude (I
0
), position (2
0
), full
width at half maximum (FWHM), exponent (m), and peak area.
The Pearson function can be written in terms of the above
parameters as follows:
I x
I
0
1 x
2
2
1/m
1
m
x
2 2
0
FWHM/ 2
(17)
In principle, this function can be fitted to the data using MLE.
While accurate, this is not an easily applied methodology, since the
likelihood function is based on both the Poisson distribution and
the Pearson function. This gives rise to very complicated and
lengthy expressions in the inverse covariance matrix (which is a
4 4 matrix in this case). Therefore, a different approach is
suggested here that is more readily applicable.
August 2000 Analysis of X-ray Powder Diffraction Data Using the Maximum Likelihood Estimation Method 2063
Consider one well-defined peak, and assume that it has the
shape of a Pearson VII function. The probability of finding I(x)
obeys the Poisson distribution function. In particular, the deviation
in I
0
is (I
0
)
1/ 2
. Thus, we evaluate the standard deviation in x by the
equation
Ix I
0
I
0

1/ 2
(18)
which leads, along with Eq. (17), to the formula
2
FWHM
2

1 I
0
1/ 2

1/m
1
2
1/m
1

1/ 2
(19)
Note the limiting case for (2) when m 1 and I
0
1, Eq. 19
reduces to the simple form (2) FWHMI
0
1/4
. It is also useful
to point out that (2) is a weak monotonic increasing function of
m, within the regime of interest.
Equation (19) gives a simple, and yet accurate, evaluation of the
standard deviation in the ideal case. In practice, it can be used with
the following modifications:
(i) After fitting to the Pearson function, it is worth trying to
improve the fitting using split-Pearson function. The standard
deviation is then evaluated on both sides, and the bigger standard
deviation is taken.
(ii) If the result is less than half the step size of the scan, the
standard deviation should be set to that value (in the present case,
0.01).
(5) Correcting Systematic Errors Using a Standard
Instrument and sample factors influence the positions of the
diffraction intensity maxima.
5
The most important factors are flat
sample surface, absorption,
6
vertical divergence,
7
and misalign-
ment. The best way to compensate for such errors is to measure
peaks of a known phase along with the phase under investigation.
It is then possible to correct the whole diffraction pattern in a way
that the peaks of the known phase are standardized. One can then
compare lattice parameters from different runs. The objective here
is to develop a protocol by which the corrections are consistently
made. It is important to keep in mind that the accuracy of the
measurement pose limits on the accuracy of this correction.
Therefore, it is sufficient to use a simple correction function. In
particular, for simplicity with MLE or WLS, it is plausible to write
a correction function that is linear in its unknowns.
For simple, but yet accurate, treatment of this problem the
correction is written in the following manner:

corr.
A B sin 2 Cf LIT (20)
where LIT stands for less-important terms. Examining results of
theoretical work of these corrections
5
it seems that the most-
suitable functions for f() are either cot or cot 2. However, in
this work it was found that, after removing the sin 2 part, the best
fit is to tan . In addition, using f() tan , reasonable values for
A are obtained (of the order of the machine alignment accuracy of
0.01), unlike the other options, which give rise to A of the order
of 0.02.
The correction procedure is, therefore, as follows. A standard
material is used that fulfills the following conditions:
(i) It is stable and does not interact with the sample, in
ambient conditions.
(ii) There are at least four identifiable peaks of the standard
that do not overlap with peaks of the material under investigation.
These peaks should be taken both from small and large angles.
(iii) There are as many as possible peaks of the material under
investigation that do not overlap with peaks of the standard.
Knowledge of the correct positions of the standards peaks,

i
,
is assumed. The vector of unknowns is now u ( A, B, C) and Eq.
(2) is used to find it:

i1
p

i

i
u

i
2
0

i1
p

i

i
u

i
2
sin 2
i
0

i1
p

i

i
u

i
2
tan
i
0
(21)
Once the vector of unknowns is found one can check that A is of
the order of 0.01 and all the corrected positions are within an
interval of 0.005 from the theoretical ones. All the peaks of the
material under investigation are then corrected by

corr.
A B sin 2 C tan (22)
III. Experimental Procedure
In order to demonstrate the methodology we measured samples
of BaTiO
3
doped with yttrium and fired under reducing atmo-
sphere. The samples were prepared with different stoichiometry of
Ba/Ti ratio. Since the yttrium cation can occupy both the barium
and the titanium sites, it is expected that for lower titanium
chemical potential (barium-rich samples) more yttrium occupies
the titanium site, and the lattice expands. A more detailed paper of
the specifics of this defect and crystal chemistry is to be published
soon.
8
The data collection was done with fixed slits using step scan,
0.02 per step, 10 or 20 s/step, as described in Table I. The total
time of the measurement is 8.7 h.
Our standard material was tungsten (99.9%, Strem Chemicals,
Newburyport, MA.), which is cubic with lattice parameter of
3.16524 .
1
Approximately 1:6 weight tungsten was added, in
accordance with the electron density of the two materials. Four
peaks of the standard were measured, and typically errors in 2 of
0.002 or less were obtained after correction.
IV. Results and Discussion
Table II presents the results for one of the samples. As
explained above, FWHM and the exponent of the Pearson VII
formula (m) are fitted. In cases were split Pearson VII was used,
only the pair which generates the larger calculated standard
deviation is presented.
Table III presents the lattice parameters of five different
samples. Note that the volume difference between barium-rich and
Table I. Measurement Protocol
2 range (deg) Peaks covered Step scan (s/step)
38.439.5 1 10
4040.8 2 10
44.546 3, 4 10
55.557 5, 6 10
5859 7 20
6567 8, 9 10
72.873.8 10 20
7880.4 11, 12 20
8384.2 13 20
90.393.3 1416 20
116.4120.7 1719 20
122125.3 2022 20
127133 2325 20
138143 26, 27 20
Peak numbers refer to Table II.
2064 Journal of the American Ceramic SocietyTsur and Randall Vol. 83, No. 8
titanium-rich is significant, taking into account the likelihood
standard deviations. Different measurements on samples prepared
under the same conditions yielded the same lattice parameters,
within the standard deviations.
Table IV presents the results of the analysis of one of the
samples, where some of the peaks are omitted. This was done in
order to check the sensitivity of the method. It can be seen that less
peaks means higher standard deviation, while the lattice parame-
ters remain in agreement with those calculated for 23 peaks.
V. Conclusions
(1) MLE was applied for XRD analysis. Under the assumption
of a normal distribution of the measured peak position about its
true position, the lattice parameters are found by solving the same
equations as in WLS analysis. However, the estimated standard
deviations of the lattice parameters are different and can be more
accurately determined with the MLE.
(2) Two systems were investigated: cubic and tetragonal. A
complete analysis was applied to yttrium-doped BaTiO
3
in the
tetragonal phase, at room temperature.
(3) A link between the diffractometers software output and
the standard deviation in the peak position is suggested (Eq. 19).
This, along with some restrictions described in Section II (4) is
used to evaluate the
i
values that are needed for MLE or WLS
analysis.
(4) A protocol for measuring the lattice constants of BaTiO
3
is
described (Table I). It should be possible to compare results from
different laboratories if this protocol is to be followed. The authors
can also supply a program for the MLE analysis in the form of an
MSExcel template on request.
Table II. Results of Sample No. 1.
Peak No. I (counts) 2 (deg) FWHM (deg) m 2 (deg) hkl Corrected (deg) Calculated (deg)
1 5854 38.936 0.0757 1.035 0.010 111 19.445 19.446
2 2196 40.308 0.0742 1.114 0.010 110W 20.130 20.130
3 2791 44.941 0.0864 0.825 0.010 002 22.445 22.442
4 2561 45.418 0.0895 0.971 0.010 200 22.684 22.690
5 2630 56.023 0.0951 0.817 0.010 112 27.983 27.981
6 5946 56.327 0.0839 1.317 0.010 211 28.135 28.140
7 372 58.308 0.1054 1.054 0.012 200W 29.125 29.125
8 2440 65.793 0.1038 0.919 0.010 202 32.867 32.868
9 971 66.183 0.1010 1.453 0.010 220 33.062 33.060
10 1284 73.242 0.1054 0.863 0.010 211W 36.591 36.591
11 571 78.790 0.1441 0.926 0.015 113 39.365 39.366
12 198 79.497 0.1137 1.150 0.016 311 39.718 39.728
13 1874 83.546 0.1160 0.998 0.010 222 41.743 41.746
14 3446 91.649 0.1223 0.988 0.010 213 45.796 45.796
15 2248 92.095 0.1395 1.213 0.011 312 46.019 46.016
16 2454 92.339 0.1129 1.114 0.010 321 46.141 46.147
17 1070 117.643 0.2250 1.317 0.021 204 58.802 58.806
18 1148 118.860 0.2055 0.838 0.017 402 59.412 59.402
19 1573 119.243 0.1620 1.279 0.014 420 59.603 59.603
20 498 122.554 0.1972 1.118 0.022 214 61.261 61.269
21 861 123.838 0.1844 0.816 0.017 412 61.904 61.897
22 420 124.154 0.1856 2.390 0.023 421 62.056 62.056
23 1086 128.554 0.2289 0.802 0.019 323 64.266 64.267
24 976 129.126 0.2101 0.954 0.019 332 64.552 64.548
25 1664 131.183 0.2392 1.043 0.019 321W 65.591 65.591
26 977 139.568 0.3576 1.133 0.033 224 69.783 69.779
27 2629 141.211 0.3005 1.125 0.022 422 70.607 70.603
W indicates peaks of the tungsten phase.
Table III. Results of the Analysis of Various Samples
Sample
No.
Firing
Temperature
(C) Ba/Ti a () a () c () c () V (
3
) V (
3
)
1 1350 0.99 3.99377 26 10
5
4.03554 49 10
5
64.368 14 10
3
2 1400 0.99 3.99390 29 10
5
4.03592 60 10
5
64.378 16 10
3
3 1400 1.01 3.99665 39 10
5
4.03532 76 10
5
64.457 21 10
3
4 1400 1.01 3.99581 31 10
5
4.03716 61 10
5
64.459 17 10
3
5 1400 1.01 3.99623 34 10
5
4.03717 57 10
5
64.473 17 10
3
Table IV. Results of the Analysis of Sample No. 1 Taking into Account Different Peaks
Peaks omitted a () a () c () c () V (
3
) V (
3
)
None 3.99377 26 10
5
4.03554 49 10
5
64.368 14 10
3
3, 4 3.99373 27 10
5
4.03561 52 10
5
64.368 15 10
3
11, 12, 1719 3.99381 32 10
5
4.03549 60 10
5
64.368 18 10
3
2024, 26, 27 3.99389 33 10
5
4.03544 60 10
5
64.370 17 10
3
36, 1724, 26, 27 3.99399 51 10
5
4.03547 88 10
5
64.374 27 10
3
1, 36, 8, 9, 1424, 26, 27 3.9942 11 10
4
4.0355 16 10
4
64.380 55 10
3
August 2000 Analysis of X-ray Powder Diffraction Data Using the Maximum Likelihood Estimation Method 2065
Acknowledgments
We would like to thank A. Hitomi for useful discussions throughout this work. We
would also like to thank Y. Huang for her comments on the statistical analysis.
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2066 Journal of the American Ceramic SocietyTsur and Randall Vol. 83, No. 8