TFJD093-03-64129 FEL May 5, 2005 16:45

New Study of Defect Structure

in Nonstoichiometric Lithium Tantalate
S. JEBBARI,1,2 F. BENNANI,3 A. JENNANE,1 and N. MASAIF1,4

QUERY SHEET

Q1: Au: Pls. provide keywords.

Q2: Au: Some Thing is missing in place of
.

0
TFJD093-03-64129 FEL May 5, 2005 16:45

Ferroelectric Letters, 32:1–16, 2005

Copyright
C Taylor & Francis, Inc.

ISSN: 0731-5171 print / 1543-5288 online

DOI: 10.1080/0731517059096366

New Study of Defect Structure

in Nonstoichiometric Lithium Tantalate
S. JEBBARI,1,2 F. BENNANI,3 A. JENNANE,1 and N. MASAIF1,4
1 LMM, Département de Physique Appliquée, Faculté des Sciences et Techniques,
5 BP 577 Settat, Morocco
2 LPTN,
Département de Physique, Faculté des Sciences Semlalia, BP S15,
Marrakech, Morocco
3 LPVC, Département de Physique, Faculté des Sciences, BP 133 Kénitra, Morocco
4 LPNA, Département de Physique, Faculté des Sciences, BP 133 Kénitra, Morocco

10 (Received March 29, 2002; in final form November 4, 2004)

Experimental and analytical study of the Curie temperature and density for different composi-
tions of nonstoichiometric lithium tantalate are presented in this work. Our results show that
the Curie temperature decreases and the density increases linearly with increasing composi-
tion. Using the theoretical approach to the defect structure analysis, developed by Safaryan, a
15 comparison between three defects models (oxygen vacancies, tantalate vacancies and lithium
vacancies) has been proposed. The calculated and measured values show that the lithium va-
cancy model effectively describes the defect structure in nonstoichiometric lithium tantalate.
The experimental procedures employed indicate that the errors in the formulae obtained have
been estimated to be about 0.8%
a for Li, 1% for aTa and in the crystal parameters they have been
20 estimated to be about 0.001 A for a and 0.005 A for c.

Keywords: Q1

INTRODUCTION

Lithium tantalate is well known as a single crystal oxide material with a

variety of significant technological applications. Although commonly des-
25 ignated LiTaO3 , the phase admits a broad range of nonstoichiometry, from
roughly 46 to 50.4 mol % of Li2 O at room temperature [1].
Lithium tantalate is ferroelectric at room temperature and its structure is
of type of lattice ABO3 with oxygen octahedron to construct the original
example of a compound of “ideal” compact hexagonal structure [2]. The
30 structure of ferroelectric LiTaO3 belongs to the space group R3c and can be
considered as a superstructure of the α-Al2 O3 corundum structure. Within
the oxygen cages, the cations appear along a trigonal polar c-axis, in the
sequence: Li+ , Ta5+ , vacancy [3].
1
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2 S. JEBBARI et al.

Lithium tantalate is also well known as an oxide compound which exhibits

wide nonstoichiometry in the Li/Ta cation ratio. 35
Temperature and density of nonstoichiometric lithium tantalate were
experimentally measured and analytically estimated to determine their rela-
tionship to composition x. So, quantitative and qualitative models proposed
in this work are based on nonstoichiometric defect structure to explain the
influence of the temperature and density on composition. 40
Dielectric measurements have shown that there is a considerable effect
of the nonstoichiometry on the phase transition temperature in ferroelectric
LiTaO3 and LiNbO3 solid solutions. These compounds are characterized in
order to clarify the relationships between the defect structure, temperature
(or density) and optical properties. 45
In a previous paper [4], the successive phase transitions corresponding
to the various compositions in LiTaO3 system have been re-examined. In
brief, the ceramic specimens of LiTaO3 in different compositions are studied
by the impedance spectroscopy in the 1 Hz-1 MHz-frequency range and the
500–1200 K temperature range. The temperature dependence of the dielec- 50
tric permittivity of these specimens was measured in order to determine the
temperature of the phase transition.
The density of each ceramics is determined by using a liquid of
known density. The experimental procedures described here, are based on
Archimedes principle where the weight of the samples is measured as func- 55
tion of fluid density. The standard errors are calculated using the experimental
and statistical weighting methods. Note that the major experimental error
comes from the volume measurements.
The analysis of the ceramic samples, which are prepared from Li2 O and
Ta2 O5 , indicates that there is a modification of the optical properties of 60
LiTaO3 with different nonstoichiometric compositions. To understand the
mechanism responsible for the optical properties modification of LiTaO3 , it
is necessary to introduce the indispensable defect structure. Namely, each
type of vacancy defect is characterized and described by a vacancy model.
Finally, we propose quantitative and qualitative defect models in order to 65
interpret some observed phenomena such as change of the Curie temperature
and density according to the composition.
As LiTaO3 is isomorphism with LiNbO3 , several defect models given in
the literature have been introduced for LiNbO3 . Fay et al. [5] described a
ceramic sample assumed containing oxygen and lithium vacancies by oxygen 70
vacancy model, having the formula [Li1−2x θ2x ][Nb][O3−x θx ] where [.] repre-
sents the sublattice and θ denotes the vacancies. This model presents certain
anomaly to describe the density variation as a function of the composition.
TFJD093-03-64129 FEL May 5, 2005 16:45

DEFECT STRUCTURE IN NONSTOICHIOMETRIC LiTaO3 3

In order to correct this anomaly, Lemer et al. [6] have predicted that an
75 excess of niobium ions might occupy the lithium sites. This is the lithium
vacancy model which is based on the formula [Li1−5x Nbx θ4x ][Nb]O3 ; where
the lithium vacancies are introduced by taking into account the charge com-
pensation. However, Peterson and Carnevale [7] have observed a new defect
structure corresponding to the Nb-site vacancy type using the NMR tech-
80 nique. Then, the niobium vacancy model, which is elaborated by these
authors, is arranged as follows: [Li1−5x Nb5x ][Nb1−4x θ4x ]O3 . Contrarily to
results pointed out by Abrahams and Marsh [8], Donnerberg et al. [9] proved
that the niobium vacancy model is unfavorable in comparing the energetic
aspect of these defect structure models. A comparative study between the
85 densities of these models allows Iyi et al. [10] to reject the oxygen vacancy
model.
A theory of ferroelectric transition in the crystal LiNbO3 has been per-
formed to understand and predict the properties of this crystal [11]. Par-
ticularly, the solution of the dynamic problem of the plans system of the
90 crystal exhibits the existence of the “soft mode” at the ferroelectric transi-
tion. These recent studies provide a useful understanding of the dynamic
behavior of phase transition and the defect structure of LiNbO3 .
For example, this method has been applied to the defect structure analysis
of the lithium niobium single crystals [12]. It allows a comparison between
95 the calculated values and the experimental data of the Curie temperature for
the three vacancy models.
In this study, we present the experimental method used and the results
obtained. So, we examine the effect of the composition on the temperature
and density.

100 EXPERIMENTAL RESULTS

The best part of the experimental study has been presented in reference 4
where the experimental procedures are well detailed. In this section, we
briefly present the experimental results of solid solutions of the LiTaO3
system. The ceramic specimens of these solid solutions with various com-
105 positions were prepared from Li2 O and Ta2 O5 in stoichiometric quantities.
Lithium tantalate were prepared according to the general formula
Li1−x Ta1+x/5 O3 (0 < x < 0.1). Li2 CO3 (99.9%) and Ta2 O5 (99.99%) are
mixed by attrition with ZrO2 balls in isopropanol in the 1/3 ball, 1/3 iso-
propanol and 1/3 solid phase ratio and shaken for 12 h. After the sedimen-
110 tation, the suspension was dried in a rotovapor and calcined at 1100 K for
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4 S. JEBBARI et al.

TABLE I Chemical formula obtained by the analysis and the proposed formula
according to (b) and (c) models with different Li/Ta ratios

Proposed formula
Experimental
Li/Ta formula [4] (b) (c)

1 LiTaO3 [Li1.0 ][Ta1.0 ]O3 [Li1.0 ][Ta1.0 ]O3

Q2 0.976 Li0.98 Ta1.005 O3 [Li0.98 Ta0.02 ][Ta0.985
0.015 ]O3 [Li0.98 Ta0.005
0.015 ][Ta]O3
0.95 Li0.958 Ta1.008 O3 [Li0.958 Ta0.0042 ][Ta0.966
0.034 ]O3 [Li0.958 Ta0.008
0.034 ][Ta]O3
0.88 Li0.90 Ta1.02 O3 [Li0.90 Ta0.10 ][Ta0.92
0.08 ]O3 [Li0.90 Ta0.02
0.08 ][Ta]O3

10 h. Powders were then isostatically pressed at 2500 bars to give pellets of

13 mm diameter and 1 mm thickness and were sintered at 1500 K for 4 h
heating rate of 100 K/h.
All the prepared compositions were characterized by X-ray diffraction
with a Philips PW 1729 diffractometer by using the CuKα wavelength and 115
scanning electron microscopy in the Service Central d’Analyse of CNRS
at Vernaison (France). They exhibit the structure of pure LiTaO3 [8] and a
uniform grain size of about 2 µm. Then, they were analyzed by the ICP-AES
(Inductively coupled plasma-atomic emission spectroscopy) technique and
the formulae obtained are reported in Table I. The errors in the formulae 120
obtained were estimated to be about 0.8% for Li and 0.1% for Ta. We denote
by (a), (b) and (c) the oxygen, tantalate and lithium vacancy models.
The dielectric permittivity was studied between 600 and 1200 K with a
heating rate of 2 K/min. The errors in the reported temperatures are estimated
at ±2 K. 125
The temperature dependence of the dielectric constant at 1 KHz for the
ceramic samples of the lithium tantalate with different nonstoichiometry
compositions is illustrated in Fig. 1. For each composition, the dielectric
constant shows a clear peak at the Curie point whose the shape varies with
the composition x and sharpens when x increases. The peak value of the 130
dielectric constant at the Curie point, increases with the composition x.
Moreover, the crystal parameters were determined with the X-ray and
were refined by the least square method calculations. They are reported in
Table II where a and c indicate the cell parameters.
The reduction in the report of Li/Ta ratio causes at the same time variation 135
of the lattice parameter and the Curie temperature. The errors of crystal
parameters, have been estimated to be about 0.001 Å for a, and 0.005 Å
for c.
The density of each nonstoichiometric LiTaO3 sample was determined by
the standard Archimedes immersion method using pure water as a medium. 140
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DEFECT STRUCTURE IN NONSTOICHIOMETRIC LiTaO3 5

Figure 1. Dielectric permittivity vs temperature for different compositions at 1 KHz

frequency measurement.

LiTaO3 ceramics of different compositions were then cut into slug where
the diameter and length are well determined and optically polished. The
accuracy of the measurement was checked by the density measurement of a
reference cylinder and compared with their calculated value.
145 This experiment is important and deserves our attempt. In fact, we need to
determine the density of the different samples of nonstoichiometric lithium
tantalate once to know the volume of each.
Since the masses were measured using analytical balance, the error on
each density dominated by the error on each volume determination. To cal-
150 culate the errors of measurement, we analyzed each sample 4 times by
Archimedes method and the errors obtained are of the standard deviations
of repeated measurements. Results obtained are reported in Table III.

TABLE II Values of cell parameters, Curie temperatures for different Li/Ta ratios
studied
a a a
Li/Ta a ( A) c ( A) c/a Volume ( A) [3] T∗c (K)

1 5.152 ± 0.001 13.767 ± 0.005 2.672 316.46 ± 0.24 917

0.976 5.152 ± 0.001 13.768 ± 0.005 2.672 316.52 ± 0.24 906
0.95 5.153 ± 0.002 13.770 ± 0.005 2.672 316.72 ± 0.24 861
0.88 5.156 ± 0.002 13.776 ± 0.005 2.671 317.27 ± 0.24 783
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6 S. JEBBARI et al.

TABLE III Masses, volumes and densities

for different Li/Ta ratios studied

Li/Ta m (g) Volume (cm3 ) d∗ (g/cm3 )

1 0.962 0.129 ± 0.008 7.448 ± 0.016

0.976 1.004 0.134 ± 0.006 7.471 ± 0.012
0.95 1.043 0.140 ± 0.006 7.475 ± 0.009
0.88 1.081 0.144 ± 0.005 7.523 ± 0.006

At this level, we have proposed a theoretical investigation that explains

the experimental observations.

THEORETICAL APPROACH 155

In this work, we suppose that the LiTaO3 ceramic samples consist of a

single crystal on the basis of their structure. Such an assumption is based
on experimental fact such as that ferroelectric phase transition occurred in
the ceramic samples, which are formed by parallel planes along the polar
“c” axis. In Fig. 2, distances between planes (Li, Ta and O at T = 0 K) are 160
denoted in the following way: RO−O (a = 2.30 Å), RLi−O (R20 = 0.601 Å),
RTa−O (R10 = 0.954 Å), RLi−Ta (R12 = a − R10 − R20 ) [2].
The new approach proposed by Safaryan et al. on ferroelectric transition
in the LiNbO3 crystal is tested by new experimental results of the LiTaO3
compound to discuss the main role of the nonstoichiometric compositions. 165

Figure 2. Different planes in an elementary cell of crystal LiTaO3 .

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DEFECT STRUCTURE IN NONSTOICHIOMETRIC LiTaO3 7

However, this approach is expressed thereafter like a new tool to describe the
defect structure mechanism in the lithium tantalate where several physical
quantities are relatively sensitive to the nonstoichiometric composition and
each of them can be independently used.
170 We avoid the detail of the theory of ferroelectric transition in the LiTaO3
crystal that is similar to that given in reference [11] and we report only the
useful expressions in the appendix.
At 0◦ K, the soft mode frequency, ω2 , is proportional to the Curie temper-
ature, Tc . We substitute, ω2 , by the expression I.10 to obtain the following
175 relation that allows calculating the Curie temperature:


∗ 

T∗c M∗ + M∗2 + M∗0 M1 M2 M0 P1 P2
= 1 (1)
Tc M1 + M2 + M0 M∗1 M∗2 M∗0 P1 P∗2

X∗ and X represent the exact stoichiometric compositions and the nonstoi-

chiometric compositions, respectively.
This expression allows us to determine the Curie temperatures of the
defect structure models.
180 In order to validate the hypothesis that the defect structure in the non-
stoichiometric lithium tantalate is due to lithium vacancies, a comparison
between the calculated and experimental values is reviewed. So, we analyze
the defect structure effect on the Curie temperature that depends on the ion
masses, charges and distance between these ions.
185 We are also interested in the density to explain the role of the defect
structure in the nonstoichiometric lithium tantalate compound. The density
relations for the three vacancy models can be obtained by using the crystal
parameters. The density of a sample is defined as the relationship between
the mass and volume of a specific amount of material. Then, the density of
190 a sample can therefore be determined by,

ZM
d= (2)
NV

V, Z, M and N are the volume of the unit cell, number of Li or Ta ions per
cell, molecular weight and Avogadro’s number, respectively.
We can easily deduce the density, d∗ , such that:

M∗ V
d∗ = d (3)
M V∗
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8 S. JEBBARI et al.

The density of our specimens was calculated within the range of the nonsto-
ichiometric composition of the solid solution. 195
The above expressions can be used to analyze the three models
of the defect structure in the lithium tantalate. However, we represent
these models, previously described, in the following condensed form:
[Liα1 Taα2 θα3 ][Taβ1 θβ2 ][O3γ1 θγ2 ]; and K∗ = g k with K = M, q and g = α, β
or γ . Here α, β and γ allow identifying the three models as follows: 200

i) Oxygen vacancy model corresponds to α1 = 1 − 2x, α3 = 2x, β1 = 1,

γ1 = 1 − x/3 and γ2 = x; and K∗2 = α1 K2 , K∗1 = β1 K1 and K∗0 = γ1 K0 .
ii) Tantalate vacancy model corresponds to α1 = 1 − 5x, α2 = 5x,
β1 = 1 − 4x, β2 = 4x and γ1 = 1; and K∗2 = α1 K2 + α2 K1 , K∗1 = β1 K1
and K∗0 = γ1 K0 . 205
iii) Lithium vacancy model corresponds to α1 = 1 − 5x, α2 = x, α3 = 4x,
β1 = 1andγ1 = 1;andK∗2 = α1 K2 + α2 K1 , K∗1 = β1 K1 and K∗0 = γ1 K0 .

In this representation, α = β = γ = 0 means that the ions and the vacancies

are absent in these nonstoichiometric models.
The oxygen vacancy model is constructed by taking into account the 210
charge compensation for the nonstoichiometry in LiTaO3 by the oxygen and
the lithium vacancies. However, the tantalate vacancy model is arranged so
that the vacancy does not exist at the Li site but at the Ta one.
We want to point out that the vacancy models, described in this investi-
gation, containing niobium or tantale antisites. 215
In order to provide an adequate description of the defect structures
in the nonstoichiometric lithium tantalate, we have analytically per-
formed the calculations of different physical quantities, which are il-
lustrated in Table IV. Estimates of T∗c and d∗ for LiTaO3 have been
obtained by using the following values of the charges and masses 220

TABLE IV The Curie temperature T∗c and density d∗ as a function of the

nonstoichiometric composition x

(a) (b) (c)

P∗1 (1 + 1.66x)P1 (1−17.88x)P1 P1

P∗2 1−064x
(1−2x)(1−0.33x) P2
1+78.01x
(1−4x)(1+20x)(1+125.38x) P2
1+10.86x
1+21.07x P2

T∗c (1−0.13x)(1+1.16x)
(1−0.64x) Tc (1−17.88x)(1+0.62x)(1+20x)
(1+78.01)x) Tc 1+0.62x
1+10.86x Tc
d∗ (1 − 0.13x) VV∗ d (1 + 0.62x) VV∗ d (1 + 0.62x) VV∗ d

(a), (b) and (c) represent the three vacancy models.

TFJD093-03-64129 FEL May 5, 2005 16:45

DEFECT STRUCTURE IN NONSTOICHIOMETRIC LiTaO3 9

of ions: q0 = 2, q1 = 5, q2 = 1, M0 = 48, M1 = 180.95, M2 = 6.94. So,

b = 5.148 Å is the constant of lattice in the perpendicular direction of the
c-axis and n ≈ 1 is the index of the non electrostatic repulsion.

RESULTS

225 In principle, one could test these models by comparing the experimental
results with the calculated values according to the theoretical approach
previously mentioned.
To make the comparison between the three models, we have used the
experimental data of the Curie temperatures and crystal parameters measured
230 by Bennani and Husson [4].
To calculate the Curie temperatures suggested in Table IV, we needed to
know the Curie temperature of the exact stoichiometric compositions. So, we
used the following estimations of the Curie temperatures in stoichiometric
lithium tantalate: 917 K [4], 928 K [13] and 913 K [14]. The average value
235 of these three estimations is Tc = 919 K.
The calculated and experimental values of T∗c with different nonstoi-
chiometric compositions are illustrated in Fig. 3. The experimental data are
indicated by down triangles and the solid error bars show the uncertainties
on temperature and composition.
240 Comparing the experimental data with the theoretically calculated values,
one can see a good agreement between the measured temperatures and the
lithium vacancy model values (Fig. 3.2). The obtained results show clearly
that the Curie temperatures of the lithium vacancy model coincide with
the experimental values. So, this model shows that the Curie temperature
245 decreases as the composition x increases. It is the first direct quantitative
evidence that the lithium vacancies are indeed dominant in nonstoichiometric
LiTaO3 .
The oxygen and tantalate vacancies do not significantly contribute to the
nonstoichiometry in these samples.
250 The experimental and analytical studies have shown the important ef-
fect of different compositions of lithium tantalate on its corresponding
temperatures.
Let us analyze now the behavior of the density for the LiTaO3 ceramics
with different Li/Ta ratios.
255 To illustrate the defect structure of the nonstoichiometric LiTaO3 , we
report in Fig. 4 the variation of the density d∗ versus the composition x.
The values of the density determined by the Archimedes method
(Table III) and those estimated from the vacancy models are represented
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10 S. JEBBARI et al.

Figure 3. Curie temperature T∗c variation versus nonstoichiometric composition

x. (1) The calculated values according to the (a), (b) and (c) vacancy models are
compared to the experimental data. (2) Lithium vacancy model and the experimental
data with error bars.
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DEFECT STRUCTURE IN NONSTOICHIOMETRIC LiTaO3 11

Figure 4. Density variation d∗ as a function of the nonstoichiometric composition

x. (1) The estimated values from (a) and (c) (or (b)) vacancy models are compared
to the experimental data. Error bars indicate standard errors. (2) The open down
triangles are experimental data and the solid line represents the linear fits to the data.
Dash and dot lines indicate the linear fits of the (a) and (c) (or b) models respectively.
TFJD093-03-64129 FEL May 5, 2005 16:45

12 S. JEBBARI et al.

in this figure. Error bars indicate the maximum and minimum values of the
measured and calculated densities. Experiments show that density increases 260
with composition. Similar behavior is observed for the lithium (or tantalate)
vacancy model. A comparison between experimental and analytical values
of the density shows clearly that the density curve of the lithium vacancy
model draws near the measured one. This behavior is compatible with the
measured densities of LiNbO3 with different compositions [10]. 265
The experimental density is compatible with that calculated from (c) (or
(b)) model. In particular, the calculated value of the density for stoichiometric
LiTaO3 (d = 7.426 g/cm3 ) is compared with the measured density in this
work (d = 7.448 g/cm3 ) and that indicates in ref. [14] (d = 7.428 g/cm3 ).
Then, we suggested that the lithium vacancies contribute to the density of the 270
nonstoichiometric LiTaO3 . The agreement observed between the calculated
and measured values for the density of our samples supports the proposed
solid solution mechanism given in ref. [4].

DISCUSSION

The lithium vacancy model illustrated in Figs. 3 and 4 exhibits that the 275
agreement between the experimental facts and theoretical predictions is quite
satisfactory. In the present case (Fig. 3), there is a linear decrease in T∗c versus
increase of the composition x. The decrease of the Curie temperature can be
interpreted in terms of competition between Li+ and Ta5+ ions. The values
of the lithium vacancy model are in excellent agreement with experimental 280
data.
However, this experimental study, concerning the measurement of the
density with different nonstoichiometric compositions excludes the oxygen
vacancy model. This result is in agreement with the experimental search
developed in ref. [10]. As shown in Fig. 4, the density increases linearly with 285
increasing compositions. This is expected because Ta ions tend to occupy
Li sites. Therefore, a greater mass exists in just a slightly increased volume,
and density increases.
According to results of these three vacancy models, we conclude that the
lithium vacancy model is quantitatively and qualitatively imposed as the best 290
model to interpret the defect structure in the lithium tantalate.

CONCLUSION

Experimental and analytical study of the Curie temperature and density of

the solid solutions of nonstoichiometric LiTaO3 manifested the following
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DEFECT STRUCTURE IN NONSTOICHIOMETRIC LiTaO3 13

295 observations:

– The nonstoichiometric compositions of LiTaO3 influence the temperature

and density.
– The temperature is decreasing with increasing the composition.
– The density observed for the ceramic samples shows a linear increase with
300 the composition
– The Safaryan theory combined with the lithium vacancy model explains
this large dependence of the Curie temperature and the density on the
ceramic composition
– This method enables us, namely, to determine the mechanism of substitu-
305 tion, which is responsible in this material.
– This theoretical approach shows that the lithium vacancy model is the
defect model that can be suggested to describe the defect structure in
nonstoichiometric lithium tantalate.
– It allows estimating several important physical parameters as: the Curie
310 temperature and density of different compositions of nonstoichiometric
lithium tantalate.
– The calculated values are in a good agreement with the data obtained by
the experimental study.

ACKNOWLEDGMENTS

315 We are very grateful to Pr. M. Misdaq (LPTN, faculté des sciences Semlalia,
Marrakech) for critical reading of this paper and helpful suggestions.

REFERENCES

[1] M. Paul, M. Tabuchi, and A. R. West, Chem. Mater. 9, 3206 (1997).

[2] M. E. Lines and A. M. Glass, Principles and Application of Ferroelectrics and Related
320 Materials (Clarendon Press, Oxford, 1977).
[3] S. C. Abrahams and L. J. Bernstein, Phys. Chem. Solids 28, 1685 (1967).
[4] F. Bennani and E. Husson, J. of European Ceramic Society 21, 847 (2001).
[5] H. Fay, W. J. Alford, and H. M. Dess, Appl. Phys. Lett. 12, 89 (1968)
[6] P. Lerner, C. Legras, and J. P. Dumas, J. Cryst. Growth 3/4, 231 (1968).
325 [7] G. E. Peterson and A. Carnevale, J. Chem. Phys. 56, 4848 (1972).
[8] C. S. Abrahams and P. Marsh, Acta Crystallogr. Sect. B 42, 61 (1986).
[9] H. Donnerberg, S. M. Tomlinson, C. R. A. Catlow, and O. F. Schirmer, Phys. Rev. B 40,
909 (1989).
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[10] N. Iyi, K. Kitamura, F. Izumi, J. K. Yamamoto, T. Hayashi, H. Asano, and S. Kimura,

J. of Solid State Chem. 101, 340 (1992). 330
[11] F. P. Safaryan, Physics Letters A 191, 255 (1999).
[12] F. P. Safaryan, R. S. Feigelson, and A. M. Petrosyan, J. Appl. Phys. 85, 8079 (1999).
[13] S. C. Abrahams, J. M. Reddy, and J. L. Bernstein, J. Phys. Chem. Solids 27(69), 997
(1966).
[14] A. Huanosta and A. R. West, J. Appl. Phys. 61, 12, 5386 (1987). 335

APPENDIX

The energy of the electrostatic interaction of two charged long lines is,

2l
W = e2 δi δj b2 ln (I.1)
Rij

where δi = Nlbi qi with b, l, Rij , qi and Ni is the cell parameter, the line length,
the distance between the lines, the charge of ions and their number respec-
tively. We deduce the full energy of interaction of planes such as: 340

e2 qi qj 2l Bij
Uij = − ln + n (I.2)
b Rij Rij

e2 q q
where Bij = bni j (R0ij )n with R0ij is the equilibrium distance between planes
and n is the index of non electrostatic repulsion for interacting planes.
If we put: xij = Rij − R0ij , then the energy writes

  2
e 2 q i qj 1 2l e2 qi qj n xij
Uij = − ln 0 +  2 (I.3)
b n Rij b R0ij 2

e2 q q
The coefficient Cij = b(R0i )j2 n describing the interaction between Li and O
ij
planes (as well as for Ta and O) are obtained by differentiating (1.3) from 345
Xij .
However, the interaction between Li and Ta will deduce from the total
energy:

e 2 q i qj 2l Bij
Uij = ln 0 − (I.4)
b Rij Rij
TFJD093-03-64129 FEL May 5, 2005 16:45

DEFECT STRUCTURE IN NONSTOICHIOMETRIC LiTaO3 15

Figure 5. Displacement of Li+ , Ta5+ and 3O2− ions in a linear lattice.

2
Finally, for LiTaO3 crystal Cij coefficients are: CLi−O ≡ C20 = −3 qb0 qR22e n,
20
350

q0 q1 e2
CTa−O ≡ C10 = −3 n,
b R210
q1 q2 e2
CLi−Ta ≡ C21 = n. (I.5)
b R221

q1 , q2 and q0 are respectively the electric charges of Ta5+ , Li+ and O2− ions.
To solve the dynamic problem, we reduced the structure of the charged
planes to a system of vibration of linear lattice (Fig. 5).
The displacements of the three ions are indicated by vs (Li+ ), us (Ta5+ )
355 and ξs (O2− ). Then, the system is described by the differential equations as

M1 üs = C10 (ξs+1 − us ) + C21 (vs − us )

M2 v̈s = C21 (us − vs ) + C20 (ξs − us )
M0 ξ̈s = C20 (vs − ξs ) + C10 (vs−1 − ξs ) (I.6)

M1 , M2 , M0 are respectively the masses of the elements Ta, Li and 3O.

The choice of solutions in the form of plan waves,

gs = gei(ωt+ask) with g = u, v or ξ (I.7)

leads to a system, of linear equations, which has a nontrivial solution.

In order to obtain the fundamental frequencies of the optical branches, we
360 put k = 0 in the determinant equation ( = 0). Then, we get the following
equation,

ω4 − Bω2 + D = 0
TFJD093-03-64129 FEL May 5, 2005 16:45

16 S. JEBBARI et al.

where




1 1 1 1 1 1
B = C10 + + C21 + + C20 +
M M0 M1 M2 M2 M0

and

M1 + M2 + M0
D= (C10 C20 + C10 C21 + C21 C20 ). (I.8)
M1 M2 M0

The two optical modes are given by

1/2
1 1 2
ω12
2
= B± B −D (I.9)
2 4

For small parameter ((4D/B2 )  1) we deduce, 365

D ne2 M1 + M2 + M0 P1
ω22 = = , ω12 = B − ω22
B b M1 M2 M0 P2

where

P1 = 3q0 R212 − q1 R220 − q2 R210 ,

and



(R20 R21 )2 1 1 (R10 R21 )2 1 1
P2 = + + +
q2 M1 M0 q1 M2 M0
2

(R10 R20 ) 1 1
− + (I.10)
3q0 M1 M2