Impedance spectroscopy study of the electrical conductivity and dielectric constant of

polycrystalline LiNbO 3
S. Lanfredi and A. C. M. Rodrigues
Citation: Journal of Applied Physics 86, 2215 (1999); doi: 10.1063/1.371033
View online: http://dx.doi.org/10.1063/1.371033
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JOURNAL OF APPLIED PHYSICS

VOLUME 86, NUMBER 4

15 AUGUST 1999

Impedance spectroscopy study of the electrical conductivity

and dielectric constant of polycrystalline LiNbO3
S. Lanfredi
o Carlos, C.P. 676,
Departamento de Qumica, Universidade Federal de Sa
o Carlos, S.P., Brazil
13.565-905 Sa

A. C. M. Rodriguesa)
o Carlos, C.P. 676,
Departamento de Engenharia de Materiais, Universidade Federal de Sa
o Carlos, S.P., Brazil
13.565-905 Sa

Received 4 August 1998; accepted for publication 3 May 1999

The electrical properties of LiNbO3 ceramic pellets were investigated by impedance spectroscopy in
the temperature range of 450800 C. Impedance data are presented in the Nyquist plot which, in
addition to the separation of grain and grain boundary contributions, allows the determination of the
relaxation frequency of samples. The results of bulk electrical conductivity and its activation energy,
confirmed by measuring samples with different geometrical parameters, are presented. Relaxation
frequencies follow an Arrhenius behavior with the same activation energy found for the electrical
conductivity. Relaxation frequencies were also used to calculate bulk dielectric constants and the
results are compared to the behavior of the real part of the sample dielectric constant. 1999
American Institute of Physics. S0021-89799901516-9

I. INTRODUCTION

The ferroelectric behavior of LiNbO3 was first reported

by Mathias and Remeika1 and later confirmed by Nassau and
Levinstein.2 LiNbO3 presents an unusually high Curie temperature of about 1210 C that is very close to its melting
temperature, 1260 C.3
The study of single-crystal LiNbO3 is of great interest
due to its electro-optic and piezoelectric properties. Its dielectric properties have been studied at fixed frequencies3,4
or in various frequency ranges.5 The conduction processes in
LiNbO3 crystals have also been studied by the ac method
with fixed frequencies5 and with different partial oxygen
pressures.68 It was found that the electrical conductivity in
1/4
at low P O2 1
LiNbO3 single crystals depends on P O
2
atm and that this dependency is attributed to singly ionized
oxygen vacancies.6,7 Jorgensen and Bartlett7 propose that, at
low P O2 , LiNbO3 presents an electronic conduction, whereas
at high P O2 , the conduction process is ionic, caused by
lithium ions, and independent of P O2 . The conductivity of
single-crystal LiNbO3 may also depend on the Li/Nb ratio in
both low and high P O2 regions.8
The electrical properties of polycrystalline LiNbO3 have
been less studied, although some related works are found in
the literature.9,10 This study presents the contribution of the
complex impedance spectroscopy to the investigation of the
properties of conductivity and dielectric behavior of polycrystalline LiNbO3 in the 450800 C temperature range, in
an air atmosphere. Impedance spectroscopy is a powerful
tool for the study of the electrical properties of ionic, electronic, or mixed conductor ceramics. It has already been apa

Author to whom correspondence should be addressed; electronic mail:

acmr@power.ufscar.br

plied successfully in the investigation of ferroelectric materials such as LiTaO3 ceramic11 and single crystal,12 and
polycrystalline Bi4Ti3O1213 and BaTiO3 . 14
This work presents impedance data in the complex impedance plane plot, the so-called Nyquist diagram. In this
representation, grain and grain boundary contributions are
easily identified and the electrical properties of the bulk material can be studied separately from grain boundary interference. Thus, bulk properties may be related to single-crystal
properties. Moreover, this representation allows determination of the relaxation frequency of the material ( f 0 ) at the
apex of the bulk semicircle. At a given temperature, the relaxation frequency is an intrinsic characteristic of the material, independent of the geometrical parameter of the sample
and might be used to determine dielectric constants. Thus,
results obtained using the relaxation frequency are unambiguous and have a stronger physical significance than those
obtained at arbitrarily chosen fixed frequencies. The comparison of the behavior of the dielectric constant calculated
using f 0 with the behavior of the real part of the complex
dielectric constant supports this assumption.

II. THEORY

Impedance data of materials that have capacitive and

resistive components, when represented in the Nyquist diagram i.e., the negative of the imaginary part (Im Z) in the
y axis and the real part (Re Z) in the x axiseach point
corresponding to a different frequency, lead to a succession
of semicircles. For example, a polycrystalline material usually presents grain and grain boundary properties with different time constants leading to two successive semicircles. In
this case, the second intercept of the high frequency semi-

0021-8979/99/86(4)/2215/5/$15.00
2215
1999 American Institute of Physics
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2216

J. Appl. Phys., Vol. 86, No. 4, 15 August 1999

S. Lanfredi and A. C. M. Rodrigues

circle with the real axis is the bulk resistance (R b ) of the

sample. Hence, the bulk electrical conductivity ( b ) is written

b 1/R b * l/A,

where l is the thickness and A the area of the electrode deposited on the sample.
Electrical conductivity of ceramic materials is thermally activated and follows an Arrhenius law

0 expEa/kT ,

where 0 is a pre-exponential factor and a characteristic of

the material, Ea, k and T are, respectively, the activation
energy for conduction, Boltzmanns constant, and the absolute temperature. Thus, the activation energy for conduction
Ea can be calculated from the slope of the straight line
given by log 1/T.
The relaxation frequency ( f 0 ) of the material, independently of the geometrical parameter of the sample, is found
at the apex of the Nyquist semicircle15 and fulfills the condition
2 f 0 R b C b 1.

From this relation, the bulk capacitance of the material (C b ),

also called the geometric capacitance,15 can be calculated
and the bulk dielectric constant b can be determined using
C b b 0 A/l,

where 0 is the vacuum permittivity.

The dielectric constant is also written as a complex number

with

Z / 2 f 0 A/lZ ,

Z / 2 f 0 A/lZ 2 ,

where Z and Z are the real and imaginary parts of the

module of the impedance Z measured at frequency f.
III. EXPERIMENT
A. Sample preparation

Lithium niobate was synthesized by a chemical evaporative method using lithium nitrate and a soluble niobium salt,
NH4H2NbOC2O433H2O as starting reagents. This method,
described elsewhere,16 employs a low calcination temperature 550 C, leads to the formation of very fine mean crystallite size88 nm16 and homogeneous LiNbO3 powder,
and provides good sintering of the ceramic pellets under
study.
The calcinated powder was dispersed by dry milling in
an agate mortar. After dispersal, 2 wt% of polyvinyl butiral
was added as a binder. This mixture was pressed under 190
MPa uniaxial pressure into disk forms. The pellets were then
burned out at 500 C for 5 h to complete binder elimination.
Sintering was performed in an air atmosphere with the
pellets placed in an alumina crucible, using LiNbO3 powder
as a substrate to prevent the sample making contact with the

FIG. 1. Complex impedance data at different temperatures of LiNbO3 ceramic sample sample a. The smallest semicircle corresponds to a measurement taken at 700 C.

alumina. The pellets were heated up to 700 C heating rate

10 C/min held for 30 min at the same temperature, then
heated up to 1080 C heating rate 6 C/min, held at this
temperature for 2 h and then furnace cooled.
After sintering, the ceramic pellets presented a relative
density of 96%. Samples a and b were pressed using around
1.0 and 0.5 g of LiNbO3 powder, respectively. Thus, although the pellets presented the same area, sample b was
approximately half of the thickness l of sample a. Their
final geometrical parameters were A being the area of samples electrode: sample a: l0.205 cm, A1.024 cm2 (l/A
0.200 cm1 ); sample b: l0.103 cm, A0.980 cm2 (l/A
0.105 cm1 ).
B. Electrical measurements

The electrodes required for the electrical measurements

were deposited on both faces of the ceramic samples by applying platinum paste Demetron 308A, which was dried at
900 C for 15 min. Electrical measurements were taken by
means of complex impedance spectroscopy, in the 5 Hz13
MHz frequency range, using a Hewlett-Packard HP 4192A
impedance analyzer controlled by a personal computer. This
equipment was checked with a Boonton 76-3A precision decade capacitor. The difference between the measurements
and the standards was within the standards accuracy
0.1%0.001 pF at 1 MHz.
Electrical measurements were performed in an air atmosphere from 450 to 800 C, with samples placed in an appropriate sample holder with two-electrode configuration. The
capacitance of the sample holder without the sample was
measured and was equal to 0.5 pF. The applied voltage was
0.1 V.
IV. RESULTS AND DISCUSSION

The impedance spectra obtained at different temperatures for samples a (l/A0.200 cm1 ) and b (l/A
0.105 cm1 ) are shown in Figs. 1 and 2. It can be observed
that, at the same temperatures, the resistances of sample a are
approximately twice those of sample b. This confirms that
the high frequency semicircle is really representative of the
materials bulk electrical properties. It is also important to

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J. Appl. Phys., Vol. 86, No. 4, 15 August 1999

S. Lanfredi and A. C. M. Rodrigues

2217

TABLE I. Bulk resistance (R b ), bulk capacitance (C b ), and ralaxation frequency ( f 0 ) of LiNbO3 ceramic samples and R b C b product.
T (C)
450
500
550
600
650
700
750
800
FIG. 2. Complex impedance data at different temperatures of polycrystalline
LiNbO3 , sample b. The smallest semicircle corresponds to a measurement
taken at 700 C.

note that the distribution of frequencies in the bulk semicircle is the same for both samples at the same temperature,
proving that the relaxation frequency is independent of the
samples geometrical parameter and is an intrinsic characteristic of the material. The second semicircle, at low frequencies, is depressed by angles up to 50, indicating the nonhomogeneous electrical behavior of grain boundaries. A
parallel RC equivalent circuit Fig. 3 accurately fit the high
frequency data. Hence, the electrical grain properties of polycrystalline LiNbO3 can be associated to a simple RC equivalent circuit, in which R represents the bulk resistance (R b )
and C the bulk or geometric capacitance (C b ) of the sample.
The fitting procedure used here is the same as the one described by Kleitz and Kennedy17 and allows determination of
resistance and relaxation frequencies with a precision better
than 3%.18 Table I indicates the values of R b and C b of both
samples at all the measurement temperatures. The measured
cell capacitance 0.5 pF was negligible in relation to the
measured bulk capacitances. Therefore, no correction of the
capacitance was necessary. In order to check the consistency
of the results, Table I also indicates the relaxation frequencies, obtained from the fitting procedure, and the product
RC which is expected to be equal to 1.
The bulk electrical conductivity, obtained from the complex impedance plot using Eq. 1, is plotted against temperature in an Arrhenius fit Fig. 4. The activation energy
for conduction deduced from those plots was found to be

450
500
550
600
650
700
750
800

R b ()

C b (F)

f 0 (Hz)

LiNbO3 sample a (l/A0.200 cm1 )

1.15106
2.901011
4.80103
5
11
4.0010
2.8410
1.40104
7.95104
2.791011
7.17104
4
11
3.9310
2.8010
1.45105
1.87104
2.851011
2.98105
3
11
8.9310
2.9510
6.04105
4.65103
3.051011
1.12106
3
11
2.5910
3.1010
2.06106
LiNbO3 sample b (l/A0.105 cm1 )
5.74105
6.051011
4.59103
2.10105
5.861011
1.29104
4
11
4.1610
5.7710
6.63104
2.01104
5.841011
1.35105
3
11
9.8010
5.9310
2.74105
4.87103
6.061011
5.39105
3
11
2.7810
6.1610
9.28105
1.38103
6.251011
1.84106

R bC b
1.0058
0.9992
0.9992
1.0025
0.9979
0.9997
0.9980
1.0392
1.0015
0.9974
0.9999
0.9957
1.0005
0.9995
0.9985
0.9971

1.17 and 1.15 eV for samples a and b, respectively. Figure 5

shows the temperature dependence of the relaxation frequencies for both samples, which follows the same Arrhenius law
same activation energy as the electrical conductivity.
Bulk dielectric constant b , calculated from the relaxation frequency Eq. 4 of the thinnest sample and the real
part of dielectric constant Eq. 6, calculated for different
frequencies, are plotted against temperature in Fig. 6. The
values of each relaxation frequency are indicated. Bulk dielectric constants for the ceramic sample presented here are
in the same range and consistent with those reported by Nassau, Levinstein, and Loiacomo,3 Smolenskii et al.,4 and
Tomeno and Matsumura19 for the LiNbO3 single crystal.
These values are also in accordance with the results obtained

FIG. 3. Experimental and calculated solid line complex impedance data,

FIG. 4. Arrhenius plot of electrical conductivity of polycrystalline LiNbO3
with the corresponding RC equivalent circuit.
samples a and b.
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2218

J. Appl. Phys., Vol. 86, No. 4, 15 August 1999

S. Lanfredi and A. C. M. Rodrigues

FIG. 7. Frequency dependence of sample b for different temperatures:

a from 5 to 107 Hz, b from 105 to 107 Hz.
FIG. 5. Temperature dependence of relaxation frequency of LiNbO3 ceramic samples a and b.

by Bhatt and Semwall10 for polycrystalline LiNbO3 . Of

note is the fact that the bulk dielectric constant ( b ) calculated using f 0 agrees with the value of calculated at the
nearest frequency and that b , has almost no perceptible
variation in the investigated temperature range. For each
temperature, the relaxation frequency remains near the plateau of frequencies in which shows only minor variations
Fig. 7. However, if the measurement frequency is reduced
to far below the relaxation frequency, it might be found at
the grain boundary frequency range in the Nyquist diagram
Fig. 2. In this case, differs by orders of magnitude from
b Fig. 7. In fact, frequencies out of the bulk or high frequency semicircle range on the Nyquist diagram do not describe bulk properties. Hence, the behavior of the bulk di-

electric constant calculated from the relaxation frequency

remains a reliable and fiducial description of the temperature
dependence of the grain dielectric properties of polycrystalline LiNbO3 .
V. CONCLUSION

The impedance spectroscopy data of polycrystalline

LiNbO3 show a semicircle in the high frequency region corresponding to the grain properties of ceramic pellets, followed by a second and more depressed semicircle attributed
to the grain boundary properties. The electrical properties of
polycrystalline LiNbO3 can, thus, be described as a parallel
RC circuit in which R represents the bulk resistance and C
the bulk capacitance of the material. The bulk electrical conductivity of LiNbO3 ceramic pellets follows an Arrhenius
law with an activation energy of 1.15 eV. The same activation energy is found for the Arrhenius plot of relaxation frequencies. Dielectric constants that were determined using the
relaxation frequency present no significant variation in the
studied temperature range and lead to reliable and unambiguous results when compared to the real part of the dielectric
constant obtained at arbitrary frequencies.
ACKNOWLEDGMENTS

The authors gratefully acknowledge Dr. Laurent Dessemond LEPMI, Grenoble, France and Dr. Rinaldo Gregorio
Filho UFSCar-DEMa, Brazil for their valuable discussions.
S. Lanfredi extends her thanks to Capes and Fapesp for their
financial support.
B. Mathias and J. P. Remeika, Phys. Rev. 82, 727 1951.
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G. A. Smolenskii, N. N. Krainik, N. P. Khuchua, V. V. Zhdanova, and I.
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A. Mansingh and A. Dhar, J. Phys. D 18, 2059 1985.
6
FIG. 6. Temperature dependence of the real part of dielectric constant ,
G. Bergmann, Solid State Commun. 6, 77 1968.
7
Eq. 6 and of the bulk dielectric constant b , Eq. 4, sample b.
P. J. Jorgensen and R. W. Bartlett, J. Phys. Chem. Solids 30, 2639 1969.
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S. Lanfredi and A. C. M. Rodrigues

2219

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