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Journal of Physics and Chemistry of Solids 70 (2009) 1231–1241

Contents lists available at ScienceDirect

Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

Electrical and electromechanical properties of

lead–potassium–yttrium–niobate ceramics—piezoelectric applications
K. Sambasiva Rao a,, P. Murali Krishna a,1, D. Madhava Prasad a,2, Joon Hyung Lee b
a
Centre for Piezoelectric Transducer Materials, Department of Physics, Andhra University, Visakhapatnam–530 003, Andhra Pradesh, India
b
Department of Inorganic Materials Engineering, Kyungpook National University, Daegu, 702701, Republic of Korea

a r t i c l e in fo abstract

Article history: Tungsten bronze (TB)-type oxide ceramic Pb0.74K0.13Y0.13Nb2O6 (PKYN) has been synthesized by the
Received 10 February 2008 standard solid state reaction method. Single phase formation, orthorhombic crystal structure was
Received in revised form confirmed by X-ray diffraction (XRD). The substitution of Y3+ in Pb0.74K0.52Nb2O6 (PKN) decreased the
14 June 2009
unit cell volume and TC ¼ 260 1C. PKYN exhibited the remnant polarization, Pr ¼ 8.5 mC/cm2, and
Accepted 20 June 2009
coercive field, Ec ¼ 28.71 kV/cm. Electrical spectroscopy studies were carried out over the temperature
(35–595 1C) and frequency (45 Hz–5 MHz) ranges, and the charge carrier phenomenon, grain–grain
Keywords: boundary contribution and non-Debye-type relaxation were analyzed. The relaxation species are
A. Ceramics immobile charges in low temperature and oxygen vacancies at higher temperature. The theoretical
D. Dielectric properties
values computed using the relations, e0 ¼ eN+sin(n(T)p/2)(a(T)/e0)(on(T)1); s(o) ¼ sdc+Aon are fitted
D. Ferroelectricity
with the experimental one. The n and A parameters suggested that the charge carrier’s couple with the
D. Electrical properties
soft mode and become mobile at TC. The activation enthalpy, Hm ¼ 0.38 eV, has been estimated from the
hopping frequency relation op ¼ oe exp(Hm/kBT). The piezoelectric constants Kt ¼ 35.4%,
d33 ¼ 69  1012 C/N, d31 ¼ 32  103 mV/N, SE11 ¼ 17.8 pm2/N, etc., achieved in PKYN indicate the
material is interesting for transducer applications. The activation energies from different formalisms
confirmed the ionic-type conduction.
& 2009 Elsevier Ltd. All rights reserved.

1. Introduction much scientific and commercial attention because of their

The frequency and temperature domain analyses of dielectric
materials have gained much importance in view of its simplicity
and clarity in describing the electrical properties. The basic
information about the dielectric properties of materials can be
obtained from the complex impedance analysis. The impedance
analysis allows the separation of several contributions of total
impedance, arising from bulk conductance and interfacial phe-
nomenon, viz. grain, grain boundary and other electrode interface
effects with an equivalent R–C circuit model under an applied AC
field. In ferroelectrics, the study of electrical conductivity is very
important. It reflects the strategy of poling and nature of
conductivity in these materials [1].
Niobates with tungsten bronze (TB) structure materials, e.g.
PbNb2O6 (20 molecules in unit cell) found by Goodman,
K2Li2Nb10O30 (KLN) and SrxBa1xNb2O6, etc. [2–6], have attracted
 Corresponding author.
E-mail address: konapala@sify.com (K. Sambasiva Rao).
1
Department of Physics, Gayatri Vidya Parishad College of Engineering,
Visakhapatnam, India.
2
Department of Basic Sciences and Humanities, GIT,GITA UNIVERSITY,
Visakhapatnam, India.
potential applications as ferroelectric, pyroelectric, piezoelectric
and non-linear optical properties. Ferroelectric TB-type oxide
material, lead potassium niobate, Pb(1x)K2xNb2O6, is considered
to be isomorphous with PbNb2O6 and belongs to space group
C2v14–Cm2m with four formula units per unit cell [7–11]. The
structure basically consists of a complex array of distorted BO6
octahedra sharing corners in such a way that three interstitial
sites (A, B and C) with coordination numbers 15, 12 and 9,
respectively, are available for cation occupation in the general
formula A6C2B10O30. If all A-sites are filled, then the structure is
called filled structure, e.g. PKN (material under investigation). By
substituting proper cations in these sites, one can tailor various
physical properties required for device applications [3–8].
The ferroelectric, thermal expansion and optical properties in
single crystals and ceramic of Pb(1x)K2xNb2O6 for x ¼ 0.2, 0.23
and 0.34 have been reported by Nakano et al. and Jana et al. [2,3].
It is also reported that the composition with x ¼ 0.2 is a leading
material for high-speed broadband surface acoustic wave devices
and the samples with x ¼ 0.43 and 0.50 did not exhibit any
ferroelectric behavior. Neurgaonkar et al. [6] revealed the
xKNbO3–(1x)PbNb2O6 ceramics showed complete solid solubi-
lity for x ¼ 0.0–0.33, but no ferroelectric phase was found when
xZ0.43. It is also reported that the Pb–K–niobate (x ¼ 0.2) crystals

0022-3697/$ - see front matter & 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2009.06.018
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exhibited larger values of piezoelectric d15 ¼ 470, coupling
constant k15 ¼ 0.69 and K24 ¼ 0.73, and anomalous elastic con-
stant temperature coefficients [7,12]. These parameters assure the
possibility of building a low insertion loss SAW device with low
thermal runaway and larger bandwidth compared to those made
with ST-cut quartz crystal. Further, Pb–K–niobate materials are
useful for high-temperature piezoelectric device applications,
which are useful in various industries like steel, automobile,
aviation, etc. Recently, structure, microstructure, electromechani-
cal, dielectric, impedance and modulus studies of Pb(1x)K2xNb2O6
for x ¼ 0.2–0.32 ceramics modified with Li ,Ti and certain rare-
earth ions have been reported by Rao et al. [13–16].
Our literature survey indicated that only few papers have been
published on lead potassium niobate ceramics modified with rare-
earth ions. In view of the excellent properties exhibited by PKN, an
attempt has been made to study the preparation, structural,
microstructure, piezoelectric, dielectric, electric impedance and
modulus and conductivity properties of lead–potassium–yt-
trium–niobate, Pb0.74K0.13Y0.13Nb2O6 (PKYN) ceramics. The im-
pedance (Z*), electrical modulus (M*), permittivity (e*) and
conductivity (s*) spectroscopy technique has been utilized to
understand the contribution of microstructure to the bulk.
2. Compound synthesis and experimental
Polycrystalline yttrium-substituted lead potassium niobate,
Pb0.74K0.13Y0.13Nb2O6 (PKYN), has been synthesized by high-
temperature solid state reaction technique. Initially, AR-grade
powders of oxides and carbonates of PbO, Y2O3, Nb2O5 and K2CO3
were mixed and ground well in methanol medium before each
thermal treatment. The powder was placed in a platinum crucible
covered with a lid and then calcined at 900 1C for 4 h for the
complete chemical reaction. The process of grinding and calcina-
tion has been repeated three times to achieve homogenous and
single-phase powder. The formation of the single-phase com-
pound was confirmed via X-ray powder diffraction technique. To
the fine calcined powder an adequate amount of organic binder,
poly vinyl alcohol (PVA), was added and ground well to provide
strength and ability to flow and to reduce the brittleness of the
sample. This powder was compacted into discs of 11 mm diameter
and 3 mm thickness under a hydraulic press with 580 MPa
pressure. The green pellets were placed on a platinum foil by
sprinkling a small amount of calcined powder on both surfaces to
compensate the loss of lead, and then covered with an inverted
Fig. 1. X-ray diffractogram of PKYN.
crucible. The pellets sintered at 1225 1C for 60 min exhibited good
density and were crack-free.
The structural and phase formation analyses of the calcined
powder were performed using a Philips X-ray diffractometer
operated by CuKa radiation l ¼ 1.5406 Å over a wide range of
Bragg’s angle, 2y (101r2yr901) at a scanning rate of 21/min. The
lattice parameters are computed using ‘‘interpretation and
indexing program (POWD)’’ by E. Wu, School of Physical Sciences,
Flinders University of South Australia, Bed Ford Park, Australia.
The microstructural study was carried out by a computer-
controlled scanning electron microscope (SEM) (JEOL_JY:Mo-
del5800F) on optically polished surfaces of pellets. The measure-
ment of impedance, electrical modulus, conductivity and
permittivity as a function of temperature (from room temperature
(RT) to 600 1C) and frequency (45 Hz–5 MHz) have been carried
out using a computer interfaced HIOKI 3532-50 LCR Hi-Tester,
Japan. Impedance/gain phase analyzer HP-4194A and Berlin Coert
piezo-d-meter were used for the estimation of piezoelectric
constants. Silver electrodes were deposited on the faces of the
ceramic samples to perform the above studies.
3. Results and discussion
3.1. Structure
The X-ray diffractogram of PKYN is shown in Fig. 1. The peaks’
patterns are observed to be sharp and all the peaks were indexed,
revealing the single phase formation of the compound. The 100%
intensity peak in PKYN is found at 2y ¼ 29.331. For ceramics of
Pb2KNb5O15 the same is reported at around 2y ¼ 321 (JCPDS card
no.33-1020). Our studies in PKN system modified with different
rare-earth ions in A-sites (i.e. in K+) showed a shift in 100%
intensity peak towards the lower angle side [16]. The computer
program package ‘POWD’ calculated the inter-planar spacing (dcal)
for the observed values of inter-planar spacing (dobs) in XRD in
different crystal systems. Finally, the orthorhombic crystal system
P P
was confirmed as the difference, Dd ¼ (dobs–dcal), is minimal.
The values of Miller index and inter-planar spacing is given in
Table 1.
The lattice parameters of PKYN are found to be less than the
unsubstituted PKN [14], which may be due to the smaller ionic
radii of the substituted element Y3+ (0.893 Å) compared to Pb2+
(1.20 Å) and K+ (1.33 Å). This decrease in lattice parameters
reflected in an increase in density, i.e. theoretical density (dthe)
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Table 1
Comparison of observed and calculated d-values (Å) of PKYN.

dobs (Å) dcal (Å) hkl I/I0

5.0764 4.9145 23 0 7.88

3.0444 3.0440 35 0 100
2.9690 2.9892 06 0 75.53
2.7547 2.7850 45 0 5.96
2.5793 2.5848 43 1 4.46
2.1425 2.1422 81 0 33.67
1.9623 1.9595 73 1 7.24
1.9059 1.9057 10 2 11.8
1.7934 1.7935 0 10 0 7.51
1.7507 1.7495 86 0 50.25
1.6118 1.6121 77 1 33.03
1.5396 1.5416 63 2 5.21
1.5045 1.5032 64 2 15.62
1.3563 1.3560 90 2 20.89
1.2898 1.2899 12 4 1 15.57
1.2399 1.2397 9 10 1 8.37

Table 2
Lattice parameters of PKYN.
Fig. 2. SEM micrograph of PKYN.
Lattice Orthorhombic Density Particle Porosity %
parameters distortion (g/cm3) size Density
(Å) (b/a) (Å) (nm)
X-ray Exptl
15 Pb0.74K0.13Y0.13Nb2O6
A ¼ 17.2612 1.039 6.31 6.06 83.6 0.04 96
B ¼ 17.9353
C ¼ 3.8349
10

6.31 g/cm3. The experimental density has been estimated by the 5

Archimedes principle and found to be dexp ¼ 6.06 g/cm3, i.e. 96%
Pr [ μC/cm2]

of dthe. The orthorhombic distortion, b/a ¼ 1.039 in PKYN reveals

the substitution of Y3+ in PKN does not distort its orthorhombic 0
structure. The crystallite size, t ¼ 83.6 nm, has been estimated by
Debye–Scherrer’s equation, t ¼ (0.9l)/(B cos y), where B is the -5
diffraction line broadening at half of its maximum intensity
( ¼ 0.0984 rad), t the diameter of the crystal particle and l the
X-ray wavelength [17]. The values of lattice parameters, density -10
(dexp), orthorhombic distortion (b/a), porosity, percentage of
density and crystallite size for PKYN are given in Table 2. -15

3.2. Microstructure -40 -30 -20 -10 0 10 20 30 40

Ec [kV/cm]
The SEM micrograph of PKYN is shown in Fig. 2. The surface
morphology indicates the existence of polycrystalline Fig. 3. P–E hysteresis loop of PKYN.
microstructure comprising good grain growth with shape
anisotropy. The grains of unequal size appear to be distributed
inhomogeneously throughout the sample with a certain degree of
Fig. 3. Before tracing the loop, the material has been poled at
porosity. The average grain size of (d1–4 mm) has been estimated
125 1C/30 min at an applied field of 7.00 kV/mm by field-cooled
by the linear intercept method using the relation
method [18,19]. The remnant polarization, Pr ¼ 8.5 mC/cm2, and
1:56L coercive field, Ec ¼ 28.71 kV/cm, have been calculated from the
d¼ ; loop. The unsaturated loop of PKYN suggests that the poling
MN
conditions are to be changed. In our studies, PKN exhibited the
where L is the random line length, M the magnification of
value of Ec ¼ 3.85 kV/C m and Ps ¼ 47.64 mC/cm2. Therefore, it is
micrograph and N the number of grain-boundary intercepts by
clear that the substitution of Y3+ in PKN increased the Ec. This may
line. This indicates the higher density achieved in PKYN. Further, it
be due to the lower value of polarizability of Y3+ compared to
is noticed that the grain size has been increased compared with
either Pb2+ or K+ [20]. Further, the conductivity is found to be
the unsubstituted PKN.
decreased in PKYN. In unsubstituted PKN, the room-temperature
conductivity is in the order of 108 S/cm at 1 kHz, and it is
3.3. Hysteresis increased to 106 S/cm at 590 1C. While, in PKYN the same are
changed from 109 (at RT) to 106 S/cm. Therefore, the existence
The hysteresis loop is a characteristic feature for the ferro- of low conductivity and higher loss is also ascribed to the lower
electric material. The P–E hysteresis loop of PKYN is shown in hysteresis in PKYN.
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3.4. Piezoelectric
In recent years, ferroelectric ceramics have come into promi-
nence as suitable for various electronic device applications. The
ceramic materials have potentially lower cost and greater durability
under adverse atmospheric conditions. The piezoelectric studies in
PKYN are reported for the first time by the authors as no previous
data are available in the literature. The values of electromechanical
coupling coefficients (Kp, Kt and K31), charge coefficients (d31 and
d33), voltage coefficients (g31 and g33) and stiffness constant, SE11,
mechanical quality factor, Qm and frequency constant in thickness
mode, Nt in PKYN are presented in Table 3. The parameters were
estimated on 1.2-mm-thick and 10-mm-diameter poled sample
from resonance and anti-resonance frequencies.
It was reported that the PbNb2O6 ceramics possessing the
values of Kt of about 40% and Qm of 20 or less be used for a
broadband sound transducer [21,22]. The achieved values of Kt
and Qm in PKYN indicate the material is suitable for broadband
ultrasonic transducer applications. Higher d coefficients are
desirable for motional, vibrational devices such as SONAR and
sounders. Ceramics used for electric wave filter applications
should have high eT , Kp and Qm values and also possess good
temperature stability with respect to Kp and NP values. Greater Kp
produces wider and smaller Kp produces narrow frequency
spacings in filters [23–26].
In the thickness mode, d33 ¼ S/E ¼ Dt/(t/V/t) (or) Dt ¼ d33V,
where S is the strain and E the electric field strength [27]. It
indicates the change in thickness, Dt, of the plate is dependent on
material d coefficient and voltage (V), and independent of plate
thickness, t. Hence, for an applied voltage, 100 V, charge
coefficient, d33 ¼ 69  1012 C/N may produce a change in thick-
ness, Dt ¼ 6.9 nm. Even though this change in thickness is
infinitesimally small, one can raise this value by increasing the
applied voltage. In the length extensional case, the transverse
coefficient, d31 ¼ S/E ¼ Dl/l/(V/t) (or) Dl ¼ d31 (l V/t), where l is the
length of the sample. Therefore, by substituting the values of
d31 ¼ 32  1012 C/N (the negative sign indicates contraction),
l ¼ 10 mm, t ¼ 1.2 mm and V ¼ 100 V, one may get a change in
length up to Dl ¼ 26 nm. Now, the magnitude of voltage generated
(V) by voltage coefficient (g) can be expressed as the ratio of open
Table 3
Piezoelectric data of PKYN.
% Kp % Kt % K31 d31 1012 C/N d33  1012 C/N g31 103 mV/N
19.6 35.4 12 32 69 8.2
2250
Pb0.74K0.13Y0.13Nb2O6
2000
500 Hz
1750 1 K Hz
10 K Hz
1500 50 K Hz
100 K Hz
εll
εl
1250
1000
750
500
0 100 200 300 400 500 600
Temperature °C
Fig. 4. Temperature dependence of (a) real and (b) imaginary part of dielectric constant in PKYN.
circuit electric field, E, to the applied stress, T (pressure), i.e. g ¼
E/T ¼ V/t (T). On rearranging, V ¼ g  t  T, indicating V is directly
proportional to material thickness t, g coefficient and magnitude
of applied stress, T [27]. For an applied stress of 5516  104 N/m2,
the value of g33 ¼ 17.7  103 mV/N develops a voltage 1.17 kV
across the sample of PKYN. This discharge voltage may be used to
produce a spark across 0.36 mm gap to ignite gases. Further,
Kp ¼ 19.6%, Kt ¼ 35.4% and K31 ¼ 12%, obtained in PKYN, reveal
that the conversion efficiency (electrical to mechanical or vice
versa) can be efficient. The values of piezoelectric constants in
PKYN are found to be less when compared to PKN. The values of
piezoelectric constants may exhibit further enhancement, by
poling the material at higher temperatures.
3.5. Dielectric spectroscopy
Variation in real (e0 ) and imaginary (e00 ) parts of dielectric constant
as a function of temperature at different frequencies is shown in Fig.
4(a,b). In ferroelectrics, the value of e0 initially increases with increase
in temperature up to Curie temperature (TC), where interfacial
polarization becomes higher compared to dipolar polarization and
then starts decreasing in the para region. From Fig. 4(a), the
TC ¼ 260 1C with e0 ¼ 2094 poses the phase transition from
orthorhombic (ferroelectric) to tetragonal (para electric) in PKYN.
Contribution from interfacial polarization is due to difference
in conductivity in the material. The dielectric polarization can be
modeled by space charge or oxygen vacancy hopping. In case of
polycrystalline ceramics, this is commonly observed if the grains
are semiconducting and the grain boundaries are insulating. The
point defects in oxides may occur in two ways. Firstly, the
semiconductive grains in the present ceramics are believed to lose
traces of oxygen represented by the Kroger–Vink notation [26,27]
Oo -12O2 ðgÞ þ Vo ;
Vo2V0 +e0
V0 o2V00 o +e0
E
g33  103 mV/N S11  1012 m2/N Qm Nt
17.7 17.8 33 2000
1000
Pb0.74K0.13Y0.13Nb2O6
800 500 Hz
1K Hz
10K Hz
600 50K Hz
100K Hz
400
200
0
0 100 200 300 400 500 600
Temperature °C
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where Vo is oxygen vacancy, V0 o,V00 o are oxygen vacancies with
single and double charges and e0 the electron released or captured.
Since Nb can exist in +3 and +5 states there is a possibility for
release of electrons in the above reaction and are captured by Nb5+
to generate Nb3+. Secondly, during cooling of the samples the re-
oxidation is limited only to the surface due to insufficient time.
These effects cause a difference in resistance between grain and
grain boundary with formation of a barrier. The build-up of charge
carriers at grain and grain-boundary interface leads to large
polarization, which results in a high dielectric constant at lower
frequencies. This principle is instrumental in the formation of
grain-boundary-active devices [15].
The reported value of TC in Pb0.74K0.52Nb2O6 is 465 1C [14].
Substitution of yttrium decreased the TC (260 1C) and broadened
the real dielectric constant versus temperature response. This
trend is in accordance with a number of rare-earth ion-
substituted TB-type ferroelectrics [14–17]. The broad dielectric
peak has been ascribed to the compositional fluctuations caused
by the substitution of yttrium. An anomaly has been observed in
the e00 versus temperature (Fig. 4b) curve near TC of the material.
Further, the decrease in the value of e00 at TC may be due to the
reduction in the domain wall contribution [19–23]. The dispersion
in the high-temperature region indicates the localized ionic
conductivity in the material [25,28,29]. The Curie–Weiss law,
e0 ¼ K/(TTC), has been fitted in the para region and the Curie
constant (K) calculated to be 2.3  105. The K in the order 105 is a
characteristic of oxygen octahedral ferroelectrics [16]. The values
of RT dielectric constant, eRT0, TC (1C), dielectric constant at
transition temperature, eTC , dielectric loss tangent (tan d) and
Curie constant (K) are given in Table 4.
Fig. 5(a,b) shows the variation of e0 and e00 with log f at different
temperatures (200–580 1C) in PKYN. In the conducting dielectric
materials, higher values of e0 and e00 at low frequencies are related
to the space-charge polarization and the free-charge motion
related to AC conductivity relaxation. Such strong dispersions
referred to as the low-frequency dielectric dispersion (LFDD) and
the detailed studies of this phenomenon were carried by Jonscher
et al. [29]. According to Jonscher’s universal dielectric relations,
the complex dielectric constant as a function of the frequency o
can be expressed as
e ¼ e0 r e00 r ¼ e1 þ ðs=ie0 oÞ þ ðaðTÞ=e0 ÞðionðTÞ1 Þ: ð1Þ
From this, the relation for real and imaginary dielectric
constants can be expressed as
e0 ¼ e1 þ sin ðnðTÞp=2ÞðaðTÞ=e0 ÞðonðTÞ1 Þ; ð2Þ
e00 ¼ s=e0 o þ cos ðnðTÞp=2ÞðaðTÞ=e0 ÞðonðTÞ1 Þ: ð3Þ
where eN is the ‘high-frequency’ value of the dielectric constant,
n(T) the temperature-dependent exponent and a(T) determines
the strength of the polarizability arising from the universal
mechanism. The theoretical values of e0 are estimated using Eq.
(2) and are found to be fitted with experimental data.
3.6. DC and AC conductivity spectroscopy
Fig. 6 shows the plot of electrical conductivity, s(o), as a
function of frequency at different temperatures in PKYN. From
these plots, the AC conductivity increases with increase in
frequency, revealing the bound carriers trapped in the sample.
Further, they are observed to be flattening in the low-frequency
region as temperature increases (4460 1C). According to
Jonscher’s law, electrical conduction is a thermally activated
process and the origin of frequency dependence of conductivity
lies in the relaxation phenomena arising due to mobile charge
carriers. The conduction behavior of the PKYN obeys Jonscher’s
universal law [30] as follows:
sðoÞ ¼ sdc þ Aon : ð4Þ
The columbic interactions (between lattice sites) contribute to
the conductivity dispersion followed by power law with exponent
n(0ono1). The value of n measured from the change in slope of
conductivity plots showed a minimum at TC (n ¼ 0.77) with a
subsequent increase with increase in temperature. Dissado and
Hill suggested that the exponent n characterizes the strong

Table 4
Dielectric data of PKYN.

elrt (1 KHz) TC (1C) e1TC (1 kHz) Tan d at RT Tan d at TC Curie constant K (  105) srt (  106 s/cm)

888 260 2093 0.086 0.064 2.3 4.67

3.8 200°C 480°C 4.50 200 °C

240°C 520°C 240 °C
3.6 260°C 590°C 260 °C
3.75
380°C 380 °C
3.4 480 °C
Log εll

3.00 540 °C
log εl

3.2 590 °C
2.25
3.0

2.8 1.50
Pb0.74K0.13Y0.13Nb2O6 Pb0.74K0.13Y0.13Nb2O6
2.6 0.75
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
Log f Log f

Fig. 5. The frequency dependence of (a) e0 and (b) e00 on log–log scale at various frequencies of PKYN ceramic.
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interaction between the charge carriers and polarization [31,32].
Further, according to lattice dynamics theory [30], these carriers
become mobile near TC, suggesting the energy loss is high and the
stored energy is small.
The hopping frequency, op, corresponds to transition between
the DC and AC conductivity regions and appears to shift towards
the higher frequency (Fig. 6) side with increasing temperature.
The relation between op and frequency-independent conductiv-
ity, sdc, is given by op ¼ (s dc/A)1/n . Taking ‘log’ on both the sides
we get
logA ¼ logsdc  nlogop :
The computed values of n and ‘log A’ have been plotted as a
function of the temperature and are shown in Fig. 7(a,b). The pre-
factor A shows an anomaly corresponding to TC (log A ¼ 8.96),
allowing us to determine the strength of the polarizability (or the
non-ideal conductivity) arising from the diffusive motion of the
carriers. From these results, it implies that the dynamic process
involved near TC is different from that of the other temperatures.
According to lattice dynamics theory, one of the transverse modes
(soft mode) is weakened and the restoring force tends to become
zero at the ferroelectric–paraelectric transition. Therefore, it
suggests that the charge carrier’s couple with the soft mode and
become mobile at TC [33].
10-3
Pb0.74K0.13Y0.13Nb2O6
1x10-4
A.C.Conductivity (S/Cm)
This means that the closer the material approaches the Curie
temperature, the longer it takes to relax. For 0ono1, Jonscher’s
universal capacitance term can be represented by real and
imaginary parts, which represents stored and lost energy,
respectively. The real and imaginary parts are in a frequency-
independent ratio
Energy lost np
¼ cot ;
Energy stored 2
which implies a low energy loss for a high value and vice versa.
ð5Þ Further, small value of n is due to charge carriers or to extrinsic
dipoles arising from the presence of defects or impurities. This
result reveals the slowly varying conductivity and dispersion
mechanism in dielectric constant at the low-frequency region of
the material.
Using Eqs. (2) and (4), the theoretical values of e0 and s(o)
have been estimated and are fitted with the experimental data.
From Fig. 8, one can find a good agreement between theoretical
and experimental data. The DC conductivity specifies the hopping
of charge carriers after the surrounding environment has relaxed.
Therefore, jump relaxation theory yields the Almond–West
assumption, the AC conductivity follows relation, s(o) ¼ Kop
[1+(op/o)n] and DC conductivity, sdc ¼ Kop [31]. The ion hopping
rates are thermally activated and follows the Arrhenius relation
op ¼ oe exp(Hm/kBT), where Hm is the activation enthalpy for
hopping of ions, which is estimated to be 0.38 eV (Fig. 9) in PKYN.
This also suggests that the increase in conductivity with
temperature is mainly due to increase in hopping rate op with
temperature.
The Arrhenius plots for DC and AC conductivity are shown in
Fig. 10. The change in slope of the curve reflects a change in the

1x10-5 conductivity phenomenon. This suggests the plots are broadly

divided into three regions: (i) 570–380 1C (ii) 260–200 1C, and (iii)
190–120 1C. It is observed that in region (i), the AC conductivity is
10-6
less frequency dependent. Whereas, it is slightly dependent on
200 °C 440 °C frequency in regions (ii) and (iii), and increases with increase in
10-7 480 °C frequency. The calculated DC and AC conductivity activation
240 °C
energy values are given in Table 5.
260 °C 520 °C
10-8 The conductivity was observed to be dispersive in low-
300 °C 540 °C temperature region and appeared to be merged at high tempera-
580 °C tures. It indicates that an onset of intrinsic conductivity mechan-
10-9 380 °C
ism dominates at high temperatures. The non-appreciable
400 °C 590 °C
variation of AC conductivity (Fig. 10) at low temperature indicates
102 103 104 105 106 the multiple relaxations [34,35]. The DC conductivity deviates
Log f Hz more at lower temperatures and magnitude is few orders less
than that of the AC conductivity. This may be due to the most
Fig. 6. Frequency dependence part of AC conductivity at different temperatures. difficult transition in complete percolation paths between the

1.00
-8.96
0.95
-9.10
0.90
log A
n

-9.24
0.85

0.80 -9.38
Pb0.74K0.13Y0.13Nb2O6 Pb0.74K0.13Y0.13Nb2O6
0.75
100 200 300 400 500 600 100 200 300 400 500 600
Temperature °C Temperature °C

Fig. 7. (a) Variation of critical exponent n(T) and (b) temperature dependence of the pre-factor A(T) with temperature showing minimum at TC of PKYN.
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105
590°C
1x10-4
Experimental n = 0.97 220°C
104 Theoretical logA = -9.44129

Conductivity (s/cm)
n = 0.87
log A = -9.623
10-6
103
εl

10-8 Pb0.74K0.13Y0.13Nb2O6
102
Theoritical
Pb0.74K0.13Y0.13Nb2O6 Experimental

101 10-10
102 103 104 105 106 102 103 104 105 106
f Hz f Hz

Fig. 8. Theoretical and experimental curve fittings of dielectric constant and conductivity.

Table 5
3.5 DC and AC conductivity activation energy values of PKYN.

Pb0.74K0.13Y0.13Nb2O6 Composition PKYN

3.0
Temperature range (1C) Conductivity activation energy (eV)

2.5 AC
log (ωp) (sec-1)

DC 1 kHz 10 kHz 20 kHz

2.0
570–380 0.43 0.43 0.27 0.21
260–200 0.20 0.11 0.05 0.03
1.5
190–120 0.08 0.09 0.06 0.03

1.0

0.5 region. This is due to the fact that at low frequencies the
conductivity is taken by mobility or transportation over long
distances rather than by relaxation/orientation mechanism. The
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
energy required for relaxation/orientation process is lower than
1000/T (K-1) that required for mobility of charge carriers over longer distances
Fig. 9. Ion-hopping rates as a function of T (K1) in PKYN.
[39–41]. The activation energy values obtained at high tempera-
ture are attributed to thermal motion of the oxygen vacancies or
the formation of association among the oxygen vacancies and
1x10-5 DC residual cations in the grain boundary [16,25,26]. The decrease of
Pb0.74K0.13Y0.13Nb2O6 1K Hz conductivity in PKYN may be due to decrease in the concentration
10K Hz of oxygen vacancies [42]. The values of activation energies are
20K Hz typical for ionic-type conduction mechanism in PKYN.
10-6
Conductivity (σ S/Cm )

3.7. Impedance spectroscopy

10-7 Fig. 11(a,b) shows the variation of real (Z0 ) and imaginary (Z00 )
parts of impedance as a function of frequency at different
temperatures in PKYN. From Fig. 11(a), the decrease in Z0 value
with increase in temperature indicates the reduction in the bulk
10-8 resistance of the material, which is a characteristic of negative
temperature of coefficient of resistance (NTCR) behavior [27]. The
higher values of Z0 (2  108 O at 380 1C) in low-frequency side
clearly indicate the space-charge polarization. The observed
10-9
1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
enhanced value of Z0 values in PKYN compared to PKN (below
480 1C) may be due to decrease in conduction path arising as a
1000/T (K-1)
result of lattice distortion.
Fig. 10. log (s) versus 1000/T at different frequencies of real. In Fig. 11(b), the Z00 peak frequencies shift towards the higher
frequency side with increase in temperature. The Z00 max peak
electrodes, while the AC conductivity is determined by the easiest seems to shift towards the higher frequency side with increase in
local movement [36–39]. temperature indicating the increase in relaxation, loss in the
From Table 5, the AC conduction activation energies at high material and dependence of space charges on temperature and
frequency are found to be lower than that of the low-frequency frequency [43,44]. The relaxation species may be electrons or
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360°C
340°C
380°C
380°C 420°C
440°C 440°C
500°C Pb0.74K0.13Y0.13Nb2O6 500°C Pb0.74K0.13Y0.13Nb2O6
2.0x106 2.5x106 540°C
540°C 5 5
1.6x10 560°C 1.2x10
560°C
1.6x106 2.0x106 580°C
500°C
580°C 1.2x105 540°C 9.0x104 540°C
560°C 590°C 560°C
590°C

ZllΩ
580°C
8.0x104 1.5x106 6.0x104 580°C

ZlΩ
1.2x106 590°C 590°C
ZlΩ

3.0x104

ZllΩ
4.0x104
1.0x106
8.0x105 0.0
0.0
102 103 104 105 106 102 103 104 105 106
5.0x105
4.0x105 Log f Hz Log f Hz

0.0
0.0
102 103 104 105 106 102 103 104 105 106
Log f Hz Log f Hz

Fig. 11. Variation in (a) real [Z0 ] and (b) imaginary [Z00 ] parts of impedance with frequency at different temperatures in PKYN.

1.2
Pb0.74K0.13Y0.13Nb2O6 105
1.0 380 °C Pb0.74K0.13Y0.13Nb2O6
420 °C
0.8 440 °C
104
Zll / Zllmax

500 °C
0.6 540 °C
ωmax

560 °C
0.4 590 °C
103
0.2

0.0
102
102 103 104 105 106 1.1 1.2 1.3 1.4 1.5 1.6
Log f Hz 1000/T (K)

Fig. 12. (a) Normalized imaginary parts Z00 /Z00 max as a function of frequency. (b) Temperature dependence of relaxation frequency of PKYN.

immobile charges in low temperature and oxygen vacancies at
higher temperature region. Further, irrespective of the tempera-
ture, all Z0 and Z00 curves are found to be merging above 10 kHz.
This indicates that the space–charge polarization is reduced with
increasing frequency and that the contribution from the grain
predominates [45,46].
Fig. 12(a) shows the normalized imaginary part Z00 /Z00 max of
impedance as a function of frequency in PKYN at several
temperatures. It seems from the figure that at high temperature
there is a triggering of another relaxation process. The Z00 /Z00 max
parameter exhibited a peak with slightly asymmetric degree at
each temperature especially at high temperatures. At the peak,
the relaxation is defined by the condition omtm ¼ 1, where tm is
the peak relaxation time. The relaxation frequency obeys the
Arrhenius relation given by om ¼ o0 exp[Et/KB T], where o0 is
the pre-exponential factor. From the logom1/T plot (Fig. 12(b)),
the activation energy Et ¼ 0.57 eV has been calculated in
temperature region 390–580 1C.
To study the contribution of various microscopic elements like
intra-grain, inter-grain, electrode effect and relaxation process, one
can use the Cole–Cole plots analysis [41,47]. The Z00 versus Z0 plot
drawn at different temperatures (380–590 1C) and a typical
equivalent circuit in PKYN has been shown in Fig. 13(a, b). From
Fig. 13(a), as temperature increases above 400 1C, the complex
impedance curve is observed to be semicircle with a decrease
in size revealing the increase in conductivity of the PKYN. At
high temperature (4500 1C) the semicircle can be resolved
into two, suggesting the contribution of two relaxation mechanisms
due to grain (high-frequency side) and grain boundary (low-frequency
side).
The intercept of the semicircular arcs on the real axis gives the
grain (Rg) and grain-boundary resistance (Rgb). The corresponding
capacitances (Cg and Cgb) are calculated using the relation
omax ¼ 2pfmax ¼ (RC)1 ¼ t1, where omax is the frequency
at the semicircle maxima. From these parameters an equivalent
parallel RC circuit can be represented, which is typically as shown
in Fig. 13(b) [42]. The existence of the center of semicircles below
the real axis indicates the non-Debye-type distribution of
relaxation times in PKYN. In order to establish a connection
between the microstructure and electrical properties, a ‘brick
layer model’ [42] was proposed typically as shown in Fig. 14. In
this model grains are assumed to be cube-shaped, and grain
boundaries to exist as flat layers between grains. The advantage of
adopting the ‘brick layer model’ is the determination of grain-
boundary conductivity without detailed microstructural and
electrical information [41]. The bulk values of Z0 and Z00 are
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K. Sambasiva Rao et al. / Journal of Physics and Chemistry of Solids 70 (2009) 1231–1241 1239

Pb0.74K0.13Y0.13Nb2O6
6x105 360°C
440°C
500°C
4x105 540°C
ZllΩ

590°C

2x105

0
0 2x105 4x105 6x105 8x105
ZlΩ

Fig. 13. Cole–Cole plots (a) at different temperatures and (b) equivalent circuit.

measured temperature scale, grain relaxation time is found to be

more compared to the grain-boundary relaxation time and
exhibited nearly parallel decrement up to 560 1C. These para-
meters satisfied the Arrhenius behavior and evaluated the grain
and grain-boundary conduction activation energies, Eg ¼ 0.48 eV
and Egb ¼ 0.39 eV, grain and grain-boundary relaxation activation
energies eg ¼ 0.37 eV and egb ¼ 0.59 eV, in the region 400–500 1C.
The activation energies reveal that the conduction takes place
mainly through grain boundary rather than grains in PKYN
material.

3.8. Electrical modulus spectroscopy

The dielectric modulus represents the real dielectric relaxation

process in different types of materials [44–46]. This can be
expressed as
   
1 e0 ie00
M¼ ¼ þ ¼ M 0 þ iM 00 :
e e þe02 00 2 e þe02 00 2

Fig. 14. ‘‘Brick Layer’’ model of a polycrystalline material. In practice, regions of low capacitance, such as grain interiors,
are characterized by M00 data, whereas more resistive regions such
as grain boundaries and pellet surface layers, which often have
related to Rg, Rgb, Cg and Cgb as follows [43]: higher associated capacitances, are characterized using Z00 spectra
[47]. Fig. 16(a,b) shows the real M0 (o) and imaginary parts M00 (o)
Rg Rgb of electrical modulus as a function of frequency (45 Hz–5 MHz) at
Z0 ¼ þ ð6Þ
ð1 þ oRg Cg Þ2 ð1 þ oRgb Cgb Þ2 various temperatures (220–580 1C) in PKYN.
In low frequency, high-temperature region (Fig. 16(a)) the
" # " # value of M0 approaches zero, confirming an appreciable electrode
oRg Cg oRgb Cgb and/or ionic polarization phenomenon in the material [48,49]. The
Z 00 ¼ Rg þ Rgb : ð7Þ
1 þ ðoRg Cg Þ2 1 þ ðoRgb Cgb Þ2 M0 (o) was observed to be linear from 1 kHz to 1 MHz for the
temperatureo400 1C, as temperature increases, M0 (o) is found to
increase to a higher value (4.14  104 at 590 1C, 1 MHz) then with
Fig. 15(a–c) shows variation of resistances (Rg and Rgb), a subsequent decrease. Fig. 16(b) shows the magnitude of M00 peak
capacitances (Cg and Cgb), grain relaxation time, tg, and grain- decreases with increase in temperature up to TC, beyond this there
boundary relaxation time, tgb with temperature (360–580 1C) in is an increase. Also, the peak shifts systematically towards higher
PKYN material. From Fig. 15(a), above 450 1C the Rg exhibits more frequency side with increase in temperature. The shift in
variation compared to Rgb, above which variation is nearly frequency of M00 peak corresponds to the so-called conductivity
parallel. Also, both Rg and Rgb decrease with increase in relaxation.
temperature, suggesting that the NTCR behaves like Fig. 17(a) shows the normalized imaginary part of the electrical
semiconductors. Fig. 15(b) represents the grain-boundary modulus, M00 /M00 max, as a function of logarithmic frequency at
capacitance (order of 109) is more compared to the grain several temperatures in PKYN. The M00 /M00 max parameter exhibits a
(order of 1010). Further, grain-boundary capacitance is observed peak with a slightly asymmetric degree at each temperature. The
to decrease with increase in temperature. region on the left of the peak represents the motion of the mobile
Variations in grain and grain-boundary relaxation times (eg, carriers over long distances. Whereas, the region to the right of
egb) with temperature have been shown in Fig. 15(c). In the the peak belongs to the carriers that are confined to potential
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107 1E-8 10-2

Pb0.74K0.13Y0.13Nb2O6 Rg Pb0.74K0.13Y0.13Nb2O6 Cg grain
Cgb grain boundary
Rgb

Relaxation (Sec)
Resistance (Ω)

Capacitance (F)
106 10-3

1E-9 1x10-4
105
1x10-5
Pb0.74K0.13Y0.13Nb2O6
104
1E-10 10-6
350 400 450 500 550 600 350 400 450 500 550 600 350 400 450 500 550 600
Temperature °C Temperautre °C Temperature °C

Fig. 15. (a–c) Variation of grain, grain boundary (a) resistance, (b) capacitance and (c) relaxation time with temperature of PKYN.

220°C 200°C 380°C

5x10-4 Pb0.74K0.13Y0.13Nb2O6
260°C 2x10-4 Pb K Y Nb O 240°C 440°C
0.74 0.13 0.13 2 6
340°C 260°C 540°C
4x10-4 380°C
2x10-4 340°C 590°C
440°C 360°C
480°C
3x10-4 540°C 1x10-4
Ml

590°C
Mll

2x10-4 8x10-5

1x10-4 4x10-5

0 0
102 103 104 105 106 102 103 104 105 106
Log f Hz log f (Hz)

Fig. 16. . Variation of (a) real part and (b) imaginary part of electrical modulus with frequency of PKYN.
Relaxational angular frequency, ωmax

Pb0.74K0.13Y0.13Nb2O6 340°C
360°C
105
1.0 380°C Pb0.74K0.13Y0.13Nb2O6
440°C
480°C
0.8 540°C
590°C 104
Mll/Mllmax

0.6

0.4
103
0.2

0.0
102
102 103 104 105 106 1.1 1.2 1.3 1.4 1.5 1.6 1.7
logf Hz 1000/T (1/K)

Fig. 17. M00 /M00 max as function of frequency at different temperatures (b) The Arrhenius plot of relaxation frequency as a function of 1/T in PKYN.

wells, which are mobile over short distances [32]. The frequency time and absolute temperature, respectively. From the Z00 and M00
range at and around the peak indicates the transition from short plots, it is observed that the Z00 peak broadens with increase in
range to long-range mobility, considering the decrease in temperature and in the case of M00 the curve broadens with
frequency. At the peak, the relaxation is defined by the decrease in temperature. This type of temperature and frequency
condition, ot ¼ 1, where t is the most probable relaxation time. dependence of Z00 and M00 arise due to the distribution of
The reciprocal of M00 peak frequency (fmax) represents the time relaxation times because of cationic disorder at A and B sites.
scale of transition from long-range mobility and is defined as the The effect of space-charge polarization can be represented by the
characteristic relaxation time, p ¼ (2pfmax)1. magnitude of mismatch between the M00 and Z00 curves [50]. This
The relaxation time exhibited thermally activated dependence. result again confirms the non-Debye-type relaxation involved by
The DC conductivity relaxation can be obtained from the peak the dipoles.
positions, i.e. fmax. The relation op ¼ o0 exp[Em/KT] resulted the Fig. 18 shows the variation in normalized peak parameters M00 /
relaxation activation energy 0.53 eV (Fig. 17(b)), where o0, t0 and M00 max and Z00 /Z00 max as a function of logarithmic frequency measured
T are the pre-exponential factors of angular frequency, relaxation at different temperatures. From the plot it is possible to observe the

K. Sambasiva Rao et al. / Journal of Physics and Chemistry of Solids 70 (2009) 1231–1241
1.0
Normalized to peak
0.8
0.6
0.4
0.2
0.0
102 103
Fig. 18. Normalized parameters M00 /M00 max and Z00 /Z00 max as a function of logarithmic frequency at different temperatures.
change of an apparent polarization by the inspection of the
magnitude of mismatch between the peaks. An appreciable
difference between the widths of the curves at full-width half-
maxima (FWHM) evidenced the localized conduction and the
departure from ideal Debye-like conduction [32,50]. The existence
of some overlapping or very similar peak positions of curves (Fig. 18)
proves the long-range conductivity. Hence, the studies illustrate well
that all dynamic processes occurring at different frequencies are
thermally activated and ionic-type conductivity exists in PKYN.
4. Conclusions
Tungsten bronze oxide ceramic Pb0.74K0.13Y0.13Nb2O6 (PKYN) is
a classical ferroelectric with orthorhombic crystal structure.
Substitution of Y3+ decreased the Curie temperature to 260 1C
and also the conductivity. The piezoelectric constants
d33 ¼ 69  1012 C/N, d31 ¼ 32  1012 C/N, g33 ¼ 17.7  103
mV/N, Kp ¼ 19.6%, Kt ¼ 35.4%, K31 ¼ 12% indicated that it is an
interesting material for transducer device applications. Higher e0
and e00 values in the low-frequency region are related to space–-
charge polarization. The dispersion in the high-temperature
region indicated the localized ionic conductivity. From ion
hopping rates op the activation enthalpy Hm for hopping of ions
is estimated to be 0.38 eV. An anomaly at TC in n and A parameters
revealed the charge carrier’s couple with the soft mode and become
mobile. The ‘‘brick layer model’’ showed the conduction through
grains boundary rather than grains. The magnitude of mismatch
between the M00 and Z00 curves at FWHM evidenced the non-Debye-
type relaxation. The M00 /M00 max peak separated the long range and
localized charge carriers and the DC conductivity relaxation
activation energy was found to be 0.53 eV. Three conductivity
components were recognized inside the grain: a long-range DC
conductivity at low-frequency region, a capacitive behavior at
higher frequencies and a universal power law behavior in an
intermediate frequency region. The activation energies from
different formalisms reveal the ionic-type conduction in PKYN.
Acknowledgements
Authors K.S. Rao and P. Murali Krishna thank DRDO, New Delhi,
for sanction of the research project and research fellowship.
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