Solid State Communications 132 (2004) 431–435

www.elsevier.com/locate/ssc

AC behavior and PTCR effect in PZN-PT-BT

ferroelectric ceramics
A. Peláiz-Barrancoa,*, I. González-Carmenatea, F. Calderón-Piñara, E. Torres-Garcı́ab,c
a
Facultad de Fı́sica-Instituto de Materiales y Reactivos. Universidad de La Habana. San Lázaro y L, Vedado. La Habana 10400, Cuba
b
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, México DF 07730, México
c
Facultad de Quı́mica-Instituto de Materiales y Reactivos, Universidad de La Habana. Zapata y G, Vedado. La Habana 10400, Cuba

Received 16 July 2004; received in revised form 27 July 2004; accepted 23 August 2004 by P. Wachter
Available online 11 September 2004

Abstract
The ac behavior of the PZN-PT-BT ceramic system was studied in wide temperature and frequency ranges. Two
contributions in the impedance plane were obtained: grain and grain-boundary responses. A positive temperature coefficient of
resistivity (PTCR) was observed in the temperature dependence of the ceramic resistivity, dominated by the grain response. The
results are explained on the basis of the Heywang and Jonker models. The Schottky barrier formed at grain boundary regions
acts as traps of the electrons available from the oxygen vacancies in the ceramic, whose concentration decreases with
temperature by an oxidation process when the temperature rises in air conditions, increasing the Schottky barrier height of the
samples. This provides PTCR characteristics from the transition temperature to about 220 8C.
q 2004 Published by Elsevier Ltd.

PACS: 77.84.Dy; 77.90.Ck

Keywords: A. Ferroelectrics; C. Grain boundaries; D. Dielectric response

1. Introduction found extensive applications as thermal fuses, thermistors,

It is well known that donor-doped barium titanate
ceramics sintered in air exhibit an anomalous rise in
resistivity near the ferroelectric transition temperature Tm.
This phenomenon is commonly known as positive tempera-
ture coefficient of resistivity (PTCR) effect [1–3], which is
widely associated to a grain boundary phenomenon [4–9],
where the Schottky barrier induced by the surface states
existing at the grain boundary regions leads to high
resistivity of the ceramic material above Tm. In the
ferroelectric phase the spontaneous polarization results in
compensation of surface states [10]. This kind of effect has
* Corresponding author. Tel.: C53-78788958; fax: C53-
78783471.
E-mail address: pelaiz@fisica.uh.cu (A. Peláiz-Barranco).
0038-1098/$ - see front matter q 2004 Published by Elsevier Ltd.
doi:10.1016/j.ssc.2004.08.030
safety circuits, degaussers, and other overload protection
devices [2,3].
Pb(Zn1/3Nb2/3)O3 (PZN) belongs to the relaxor ferro-
electrics family, which have received wider attention
because of their significant technical importance on the
application of electromechanical devices [11]. Pure PZN
preparation in conventional conditions is very difficult due
to the appearance of pyrochlore phase. The addition of
barium titanate (BT) has shown pure phases, being widely
investigated [12]. On the other hand, the lead titanate (PT)
modified PZN-BT has shown lower diffuseness of the phase
transition and weaker frequency dispersion of the dielectric
response [13]. Also, it has been studied that the PZN-PT-BT
ferroelectric ceramic materials show excellent dielectric and
ferroelectric for electronics applications [14]. Therefore,
this material has been widely studied [14–17].
In this paper we present the study of the PTCR effect in
432 A. Peláiz-Barranco et al. / Solid State Communications 132 (2004) 431–435

the (Pb0.8Ba0.2)[(Zn1/3Nb2/3)0.7Ti0.3]O3 (PZN-PT-BT) cer-

amics by using impedance spectroscopy.

2. Experimental procedure

The ferroelectric ceramic samples of nominal compo-

sition (Pb0.8Ba0.2)[(Zn1/3Nb2/3)0.7Ti0.3]O3 were prepared by
using the ceramic method. The reagent powders (PbO,
BaCO3, Nb2O5, TiO2, ZnO) were milled for 2 h and
calcined at 900 8C during 2 h in air with a heating rate of
508/min. Later, they were milled again for 2 h and formed as
thick disks by cold-pressing at 2!107 kg/m2. The sintering
process was made in suitable atmosphere (PbO) at 1160 8C
during 1.5 h in a well-covered platinum crucible with a
heating rate of 508/min. Ceramic samples of high density
(rZ7.45 g/cm3) were obtained and the X-ray analysis
showed a pure rhombohedral perovskite-related phase.
The scanning electronic microscopy on fractured samples
showed a lower average grain size (2.5 mm) than that of
previous report [18], which was associated to a lower
sintering time in our study.
Electrodes were fabricated on the parallel faces of the
ceramic disks (8.7 mm of diameter and 1.3 mm of thickness)
by using Au strips and an organogold paste. The ac response
was studied from 5 Hz to 13 MHz by using an impedance
analyzer HP 4192 A, applying 1V to the samples. A wide
temperature range was analyzed (18–700 8C). Thermal
analysis was made in a high-resolution thermobalance (TA
Instrument, model TG-2950) in air.

3. Results and discussion

Typical impedance planes for the studied system are

shown in Fig. 1. As the temperature is increased above the
transition temperature (TmZ39 8C) an arc is seen (Fig. 1a),
which become a distorted semicircle (Fig. 1b) at higher
temperatures (TO400 8C). At still higher temperature, a
more ideally semicircular shape is seen (Fig. 1b). From such
plots it is feasible to extract the overall resistance of the
sample (RT) since the portion of the real axis intercepted by
such as an arc is equal to RT. The total resistivity of the
ceramic (rT) was calculated from RT and plotted against
temperature showing a PTCR effect (Fig. 2).
It can be observed that the studied system appears to be
just another poor PTCR material. Because no donor-
inducing dopants or prior reducing atmosphere to create
donors were used, the grains are fairly resistive. This
accounts for the high resistivity below the transition
temperature. Then, the PTCR effect is small because the
starting resistivity is so high.
The impedance plot is very convenient for analyzing the
microstructural behavior of grain, grain-boundaries and
second phases. In single-phase systems, the complex
impedance plane (Z 00 vs. Z 0 , where Z 0 and Z 00 are,
Fig. 1. Typical impedance planes for the ceramic system showing
(a) an arc when the temperature is increased above the transition
temperature (TmZ39 8C) and (b) a distorted semicircle at higher
temperatures (TO400 8C).
respectively, the real and imaginary components of the
impedance) consists of a regular semicircle. It is modeled as
a resistance–capacitance (RC) parallel circuit [19]. Poly-
crystalline materials show complex responses resulting from
the overlap of the signals from the different components. In
such cases, circuit simulations are necessary in order to
separate each contribution.
The signal in the impedance plane for the studied sample
above 400 8C was a deformed semicircle, indicating that the
electrical response of this material was composed of two or
more overlapping individual signals. We analyzed various
element arrangements that could describe the electrical
response of the samples [19]. Taking into account that the
frequency dependence [20] of the imaginary part of
impedance showed two contributions for the studied
 A. Peláiz-Barranco et al. / Solid State Communications 132 (2004) 431–435
Fig. 2. Temperature dependence of the sample resistivity (rT),
obtained from RT, showing a PTCR effect from the transition
temperature to 220 8C approximately.
samples, the selected equivalent circuit consisted of two RC
parallel arms connected in series (Fig. 1). The distorted
semicircle was deconvolved by using the non-linear least-
squares fit program (NLLS-fit program) [21] and the R and
C values corresponding to each individual signal were
determined. The experimental response was simulated at
each of the temperatures analyzed. The overall fit was
excellent for each case and the uncertainty of the R and C
values was below 3%.
The values of the corresponding circuit elements can be
extracted as follows: the resistor values (R) are semicircle’s
diameters. At the top of each semicircle, the impedance of
the resistive and the capacitance arms are equal (RZ1/uxC,
where ux is the angular frequency, uxZ2pfx). Since this
frequency can be derived from Z 00 (f) plots (where it appears
as a maximum), C (capacitance) can be straightforwardly
calculated.
The capacitance data are shown as a function of
temperature in Fig. 3, where it can be seen that C2 is
essentially independent of temperature, whereas C1 rises
increasingly rapidly as the temperature decreases towards
the transition temperature. The C1 values show a Curie–
Weiss behavior above the transition temperature (it is not
shown here). The magnitude of the capacitance and its
temperature dependence provide criteria for establishing the
relationship between each semicircle, i.e. each phase, and
the pertinent microstructural features of the material [22].
From these results it is suggested that C1 and C2 represent
the grains and grain-boundaries, respectively [22]. C1 is
characteristic of the bulk behavior response of a ferro-
electric material [22]. The temperature-independent beha-
vior of C2 indicates that the grain-boundary region is not
ferroelectric because of any phase transition is observed.
433
Fig. 3. Temperature dependence of the capacitances of both
contributions to the ceramic response in the impedance planes. C1
is characteristic of the bulk behavior response of a ferroelectric
material and C2 is associated with the grain boundaries.
This is supported by the structural analysis of the system,
which showed a pure rhombohedral phase, a single ferro-
electric phase associated to C1 taking into account the
capacitance values and its temperature dependence. On the
other hand, from C2 values could be estimated that the grain
boundaries are very thick (wnm) because of a non-
ferroelectric response must have very low dielectric
permittivity. The thermally activated decrease in the
resistivity above 220 8C is due to the grain boundary
potential barrier with its small temperature dependences. C2,
which is deduced only above 450 8C, is a measure of the
potential barrier thickness.
From Fig. 2, it could be seen that the PTCR effect is
observed from the transition temperature of the ceramic
until 220 8C approximately. In that temperature range, the
grain-boundaries do not show an important contribution to
the ac sample response, which is associated to the high bulk
resistivity [23]. The grain boundary contribution could be
treated as separate or partly resolved second semicircle in
the complex plane plots depending on the relative
magnitudes of the resistivity for the bulk and grain
boundary, which depends on the grain size. The grain size
and the homogeneous grain structure could limit the grain
boundary contribution in the complex impedance plane [23].
The PZN-PT-BT system has been prepared taking into
account any cationic vacancies. The Arrhenius behavior of
the bulk resistivity (r1) in a wide temperature range above
the Curie point (Fig. 4) shows activation energy values from
0.20 to 0.83 eV, which could be associated to a oxygen
vacancies movement [24]. It has been known that virtually
there is no ionic transport in the perovskite lattice due to the
low mobility of the cation vacancies [25]. Therefore are the
434 A. Peláiz-Barranco et al. / Solid State Communications 132 (2004) 431–435
Fig. 4. Arrhenius dependence of the bulk contribution in a wide
temperature range. The slope change shows the inversion in the
resistivity behavior.
oxygen ions, which may show a certain motion in perovskite
ceramics. On the other hand, following the Jonker’s model
[5], it can be showed that a barrier height, B, that varies
linearly with temperature, T, yields a thermally activated
resistivity, r1. Specifically, if BZB0(TKTc), where B0 is a
constant, then ð ð 1 ÞÞ Z B T . Thus the Arrhenius resis-
d log r
dð1=kT Þ 0 c
tivity above the Curie temperature is predicted by the
Jonker’s model [5].
Oxygen vacancies are thought to be presented in reduced
specimens. The additional electrons available from the
oxygen vacancies lead to a decrease in the sample
resistivity, reducing the potential barrier. In air conditions,
the experimental condition in the present studied, a
reduction or oxidation process could take place in the
ceramics when the temperature rises. In the first case, the
concentration of the oxygen vacancies increases very
quickly with their acceptor action decreasing the resistivity
of the sample with temperature. When an oxidation process
takes place in air conditions, the concentration of the oxygen
vacancies decreases very quickly lowering their acceptor
action. Then, the resistivity of the sample increases with
temperature. The high-resolution thermogravimetric anal-
ysis (Fig. 5) shows that the sample is gradually and
continuously oxidated between room temperature and
250 8C. The resulting PTCR characteristics will therefore
be expected, which has been observed experimentally from
the transition temperature to 220 8C approximately. Accord-
ing to the Heywang and Jonker models [4–6], the PTCR
behavior primarily arises from the Schottky barrier formed
at grain boundary regions. These barriers act as effective
electron traps of the electrons available from the oxygen
vacancies and increase the Schottky barrier height of the
materials.
Fig. 5. Results of the high resolution thermogravimetric analysis for
the PZN-PT-BT ceramics from room temperature to 250 8C.
4. Conclusions
The ac behavior of the PZN-PT-BT ceramic system
shows two contributions in the impedance plane: the grain
response showing characteristics of the bulk behavior
response of a ferroelectric material and the grain-
boundaries response. An oxidation process provides an
increment of the resistivity of the sample with temperature
from room temperature to 250 8C approximately. This
promotes the PTCR characteristics, which is explained
following the Heywang and Jonker models. The PTCR
behavior primarily arises from the Schottky barrier formed
at grain boundary regions, which act as effective electron
traps of the available electrons from the oxygen vacancies in
the ceramic, increasing the Schottky barrier height of
the material.
Acknowledgements
The authors wish to thank to the Third World Academy
of Sciences for financial support (RG/PHYS/LA No. 99-050
and No. 02-225) and to the ICTP, Trieste-Italy, for financial
support of Latin-American Network of Ferroelectric
Materials (NET-43).
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