Journal of Alloys and Compounds 453 (2008) 325331

Impedance spectroscopy of (Na0.5Bi0.5)(Zr0.25Ti0.75)O3 lead-free ceramic

Lily a , K. Kumari a , K. Prasad a, , R.N.P. Choudhary b
a

Materials Research Laboratory, University Department of Physics, T.M. Bhagalpur University, Bhagalpur 812007, India
b Department of Physics and Meteorology, Indian Institute of Technology, Kharagpur 721302, India
Received 29 May 2006; received in revised form 14 November 2006; accepted 16 November 2006
Available online 19 December 2006

Abstract
Polycrystalline sample of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 was prepared using a high-temperature solid-state reaction technique. XRD analysis indicated the formation of a single-phase orthorhombic structure. AC impedance plots were used as tool to analyse the electrical behaviour of the
sample as a function of frequency at different temperature. The AC impedance studies revealed the presence of grain boundary effect, from 350 C
onward. Complex impedance analysis indicated non-Debye type dielectric relaxation. The Nyquist plot showed the negative temperature coefficient
of resistance (NTCR) character of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 . AC conductivity data were used to evaluate the density of states at Fermi level and
activation energy of the compound. DC electrical and thermal conductivities of grain and grain boundary have been assessed.
2006 Elsevier B.V. All rights reserved.
Keywords: (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 ; Impedance spectroscopy; Dielectric relaxation; Conductivity

1. Introduction
Ferroelectric materials of the perovskite family (ABO3 type) have received considerable attention for the past several
years owing to their promising potentials for various electronic
devices such as multilayer capacitors (MLCCs), piezoelectric
transducers, pyroelectric detectors/sensors, electrostrictive actuators, precision micropositioners, MEMs, etc. Till date most of
these materials are lead bearing compounds, e.g., lead titanate
(PbTiO3 ), lead zirconate titanate (PbZr1x Tix O3 ), lead magnesium niobate (PbMg1/3 Nb2/3 O3 ), etc. Lead and its compounds
are listed as toxic and hazardous in the form of direct pollution
originating from the waste produced during their manufacturing
and machining of the components. Besides, products containing
Pb-based gadgets are not recyclable. Taking into consideration the environmental, health and social aspects, manufacturers
have been constrained to reduce and ultimately eliminate the
Pb-content of the materials. Hence, the search for alternative
materials for MLCCs, piezoelectric/pyroelectric applications
has now become a focal theme of the present day research. Further, titanate-based materials are of interest as they are suitable

Corresponding author. Tel.: +91 641 2501699; fax: +91 641 2501699.
E-mail addresses: k prasad65@yahoo.co.in, k.prasad65@gmail.com
(K. Prasad).
0925-8388/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2006.11.081

for room temperature applications mainly due to their dielectric

properties. Their low temperature behaviour is often controlled
by grain boundaries and therefore the knowledge of behaviour of
grain boundary is important. Complex impedance spectroscopic
technique is considered to be a promising non-destructive testing method for analyzing the electrical processes occurring in
a compound on the application of AC signal as input perturbation. The output response of polycrystalline compound, when
plotted in a complex plane plot represents grain, grain boundary
and electrode properties with different time constants leading to
successive semicircles.
During the past few years, several investigations have been
made to study the electrical properties of the solid solutions of
(Na0.5 Bi0.5 )TiO3 with different perovskites like: BaTiO3 [15],
SrTiO3 [3,68], PbTiO3 [9,10], CaTiO3 [11], (K0.5 Bi0.5 )TiO3
[10,12,13], (K0.5 Bi0.5 )TiO3 BaTiO3 [14,15], etc. for their possible application in electronic devices. All these attempts have
been made to modify the A-site, i.e., divalent pseudo-cation
(Na,Bi)2+ . Further, it has been observed that modification at Bsite plays an important role in tailoring various properties of
perovskite [1619]. An extensive literature survey suggested
that no attempt, to our knowledge, has been made to study
(Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 . The present work is an attempt to
study the role of grain and grain boundaries on electrical properties of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 (abbreviated hereafter as
NBZT) and their dependence on temperature and frequency

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Lily et al. / Journal of Alloys and Compounds 453 (2008) 325331

using complex impedance spectroscopy technique. AC conductivity analysis has also been made.
2. Experimental
A high-temperature solid-state reaction method was used for the preparation of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 (NBZT) ceramic. To synthesize the NBZT
sample, AR grade (>99.9% pure) chemicals (Na2 CO3 , Bi2 O3 , ZrO2 and TiO2 )
were taken in stoichiometric ratios. The reactants were mixed thoroughly, using
agate mortar and pestle. The mixture was pre-sintered at 1070 C for 4 h. The
compound was prepared in accordance with the formula:
0.25Na2 CO3 + 0.25Bi2 O3 + 0.25ZrO2 + 0.75TiO2


(Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 .

Requisite amount of polyvinyl alcohol was added as a binder before making into final stage of pellets. Circular disc shaped pellet having geometrical
dimensions: thickness = 2.81 mm and diameter = 10 mm was made to applying
uniaxial stress of 6 MPa. The pellets were subsequently heated up to 1100 C for
3 h. Completion of the reaction and the formation of the desired compound were
checked by X-ray diffraction technique. The XRD spectra were taken on calcined powders of NBZT with a X-ray diffractometer (Rikagu Miniflex, Japan) at
room temperature using Cu K radiation ( = 0.15418 nm) over a wide range of
Bragg angles (20 2 80 ) with a scanning speed 2 min1 . The electrical
measurements were carried out on a symmetrical cell of type Ag|NBZT|Ag,
where Ag is a conductive paint coated on either side of the pellet. Electrical
impedance (Z), phase angle (), loss tangent (tan ) and capacitance (C) were
measured as a function of frequency (0.1 kHz1 MHz) at different temperatures
(30500 C) using a computer-controlled LCR Hi-Tester (HIOKI 3532-50),
Japan.

3. Results and discussion

3.1. Structural study
A standard computer program (POWD) has been utilized for
the XRD-profile (Fig. 1) analysis. Good agreement between the
observed and calculated inter-planer spacing (d-values) and no
trace of any extra peaks due to constituent oxides, were found,
suggesting the formation of a single-phase compound having
orthorhombic structure. The lattice parameters were found to
b = 9.738(1) A
and c = 5.547(2) A
with an
be: a = 4.141(5) A,
3

estimated error of 10 A. The criterion adopted for evaluating the rightness, reliability of the indexing and the structure
of NBZT was the sum of differences in observed and calculated

Fig. 1. Indexed X-ray diffraction pattern of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 at room
temperature.

Fig. 2. Variation of real part of impedance of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 with
frequency at different temperature. Inset shows the variation of real part of
impedance up to 250 C.



d-values [i.e., d = (dobs dcalc )] found to be a minimum.
3.
The unit cell volume (a b c) was estimated to be 223.72 A
3.2. Impedance studies
Fig. 2 and its inset show the variation of the real part of
impedance (Z ) with frequency at various temperatures. It is
observed that the magnitude of Z decreases with the increase in
both frequency as well as temperature, indicate an increase in
AC conductivity with the rise in temperature and frequency. The
Z values for all temperatures merge above 100 kHz. This may
be due to the release of space charges as a result of reduction
in the barrier properties of material with the rise in temperature and may be a responsible factor for the enhancement of AC
conductivity of material with temperature at higher frequencies.
Further, at low frequencies the Z values decrease with rise in
temperature show negative temperature coefficient of resistance
(NTCR) type behaviour like that of semiconductors.
Fig. 3 and its inset show the variation of the imaginary part
of impedance (Z ) with frequency at different temperature. The
 ) for
curves show that the Z values reach a maxima peak (Zmax


the temperatures 300 C and the value of Zmax shifts to higher
frequencies with increasing temperature. A typical peak broadening which is slightly asymmetrical in nature can be observed
with the rise in temperature. The broadening of peaks in frequency explicit plots of Z suggests that there is a spread of
relaxation times, i.e., the existence of a temperature dependent electrical relaxation phenomenon in the material [20]. The
merger of Z values in the high frequency region may possibly
be an indication of the accumulation of space charge in the material. For the temperature below 300 C, the peak was beyond the
range of frequency measurement (Fig. 3, inset).
Fig. 4 shows the plot of scaled Z (,T) versus log f [i.e.,


and log(f/fmax ), where fmax corresponds to the
Z (, T )/Zmax
peak frequency of the Z versus log f plots. It can be seen that the
Z -data coalesced into a master curve. The value of full width
at half maximum (FWHM) is found to be >1.14 decades. These

Lily et al. / Journal of Alloys and Compounds 453 (2008) 325331

Fig. 3. Variation of imaginary part of impedance of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3
with frequency at different temperature. Inset shows the variation of imaginary
part of impedance up to 250 C.

observations indicate that the distribution function for relaxation

times is nearly temperature independent with non-exponential
conductivity relaxation. This phenomenon is well defined by
a non-Debye type (polydispersive) relaxation governed by the
relation:
   
t
; (0 < < 1)
(1)
(t) = exp

where (t) stands for time evaluation of electric field within

sample and is the Kohlrausch exponent. The smaller value of
indicates larger deviation of relaxation with respect to Debye
type relaxation ( = 1). A non-exponential type relaxation gov-

327

Fig. 4. Scaling behaviour of Z for (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 .

erned by Eq. (1) suggests the possibility of ion migration that

takes place via hopping accompanied by a consequential timedependent mobility of other charge carriers of the same type in
the vicinity occurs [21].
Fig. 5 shows a set of impedance data taken over a wide
frequency range at several temperatures as a Nyquist diagram
(complex impedance spectrum). It is observed that with the
increase in temperature the slope of the lines decreases and their
curve towards real (Z ) axis and at temperature 300 C, a semicircle could be traced, indicating the increase in conductivity of
the sample. At a temperature 350 C onwards two semicircles
could be obtained with different values of resistance for grain
(Rg ) and grain boundary (Rgb ). Hence grain and grain boundary
effects could be separated at these temperatures and at 500 C

Fig. 5. Complex impedance plots of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 at different temperature. Inset shows the appropriate equivalent electrical circuit.

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Lily et al. / Journal of Alloys and Compounds 453 (2008) 325331

data show only grain boundary effect. It can also be observed

that the peak maxima of the plots decrease and the frequency for
the maximum shifts to higher values with the increase in temperature. The polydispersive (non-Debye type) nature of dielectric
relaxation could be judged through complex impedance plots.
For pure monodispersive Debye relaxation, one expects semicircular plots with the centre located on the Z -axis whereas, for
polydispersive relaxation, these argand plane plots are close to
semicircular arcs with end-points on the axis of reals and the
centre lying below this axis. The complex impedance in such
situations can be described as:
R
Z () = Z + iZ =
(2)
[1 + (i/0 )1 ]
where represents the magnitude of the departure of the electrical response from an ideal condition and this can be determined
from the location of the centre of the semicircles. When goes
to zero {i.e., (1 ) 1}, Eq. (2) gives rise to classical Debyes
formalism. It can be noticed that the complex impedance plots
are not represented by full semicircle, rather the semicircular arc
is depressed and the centre of the arc lie below the real (Z ) axis
( > 0), which suggests that the relaxation to be of polydispersive
non-Debye type in NBZT. This may be due to the presence of
distributed elements in the material-electrode system [22]. Also
the value of increases with the rise in temperature. The values of Rg and Rgb could directly be obtained from the intercept
on the Z -axis and the variation of which with temperature are
shown in Fig. 6. It can be noticed that the value of Rg decreases
with the rise of temperature, which clearly indicates the NTCR
character of NBZT and supports Fig. 2. The capacitances (Cg
and Cgb ) due to these effects can be calculated using the relation:
max RC = 1

(3)

where max (=2fmax ) is the angular frequency at the maxima

of the semicircle. Fig. 6 shows the temperature variation of Cg
and Cgb obtained from Cole-Cole plots at different temperature.

Fig. 7 shows the variation of scaled parameters (Z /Zmax



and M /Mmax ) with frequency at 400 C. It can be seen that the

peaks are not occurring at the same frequency (fZ < fM ). The

Fig. 6. Variation of Rg , Rgb , Cg and Cgb with temperature of (Na0.5 Bi0.5 )(Zr0.25
Ti0.75 )O3 .

Fig. 7. Variation of normalized Z and M with frequency for (Na0.5 Bi0.5 )
(Zr0.25 Ti0.75 )O3 at 400 C.

magnitude of mismatch between the peaks of both parameters

represents a change in the apparent polarization. The overlapping of peaks is an evidence of long-range conductivity whereas
the difference is an indicative of short-range conductivity (via
hopping type of mechanism) [23].
3.3. Conductivity studies
The AC electrical conductivity was obtained in accordance
with the following relation:
AC =

l
SZ

(4)

where l is the thickness and S is the surface area of the specimen.

The loglog plot of electrical conductivity versus frequency at
different temperature (Fig. 8) shows a frequency independent
region in the low frequency region, followed by a region which is
sensitive to the frequency as well as temperature. Also, the onset

Fig. 8. Variation of AC conductivity with frequency at different temperature

for (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 . Inset shows variation of AC conductivity with
inverse of temperature at 1 kHz and 10 kHz.

Lily et al. / Journal of Alloys and Compounds 453 (2008) 325331

329

increase in temperature and so found to be consistent with

the experimental results. Thus, the classical hopping of electrons may be the dominating mechanism in the system. This
indicates that the conduction process is a thermally activated
process. Using correlated barrier hopping (CBH) model [25], the
binding energy has been calculated according to the following
equation:
s=1

(6)

where
=

Fig. 9. Temperature dependence of N(Ef ) and Rmin of (Na0.5 Bi0.5 )(Zr0.25

Ti0.75 )O3 at 1 kHz. Inset shows the variation of exponent s and binding energy
with temperature at 1 kHz.

(switch from frequency independent to frequency dependent

region) shifts towards higher side with the rise in temperature. The frequency variation of AC found to obey universal
behaviour:
AC = A

(5)

with 0 s 1 and is angular frequency of applied AC field,

in the frequency sensitive region. We find the value of s to
decrease with the increasing temperature (Fig. 9, inset). The
model based on classical hopping of electrons over barrier
[24] predicts a decrease in the value of the index s with the

6kB T
Wm

(7)

where Wm is the binding energy, which is defined as the energy

required to remove an electron completely from one site to the
another site. The characteristic decrease in slope (inset, Fig. 9)
with the rise in temperature is due to the decrease in binding
energy as illustrated in the inset of Fig. 9. Using the values of
the binding energy minimum hopping distance Rmin is calculated
[26]:
Rmin =

2e2
0 Wm

(8)

where 0 is the permittivity of free space and is the dielectric

constant. Fig. 9 shows the variation of Rmin with temperature
at 1 kHz. A minima is observed in Rmin versus temperature
plot at Tc (phase transition temperature). In the hopping models
AC conductivity behaviour distinguishes different characteristic
region of frequencies. In the low frequency region the constant

Fig. 10. Frequency dependence of N(Ef ) of (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 at different temperature.

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Lily et al. / Journal of Alloys and Compounds 453 (2008) 325331

conductivity shows that the charge transport takes place via infinite percolation path. In the higher frequency region where the
conductivity increases the transport is dominated by contribution from hopping in finite clusters. The value of Rmin at room
temperature was found to be 5.03 1012 m.
The AC conductivity data have been used to evaluate the
density of states at Fermi level N(Ef ) using the relation [27]:
 
4
fo
2
2 5
AC () = e kB T {N(Ef )}
ln
(9)
3

where e is the electronic charge, fo the photon frequency

and is the localized wave function, assuming fo = 1013 Hz,
= 1010 m1 at various operating frequencies and temperatures.
Fig. 10 shows the Frequency dependence of N(Ef ) at different
temperature. It can be seen that the value of N(Ef ) increases
with the increase in operating frequency at room temperature up
to 250 C. At a temperature, 300 C onwards the plots show a
minima and a perfect minima can be seen at 350 C and after
this temperature the minima starts disappearing. The minima
completely vanishes and N(Ef ) decreases exponentially with the
increase in frequency at 500 C. Further, it can be noticed the
minima shifts towards higher frequency side with the rise in temperature. Fig. 9 illustrates the variation of N(Ef ) with temperature
at 1 kHz. It is observed that the value of N(Ef ) decreases up to
300 C and afterwards it increases with the rise in temperature.
The reasonably high values of N(Ef ) suggests that the hopping
between the pairs of sites dominate the mechanism of charge
transport in NBZT.
Fig. 8 (inset) shows the variation of AC conductivity (ln AC )
versus 103 /T at 1 kHz and 10 kHz. The nature of variation is
almost linear over a wide temperature region obeys the Arrhenius
relationship:


Ea
AC = o exp
(10)
kB T
where Ea is the activation energy of conduction and T is the
absolute temperature. The nature of variation shows the NTCR
behaviour of NBZT. The value Ea (= 1.061 eV at 1 kHz and
0.841 eV at 10 kHz) obtained by least squares fitting of the data
at higher temperature region. It is observed that the value of Ea
decreases with the increase in frequency.
Fig. 11 shows the variation of grain and grain boundary conductivities, obtained from the impedance data (Fig. 5) against
103 /T. The nature of variation is almost linear over a wide temperature region obeys the Arrhenius relationship. The linear least
squares fitting to the data at higher temperature region gives the
values of Ea = 1.104 and 1.383 eV, respectively, for grain and
grain boundary. The low value of activation energy obtained
could be attributed to the influence of electronic contribution
to the conductivity. The increase in conductivity with temperature may be considered on the basis that within the bulk, the
oxygen vacancies due to the loss of oxygen are usually created
during sintering and the charge compensation follows the reaction (Kroger and Vink [28]): Oo 21 O2 +Vo + 2e , which
may leave behind free electrons making them n-type [29]. The
low value of activation energy may be due to the carrier transport

Fig. 11. Variation of DC conductivity of grain and grain boundary with inverse
of temperature for (Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 . Inset shows the variation of
thermal conductivity of grain and grain boundary with temperature.

through hopping between localized states in disordered manner.

The thermal conductivity data of grain and grain boundary for
NBZT are shown in the inset of Fig. 11. NBZT represents a
semiconductor behaviour resulting in an increased electronic
conduction of the total thermal conductivity. This electronic
thermal conductivity account for the total thermal conductivity
[30] and is given by:




2 
Ea
3
(11)
= LT 1 +
+4
42
kB T
where L is the Lorentz number. It is observed that the thermal
conductivity of grain as well as grain boundary increases with
increasing temperature and it exhibits reasonably low thermal
conductivity.
4. Conclusion
Polycrystalline
(Na0.5 Bi0.5 )(Zr0.25 Ti0.75 )O3 ,
prepared
through a high-temperature solid-state reaction technique, was
found to have a single-phase perovskite-type orthorhombic
structure. Impedance analyses indicated the presence of grain
and grain boundary effects in NBZT. The value of full width
at half maximum (FWHM) is found to be >1.14 decades, indicated the distribution of relaxation times is nearly temperature
independent with non-exponential conductivity relaxation.
Sample showed dielectric relaxation which is found to be of
non-Debye type and the relaxation frequency shifted to higher
side with the increase of temperature. The Nyquist plot and
conductivity studies showed the NTCR character of NBZT. The
AC conductivity is found to obey the universal power law. The
pair approximation type CBH model is found to successfully
explain the universal behaviour of the exponent, s. Also, the
frequency dependent AC conductivity at different temperatures
indicated that the conduction process is thermally activated
process.

Lily et al. / Journal of Alloys and Compounds 453 (2008) 325331

Acknowledgement
One of us (K.P.) gratefully acknowledges Indian National
Science Academy (INSA), New Delhi, for providing visiting
fellowship.
References
[1] Y. Hosono, K. Harada, Y. Yamashita, Jpn. J. Appl. Phys. 40 (2001) 5722.
[2] J. Suchanicz, J. Kusz, H. Bhom, H. Duda, J.P. Mercurio, K. Konieczny, J.
Eur. Ceram. Soc. 23 (2003) 1559.
[3] J.R. Gomah-Pettry, S. Sad, P. Marchet, J.P. Mercurio, J. Eur. Ceram. Soc.
24 (2004) 1165.
[4] Q. Xu, S. Chen, W. Chen, S. Wu, J. Zhou, H. Sun, Y. Li, Mater. Chem.
Phys. 90 (2005) 111.
[5] R. Ranjan, A. Dviwedi, Solid State Commun. 135 (2005) 394.
[6] J.R. Gomah-Pettry, A.N. Salak, P. Marchet, V.M. Ferreira, J.P. Mercurio,
Phys. Status Solidi (b) 241 (2004) 1949.
[7] S.E. Park, K.S. Hong, J. Mater. Res. 129 (1997) 279.
[8] J.K. Lee, K.S. Hong, C.K. Kim, S.E. Park, J. Appl. Phys. 91 (2002) 4538.
[9] S. Sad, P. Marchet, T. Merle-Mejean, J.P. Mercurio, Mater. Lett. 58 (2004)
1405.
[10] S. Sad, J.P. Mercurio, J. Eur. Ceram. Soc. 21 (2001) 1333.
[11] B.V.B. Saradhi, K. Srinivas, T. Bhimasankaram, Int. J. Mod. Phys. B 16
(2002) 1.

331

[12] Y. Li, W. Chen, J. Zhou, Q. Xu, H. Sun, M. Liao, Ceram. Int. 31 (2005)
139.
[13] J. Yoo, D. Oh, Y. Jeong, J. Hong, M. Jung, Mater. Lett. 58 (2004) 3831.
[14] Y. Li, W. Chen, Q. Xu, J. Zhou, X. Gu, S. Fang, Mater. Chem. Phys. 94
(2005) 328.
[15] Y.M. Li, W. Chen, Q. Xu, J. Zhou, X. Gu, Mater. Lett. 59 (2005) 1361.
[16] Y.M. Li, W. Chen, J. Zhou, Q. Xu, X.Y. Gu, R.H. Liao, Physica B 365
(2005) 76.
[17] Y. Li, W. Chen, J. Zhou, Q. Xu, H. Sun, R. Xu, Mater. Sci. Eng. B 112
(2004) 5.
[18] T. Wada, K. Toyoike, Y. Imanaka, Y. Matsuo, Jpn. J. Appl. Phys. 40 (2001)
5703.
[19] H. Ishii, H. Nagata, T. Takenaka, Jpn. J. Appl. Phys. 40 (2001) 5660.
[20] C.K. Suman, K. Prasad, R.N.P. Choudhary, Adv. Appl. Ceram. 104 (2005)
294.
[21] K. Prasad, A. Kumar, S.N. Choudhary, R.N.P. Choudhary, Solid State Ionics
176 (2005) 1641.
[22] J.R. Macdonald (Ed.), Impedance Spectroscopy: Emphasizing Solid Materials and Systems, John Wiley and Sons, New York, 1987.
[23] M.A.L. Nobre, S. Lanfredi, J. Phys. Chem. Solids 64 (2003) 2457.
[24] S.R. Eilliot, Philos. Mag. B 37 (1978) 553.
[25] S. Mollah, K.K. Som, K. Bose, B.K. Chaudri, J. Appl. Phys. 74 (1993) 931.
[26] R. Salam, Phys. Status Solidi (a) 117 (1990) 535.
[27] I.G. Austin, N.F. Mott, Adv. Phys. 18 (1969) 41.
[28] F.A. Kroger, H.J. Vink, Solid State Phys. 3 (1956) 307.
[29] K. Prasad, C.K. Suman, R.N.P. Choudhary, Ferroelectrics 324 (2005) 89.
[30] E-Abd El-Wahabb, Vacuum 57 (2000) 339.