Current Applied Physics 11 (2011) 414e422

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Current Applied Physics

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

Impedance and modulus spectroscopy characterization of Laþ3/Mnþ4 modified

PbTiO3 nanoceramics
Archana Shukla*, R.N.P. Choudhary
Department of Physics and Meteorology, IIT Kharagpur 721302, India

a r t i c l e i n f o a b s t r a c t

Article history: Nanocrystalline samples of Pb0.92La0.08MnxTi1-xO3 (PLMT) (x ¼ 0, 0.04, 0.07, 0.10) were prepared by
Received 11 March 2010 a high-energy ball-milling followed by a solid-state reaction method. Preliminary high resolution X-ray
Received in revised form diffraction technique of PLMT ceramics showed that a single-phase was formed exhibiting a tetragonal
8 August 2010
crystal structure. The electrical behavior of PLMT ceramics was investigated by the impedance spec-
Accepted 13 August 2010
troscopy in the temperature range of 35  Ce500  C. This study was carried out by means of the
Available online 25 August 2010
simultaneous analysis of the complex impedance (Z*) and electrical modulus (M*) functions from the
measurement range of 1 kHze1 MHz. A separation of the grain and grain boundary properties has been
Keywords:
Impedance spectroscopy
achieved using an equivalent circuit model in impedance analysis. Loss spectra reveal about the presence
Modulus analysis of temperature-dependent electrical relaxation phenomena in the materials. Modulus analysis provides
Relaxation time wider information related to charge transport processes.
Scaling behavior Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction
Perovskite-structured ferroelectric crystals have a general
formula ABO3 where A is mono or divalent ions with large radius and
low valence while B is a tetra or pentavalent metal with small radius
and high valence [1]. Among the perovskite-type oxides, titanate-
ceramics have been considered as interesting materials for room
temperature applications mainly due to their high dielectric prop-
erties [2]. Lead titanate (PbTiO3) with a very high Curie temperature
of 490  C belongs to a most important perovskite family due to its
remarkable ferroelectric and piezoelectric features in poly-
crystalline form [3]. The phase transition behavior in PbTiO3 single
crystal is relatively simple; it exhibits a single transition from
paraelectric cubic phase to ferroelectric tetragonal phase [4]. It has
been observed that substitution of any suitable ions at the Pb and/or
Ti site of lead titanate results in substantial modification in their
electrical properties so as to make them suitable for a wide variety of
industrial applications. The doping subsistent can either occupy A-
site, B-site or both as donor or acceptor based on chemical valence
with respect to the original ions. The electrical properties of the
ceramics are a result of different contribution from various
* Corresponding author. Tel.: þ91 3222 283814; fax: þ91 3222 255303.
E-mail addresses: archana@phy.iitkgp.ernet.in, ashuklaiitkgp@gmail.com
(A. Shukla).
component and processes in the materials. The charge transport can
take place via mode such as dipole reorientation, charge displace-
ment and space charge formalism [5]. It is well-known that transi-
tion ions having partially filled d-orbitals like, Mn3þ, Fe3þ ions are
generally used at B-site. Fluctuation of the oxidation state of these
ions results in the formation of oxygen ion vacancies which causes
thermally activated conduction. Thus most of the multiferroic
materials show high leakage current and low ferroelectric polari-
zation [6]. In order to improve the ferroelectric properties,
lanthanum (La) has been introduced. An appropriate and optimum
amount of La lowers the leakage current, provides good bistable
polarization, which is a primary requirement for non-volatile
random access memory (NVRAM) applications [7]. High-energy
ball-milling has been used to synthesize nanocrystalline ferroelec-
trics. This method offers several advantages (such as gain of time,
energy and better homogeneity) over the other conventional
method. It was shown that the crystallization of PLMT occurred at
600  C, which temperature is inferior to that reported for the same
composition prepared by the traditional solid-state reaction tech-
nique [8].
Complex impedance spectroscopy (CIS) is a well-established
method to investigate electrical properties of materials. It describes
the electrical processes occurring in a system on application of an
ac signal as input perturbation [9]. It is a useful technique with
enormous potential and possibilities for investigation, character-
ization of the electrical and electrochemical properties of electro-
ceramics materials. The technique ensures separation among the

1567-1739/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2010.08.014
 A. Shukla, R.N.P. Choudhary / Current Applied Physics 11 (2011) 414e422 415

Table 1
Lattice parameters and crystalline size of Pb 0.92La 0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07,
0.10) compounds.

x a(Å) c(Å) (c/a) ratio P (nm) Lattice strain (%)

0.0 3.8857(5) 4.1344(5) 1.064 20 0.303
0.04 3.8827(5) 4.1266(5) 1.062 21 0.290
0.07 3.9292 (3) 4.1219 (3) 1.049 21 0.289
0.10 3.9340(8) 4.0822(8) 1.037 16 0.398

2. Experimental Details

Lanthanum (Laþ3) and manganese (Mnþ4) modified lead titanate

Fig. 1. Room temperature HRXRD pattern of Pb0.92La0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07,
0.10) compounds.
bulk, grain, grain boundaries and electrodeeelectrolyte interface
properties. It has great ability to analyze the relaxation phenom-
enon occurring in the material, whose time constants range over
several orders of magnitude [10]. A much more profound analysis is
possible by combining the impedance analysis with use of the
complex electrical formalism [11].
(PLMT) ceramics with a general formula Pb0.92La0.08MnxTi1-xO3
(PLMT) (x ¼ 0, 0.04, 0.07, 0.10) were synthesized from high purity
(99.9%) oxides; PbO (with 5 wt % excess) (M/s B.D.H Chemicals),
La2O3 (M/s Loba Chemie.Co.India), TiO2 (M/s S.d fine Chemicals Ltd.),
and MnO2 (M/s Loba Chemie.Co.India) by a high-energy ball-milling
technique followed by a solidestate reaction method. The milling
was carried out in a Fritsch Pul-verisette P5 planetary ball mill at
room temperature for different milling times (10, 20, 30, 40 and
50 h). Milling was carried out in toluene medium (toluene is
chemically inert and can be used to diffuse heat that is generated
during milling) with WC (tungsten carbide) and milling media at
a speed of 300 rpm and a ball to powder weight ratio of 10:1, the
milling stopped for 30 min after every 1 h of milling to cool down the
system. Then the powders were calcined at optimized temperature
(600  C) and time (6 h) (based on thermal analyzer and repeated
calcinations process) in a programmable furnace with an accuracy of
1  C. The formation of single-phase compounds was confirmed by

Fig. 2. Variation of real and imaginary part of impedance with temperature of Pb0.92La0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) compounds.
416 A. Shukla, R.N.P. Choudhary / Current Applied Physics 11 (2011) 414e422

Table 2
Summary of the values obtained from the electrical parameters corresponding to the equivalent circuit model used in the fitting processes of the measured data at different
temperatures for all PLMT samples.

Sample Parameter Temperature ( C)

400 425 450 475 500

x ¼ 0.0 Rb(U) 1,298,400 649,803 411,640 270,890 174,300
CPEb Q0 0.50  109 0.37  109 0.35  109 0.29  109 0.26  109
n 0.90 0.8 0.8 0.8 0.8

x ¼ 0.04 Rb(U) 160,400 97,430 44,170 26,730 17,220

CPEb Q0 0.20  109 0.20  109 01.7  109 0.18  109 0.29  109
n 0.89 0.90 0.65 0.73 0.89
Rgb(U) 6440 3270 2580 1350 2620
CPEgb Q0 0.22  109 0.28  109 0.41  109 0.66  109 0.41  109
n 0.8 0.86 0.96 0.96 0.96

x ¼ 0.07 Rb(U) 35,020 24,570 16,600 11,840 9300

CPEb Q0 0.72  109 0.46  109 0.41  109 0.42  109 0.46  109
n 0.59 0.85 0.95 0.91 0.88
Rgb(U) 1510 6800 5700 6900 1000
CPEgb Q0 0.76  109 0.62  109 0.87  109 1.36  109 13.2  109
n 0.96 0.80 0.93 0.85 0.81

x ¼ 0.10 Rb(U) 2420 1340 1080 820

CPEb Q0 0.29  109 0.16  109 0.19  109 0.11  109
n 0.68 0.56 0.52 0.46
Rgb(U) 110 70 30 40
CPEgb Q0 0.93  109 1.88  109 2.90  109 4.60  109
n 1.0 0.98 0.99 0.99

Fig. 3. Variation of real part of impedance with frequency of Pb0.92La0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) compounds.
 A. Shukla, R.N.P. Choudhary / Current Applied Physics 11 (2011) 414e422
Fig. 4. Variation of imaginary part (Z00 ) of impedance with frequency of Pb0.92La0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) compounds.
a high resolution X-ray diffraction data collected by PANalytical High
Resolution XRD-I, PW 3040/60 with CuKa radiation (l ¼ 1.5418 Å) in
a wide range of Bragg’s angles 2q (20  2q  80 ). The calcined
powders were used to make cylindrical pellets of diameter 6 mm
and thickness 1e2 mm using a hydraulic press at a pressure of
6  107 N m2. Polyvinyl alcohol (PVA) was used as a binder to
prepare the pellets. These pellets were sintered at the optimized
Fig. 5. Variation of relaxation time with inverse of temperature of Pb0.92La0.08MnxTi1-
xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) (for impedance data).
417
temperature (1000  C) for (2 h) in an air atmosphere. The electrical
measurements were carried out at an input signal level of 1.5 V in
a wide temperature range of (35e500  C) using a computer-
controlled impedance analyzer, HIOKI LCR meter, (Model: 3532) in
the frequency range of 1 kHze1 MHz.
3. Results and discussion
3.1. Structural characterization
Fig. 1 shows the high resolution X-ray diffraction (XRD) patterns
of Pb0.92La0.08MnxTi1-xO3 (PLMT) (x ¼ 0, 0.04, 0.07, 0.10). Lead
titanate is a displacive type of ferroelectric compound having
tetragonal structure with very large lattice distortion from a cubic
structure [12]. All the peaks of the XRD pattern of the PLMT
ceramics were indexed and the lattice parameters were determined
in various crystal systems using a computer program “POWDMULT”
[13]. The best agreement between observed (obs) and calculated
(cal) interplanar spacing d (i.e., SdobsSdcal ¼ minimum) was found
in the tetragonal PLMT crystal system like that of the parent
compound. Since the ionic radius of Mn4þ is smaller than that of
Ti 4þ, the tetragonal ratio (c/a) and unit cell volume decrease on
increase of Mn content in PLMT. All the lattice parameters were
refined using least-squares technique. Changes in peak position
and intensity are observed because of the change in concentration
of Mn. By using some reflections of XRD pattern (widely scattered
in 2q), the coherently scattered crystallite size and lattice strain of
the samples was calculated from the X’Pert HighScore software
418 A. Shukla, R.N.P. Choudhary / Current Applied Physics 11 (2011) 414e422
Fig. 6. Variation of real and imaginary part of modulus with temperature of Pb0.92La0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) compounds.
using Scherrer’s calculator (Phkl. ¼ 0.89l/b1/2cosq) [14]. All the
parameters are given in Table 1.
3.2. Impedance spectroscopy
Electrical behavior of the compounds has been characterized
over a wide temperature and frequency range by using ac imped-
ance methods. Data may be analyzed in terms of four possible
complex formalisms, the impedance Z*, the electrical modulus M*,
the admittance Y* (or A*) and the permittivity (3*) [15]. These
parameters are related to one another according to the expressions,

1
Y * ¼ 1=Z * ; M* ¼ juCo Z * ; 3* ¼ M* ; Y * ¼ juCo 3*
where u is the angular frequency, Co is the vacuum capacitance of the
measuring cell and electrodes with an air gap in place of the sample.
The use of the function Z* and Y* is suitable for the resistive and/or
capacitive analysis when the long-range conductivity is dominate
while the M* and 3* functions are appropriate when localized relax-
ation dominates. Especially the use of ‘Z’ formalism allows for a direct
separation of the bulk, grain boundary and electrode phenomena, and
also determination of each individual resistance [16]. Fig. 2 shows
complex impedance spectra (Nyquist plots) for PLMT ceramics over
a range of temperature. The effect of temperature on impedance
behavior is much notable at higher temperatures. The impedance
spectrum for x ¼ 0.0 sample is characterized by the appearance of
a single semicircular arc whose radius of curvature decreases as
temperature increases. The intercept of semicircular arc with the real
axis gives an estimate of sample resistance. While impedance spec-
trum for Mn doped samples two semicircular arcs have been
observed. The high-frequency dispersion curves are attributed to the
bulk properties of the material and arise due to bulk phenomena,
while the low frequency second semicircle has been assigned to the
grain boundary conduction [17]. The bulk resistance decreases with
rise in temperature. Thus the bulk conductivity of the materials
increases with temperature. This behavior of materials is analogous to
the negative temperature coefficient of resistance (NTCR) property
which is a normal behavior of semiconductor. An equivalent model
circuit is very much essential to analyze the experimental data. It
provides a realistic representation of the electrical properties. The
selection of the model circuit is based on (a) what kinds of imped-
(1) ances are expected to be present in the sample and whether they are
connected in series or in parallel, (b) inspection of the resistance and
capacitance values that are obtained in order to check that they are
realistic and that their temperature dependence, and (c) examination
of the experimental data to check whether the response is consistent
with the proposed circuit [11]. Usually it is possible to find more than
one equivalent circuit that fits, numerically, a given data set. In the
process of selecting the most appropriate equivalent circuit to
represent the electrical properties of a material many difficulties may
arise [18,19]. As there is no priority rule to choose which circuit will
perform better, once an equivalent circuit has been selected it is
necessary to establish a link between the different parts of the circuit.
[20] In an ideal case, the result of impedance spectroscopy
measurements over a wide range of frequencies can be presented by
several semicircles in the complex ZRe-Zim plane [21]. Each semicircle
represents the contribution of a particular process (electrodes and
 A. Shukla, R.N.P. Choudhary / Current Applied Physics 11 (2011) 414e422
Fig. 7. Plot of real part of modulus (M0 ) with frequency of Pb0.92La0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) compounds.
contacts, grain boundaries, grain interior) to the total impedance of
the sample. Measured values in the form of Nyquist plots are rarely
ideal semicircular. Most of the authors describe them as depressed
semicircle with their center lying below the x-axis. This phenomenon
is called non-Debye relaxation [22]. In this case pure capacitance is
treated as constant phase element (CPE). The causes of CPE are (a)
surface roughness (b) A distribution of reaction rates (c) varying
thickness or composition (d) non-uniform current distribution. For
a solitary CPE is symbolized by Q.
In Fig. 2(aed) the equivalent circuits have been given to
compare the complex impedance plots (scattered symbols) with
fitted data (line) using commercially available software ZSimp Win.
As from figure it is clear that in pure compound (x ¼ 0.0) only grain
effect is observable thus the model circuit has been represented by
a parallel combination of resistance and CPE (Q). While in the rest
samples it is clear that both the inter and intragranular impedances
are presented in the ceramics, and the simplest appropriate model
circuit is a series array of parallel RQ elements. The values of fitted
parameters have been given in the Table 2.
0
Fig. 3 shows the variation of real part of impedance (Z ) as
a function of frequency for all the samples. The nature of variation
0
shows a monotonous decrease in the value of Z with rise in the
frequency. The impedance value is higher at lower temperatures in
the low frequency region and decreases gradually with increase in
0
frequency. The value of Z also shows a decreasing trend with rise
in temperature in the low frequency domain but tends to merge
with the low temperature data in the high-frequency region. Larger
0
Z values at lower frequency and temperature indicated larger
0 s ¼ so exp
effects of polarization. The decrease in Z with rise in temperature
419
and frequency also indicates a possibility of increase in the ac
conductivity with increase in temperature and frequency. The
0
merger of real part of impedance (Z ) in the higher frequency
domain for all temperatures indicates a possibility of the release of
space charge as a result of lowering in the barrier properties of the
material [23]. These results indicate that electrical conduction will
increase with rise in temperature and the phenomenon is depen-
dent on release of space charge. Fig. 4 shows the variation of the
imaginary part of the impedance with frequency (i.e., loss spectrum)
at different temperature. A peak has been observed at higher
temperatures which further broadened with rise in temperature.
The trend of variation of Z00 with frequency is typical of the presence
of electrical relaxation phenomena in the materials which is
temperature-dependent. The asymmetric broadening of the peaks
suggests the presence of electrical process in the materials with
a spread of relaxation time [24]. The shifting of peaks indicates that
the net relaxation time is decreasing with the increase in temper-
ature. The impedance data were used to evaluate the relaxation time
(s) of the electrical phenomena in the material using the relation
1 1
s¼ ¼ (2)
umax 2pfmax
where fmax is the relaxation frequency. The nature of the variation of
the s with temperature of all the compounds is shown in Fig. 5. The
curves appear to follow the Arrhenious relation which is given by
 
Es
(3)
kT
420 A. Shukla, R.N.P. Choudhary / Current Applied Physics 11 (2011) 414e422

Fig. 8. Variation of imaginary part of modulus (M00 ) with frequency of Pb0.92La0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) compounds.

where so is a pre-exponential factor, Es is the activation energy, k is
the Boltzmaan constant and T is the absolute temperature. The
activation energy evaluated from the slope of log (s) against 103 T1
curve is 1.20, 1.15, 0.81, 0.81 eV for (x ¼ 0.0, 0.04, 0.07, 0.10)
respectively. It is clear that the value of activation energy decreases
with an increase in Mn concentration. The small value of activation
energy may be due to the ionized oxygen vacancies.
3.3. Modulus spectrum analysis
Complex modulus formalism is a very important and convenient
tool to detect the bulk phenomena properties as apparent conduc-
tivity relaxation times. It provides an insight into the electrical
processes characterized by the smallest capacitance of the material
[25]. The smallest semicircle in the Nyquist plot (i.e. M0 vs. M00 )

Fig. 9. Variation of relaxation time with inverse of temperature of Pb0.92La0.08MnxTi1-

xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) (for modulus data). Fig. 10. Arrhenius plot of dc conductivity of PLMT (x ¼ 0.0, 0.04, 0.07, 0.10) compounds.
 A. Shukla, R.N.P. Choudhary / Current Applied Physics 11 (2011) 414e422
Fig. 11. Modulus scaling behavior of Pb0.92La0.08MnxTi1-xO3 (x ¼ 0.0, 0.04, 0.07, 0.10) compounds in the master curve.
corresponds to the highest capacitance. In order to analyze interpret
experimental data; it is essential to have a model equivalent circuit
that provides a realistic representation of the electrical properties.
Those materials, which show a single circular arc in complex
modulus plane, their electrical properties are defined by the parallel
combination of grain capacitance (C) and resistance (R). Complex
electric modulus can be calculated from the impedance data using
the following relation:
1 30 ðuÞ 300 ðuÞ
M*ðuÞ ¼ ¼ i hM 0 ðuÞ þ iM00 ðuÞ
3* j3*ðuÞj 2
j3*ðuÞj2
2 3
ZN
dfðtÞ 5
¼ MN 41  expðiutÞ dt
dt
0
where, MN ¼ 1/3N, 3N is the limiting high-frequency real part of
permittivity, and the function F(t) is a relaxation function or
Kohlrausch-Williams-Watts (KWW) function [11]. Fig. 6 shows the
complex modulus spectrum of the pure and modified lead titanate
at different temperatures. The pattern is characterized by the
presence of semicircular arcs at different temperatures. This may
possibly be attributed to the presence of single electrical relaxation
phenomena in the material under investigation [26]. Two peaks
were observed in case of x ¼ 0.0 sample, which can be attributed to
the contribution from the grain boundary. While the appearance of
single arc of the rest samples even at different temperature
confirms the single-phase character of the present compounds. The
variation of real part of electric modulus M0 as a function of
frequency over a wide range of temperature for all the samples has
421
been shown in Fig. 7. It comprises of features such as a very low
value (approaching to zero) of M0 in the low frequency region and
a continuous dispersion with frequency having a tendency to
saturate at a maximum asymptotic value designated as MN in the
high-frequency region for all temperatures. This observation may
possibly be related to a lack of restoring force governing the
mobility of charge carriers under the action of an induced electric
field at higher temperatures. This behavior supports that as
frequency increases; each ion moves a shorter and shorter path of
electric field until, the electric field changes so rapidly that the ions
only “rattle” within the confinement of their potential energy wells.
It also indicates the long-range mobility of charge carriers [27].
Fig. 8 shows the variation of M00 with frequency at different
(4)
temperatures. These curves also show peaks at higher tempera-
tures and the peak frequencies increase with increase in temper-
ature. A significant asymmetry has also been observed in the peaks
and a shift in the peak positions towards higher frequency side with
rise in temperature. The low frequency side of the peak represents
the range of frequency in which charge carriers are mobile over
long distances. The higher frequency side of the M00 peak represents
the range of frequencies in which the ions are spatially confined to
their potential wells and the ions can make only short-range
motion within the well [28]. The region where peak occurs is
indicative of the transition from long-range to short-range mobility
with increase in frequency. The behavior of the modulus spectrum
is suggestive of temperature-dependent hopping type mechanism
for electrical conduction (charge transport) in the system. The peak
frequency of the pattern gives an estimate of conduction relaxation
time (s) in accordance with the relaxation umaxs ¼ 1. The relaxation
422 A. Shukla, R.N.P. Choudhary / Current Applied Physics 11 (2011) 414e422
frequencies obtained from frequency explicit plots of M00 as inverse
absolute temperature (Fig. 9). These are straight lines and follow an
Arrhenious relation, given above (equation (3)). Activation energy
calculated from the slopes is 1.19, 1.11, 0.81, 0.80 eV for (x ¼ 0.0, 0.04,
0.07, 0.10) respectively. Again activation energy decreases with Mn.
There may be a change in the concentration of oxygen vacancies
due to the variable oxidation states of Mn.
Nearly similar activation energy for relaxation obtained from
impedance (Z00 ) and modulus (M00 ) plots indicates the localized
conduction (dielectric relaxation) of the charge species in the bulk
of the sample [29].
The dc conductivity vs. inverse temperature graph has been
shown in Fig. 10. As it is well-known that activation energy values
corresponding to Z00 spectra represent the localized conduction (i.e.,
dielectric relaxation) and those of M00 spectra represents non-
localized conduction (i.e., long-range conductivity), here we see
that activation energy values obtained via Rb (representing the
long-range dc conductivity) are 0.92, 0.90, 0.86, 0.58 eV for x ¼ 0.0,
0.04, 0.07, 0.10 compounds respectively. These values are much
near to the activation energy values obtained from M00 spectra
rather to spectra of Z00 . Thus the similarity between these two
values confirms the statement [20].
The variation of normalized complex electric modulus with
normalized frequency is shown in Fig. 11. It is known as the
“modulus master curve” and represents the scaling behavior of the
sample electrical modulus for different dopant concentration. It
was studied by plotting log (f/fmax) vs. (M00 /M00 max) at different
temperatures. These curves help to have a look in the dielectric
processes occurring within the sample. The overlap of the curves at
different temperatures into a single master curve indicates that the
relaxation describes the same mechanism at various temperatures
[30]. This behavior can be represented by a non-exponential type of
conductivity relaxation governed by the relation:
"  b #
t [9]
fðtÞ ¼ exp  ð0 < b < 1Þ (5)
ss
where f(t) ¼ stands for time evolution of electric field within
sample, ss ¼ conductivity relaxation time, b ¼ Kohlrausch expo-
nent. The smaller the value of b larger the deviation of relaxation to
Debye type relaxation (b ¼ 1). A non-exponential type conductivity
relaxation suggests the possibility that ion migration takes place
via hopping accompanied by a consequential time dependent
mobility of other charge carriers of the same type in the vicinity.
The master modulus curve indicates: (i) slight shift in the modulus
peak maxima for different concentration and (ii) a similar shape
and pattern of M00 /M00 max with slight variation in full width at half
maximum (FWHM) with different doping concentration. Further,
the full width at half maximum (FWHM) of the M00 /M00 max peaks is
wider than the width of a typical Debye peak (1.14 decade) sug-
gesting the presence of non-Debye type conductivity relaxation
phenomena in the material.
4. Conclusions
The Laþ3/Mnþ4 modified PbTiO3 (PLMT) compounds were
prepared by a high-energy ball-milling method followed by some
heat treatment. Preliminary structural studies suggest that the
crystal system of parent compound remains same (in tetragonal
crystal system) even upto 10% manganese substitution. Complex
impedance spectroscopy, in terms of a simultaneous analysis of the
complex impedance, electric modulus was used to investigate the
electrical behavior of PLMT ceramics. Complex impedance spectra
indicate about the possible contribution of the bulk and grain
boundaries at higher temperatures and also about the tempera-
ture-dependent relaxation phenomena. Modulus analysis has
established the possibility of hopping mechanism for electrical
transport processes in the system.
Acknowledgement
One of the authors (AS) acknowledges with thanks the
financial support received from the Council of Scientific and
Industrial Research (CSIR), Government of India, New Delhi for
carrying out the research at the Department of Physics and
Meteorology, Indian Institute of Technology (IIT), Kharagpur
721302, India.
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