Materials Science and Engineering B 164 (2009) 165–171

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Materials Science and Engineering B

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

Impedance spectroscopy study of LaMnO3 modified BaTiO3 ceramics

Prasanta Dhak a,b , Debasis Dhak c,d,∗ , Manasmita Das a , Kausikisankar Pramanik b ,
Panchanan Pramanik a,∗
a
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, India
b
Department of Chemistry, Jadavpur University, Kolkata 700032, India
c
Department of Chemistry, Serampore College, Serampore 712201, Hoogly, India
d
Materials Engineering Department, University of British Columbia, Vancouver, BC V6T 1Z4, Canada

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

Article history: Ba0.97 Ti0.97 La0.02 Mn0.04 O3 nanocrystalline powder was prepared by chemical route with the help of soluble
Received 16 April 2009 tartarate complex of Ti4+ ion. Preliminary X-ray diffraction analysis of crystal structure showed that a
Received in revised form 15 August 2009 single-phase compound was formed exhibiting tetragonal system. Average crystallite size and particle
Accepted 5 September 2009
size were observed to be between 27 and 33 nm, which were analyzed through XRD and transmission
electron microscope respectively. Wide range impedance spectroscopy study from 200 to 600 ◦ C showed
Keywords:
the presence of both bulk and grain boundary effects up to 500 ◦ C. The bulk conductivity indicated an
Chemical route
Arrhenius-type thermally activated process and oxygen vacancies are the possible ionic charge carriers at
Nanomaterials
Impedance spectroscopy
higher temperatures. The variation of ac conductivity as a function of frequency indicated the possibility
ac and dc conductivities of hopping mechanism for electrical process in the system with a non-exponential type of conductivity
Oxygen vacancies relaxation.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction ferromagnetic as well as ferroelectric properties simultaneously

Complex impedance spectroscopy (CIS) is a nondestructive
method [1] to study the microstructural and electrical properties
of polycrystalline oxides. This can correlate the structural and elec-
trical characteristics of polycrystalline oxides in a wide range of
frequencies and temperatures. CIS also describes the electrical pro-
cesses occurring in a system by applying an ac signal as input
perturbation, which helps to separate the contribution of electroac-
tive regions (such as grain boundary and bulk effects). The output
response, when plotted in a complex plane plot, appears in the
form of succession of semicircles representing electrical phenom-
ena due to the bulk material, grain boundary effect and interfacial
polarization [2].
The studies involving barium titanate ceramics with aliovalent
cation dopants have been undertaken to improve electric proper-
ties [3,4]. La and Mn doped BaTiO3 produces defects in structure
arising oxygen vacancies that play a significant role in electrical
properties [5].
Barium titanate and modified barium titanate compounds
belong to the general formula ABO3 , where A = mono- or divalent
ions and B = tri- to hexavalent ions. BaTiO3 –LaMnO3 composite has
∗ Corresponding authors. Tel.: +91 3222 283322; fax: +91 3222 255303.
E-mail addresses: pdhak chem@yahoo.com (P. Dhak), debasisdhak@yahoo.co.in
(D. Dhak), panchanan 123@yahoo.com (P. Pramanik).
which is an interesting subject, not only for possible applications
in electronic devices, but also for the fundamental understanding
of solid state physics [6,7]. Kim et al. have studied the magnetodi-
electric effect of BaTiO3 –LaMnO3 composites [7] where the study
focused on the ferromagnetic behavior of the materials. A binary
system of BiFeO3 –BaTiO3 doped with Mn has been reported by Liu
et al. [8] who have shown the increased resistivity at a certain level
of Mn doping with an improved ferroelectric properties.
La doped on BaTiO3 ferreoectric materials also plays a signif-
icant role on the electrical properties [9,10]. Gulwade et al. [11]
have shown the decrease in Curie temperature as well as a signifi-
cant enhancement in the dielectric constant on introduction of La
and Ga doped at A and B sites of BaTiO3 solid solutions respectively.
The behavior is due to the introduction of vacancies at A site ion of
the perovskite structure, with consequent disturbance of the fer-
roelectric order [5,10]. Lj Zivkovic et al. have reported the effect
of secondary abnormal grain growth on the dielectric properties
of La/Mn co-doped BaTiO3 ceramics [12]. Chen et al. have studied
the influence of manganese on the room-temperature resistivity of
lanthanum-doped BaTiO3 [13]; the room-temperature resistivity
of La-doped BaTiO3 increases with the increase in Mn content.
In all ferroelectrics, in general, the study of electrical conductiv-
ity is very important since the associated physical properties such
as piezoelectricity, pyroelectricity, and also strategy for poling are
dependent on the order and nature of conductivity in these mate-
rials [14]. Complex impedance spectroscopy (CIS) has been found

0921-5107/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2009.09.011
166 P. Dhak et al. / Materials Science and Engineering B 164 (2009) 165–171
Fig. 1. Flow-chart diagram for the preparation of Ba0.97 Ti0.97 La0.02 Mn0.04 O3 (BTLM)
ceramics powder.
to be a very useful technique in correlating the structural and elec-
trical characteristics in polycrystalline oxides in a wide range of
frequencies [15]. This has been applied to analyze the electrical
properties of a few ferroelectric materials recently [16–18].
All these attempts have been made to modify the A site and
(or) B site ion to improve the electrical properties as well as mag-
netic properties where applicable. An extensive literature survey
suggested that no attempt, to our knowledge, has been made to
study Ba0.97 Ti0.97 La0.02 Mn0.04 O3 . The present work is an attempt
to synthesize the material by chemical route and study the role of
grain and grain boundaries on Ba0.97 Ti0.97 La0.02 Mn0.04 O3 (abbrevi-
ated hereafter as BTLM) and their dependence on temperature and
frequency, using complex impedance spectroscopy technique. ac
conductivity analysis has also been made.
2. Experimental work
Powders of Ba0.97 Ti0.97 La0.02 Mn0.04 O3 (BTLM) was prepared by
a metal-ion ligand complex based precursor solution evaporation
technique [2,17,19,20] using stock solutions of the high purity
raw materials: Ba(NO3 )2 (MERCK, Germany, GR grade) (99%), TiO2
(Aldrich, 99.99%), La(NO3 )3 (MERCK, Germany, GR grade), Mn-
acetate (Loba Chemie, Bombay, India (99%)), tartaric acid (Quest
Chemicals, Kolkata, India (99%)), TEA (triethanolamine) (SRL, Mum-
bai, India (97%)), HNO3 (65%) (MERCK, Mumbai, India, GR grade),
and NH4 OH (25%) (MERCK, Mumbai, India, GR grade). Initially pow-
der produced by this process was nanosized. A flow-chart of steps
involved is provided in Fig. 1.
The detailed preparation procedure of titanium-tartarate solu-
tion which is commercially unavailable, is discussed elsewhere
[21–23]. For the preparation of BTLM ceramic powder, appropri-
ate volume of Ba(NO3 )2 , La(NO3 )3 , Mn-acetate and Ti-tartarate was
taken from their respective stock solutions, in accordance with
the desired stoichiometries, followed by mixing together. The pre-
cursor solution was subsequently obtained by adding excess TEA
(3 mol ratio with respect to per mol of the total metal ions) to
avoid any chance of precipitation of the metal ions from the precur-
sor solution. The polydented complexing/chelating agent TEA used,
played a dual role by helping in the distribution of cations in the
precursor solution throughout the TEA network so that the selec-
tive precipitation is prevented during the evaporation process and
Fig. 2. Simultaneously recorded DTA/TG graph of BTLM precursor powder.
also aided in the formation of the fluffy, voluminous, mesoporous
carbon rich precursor materials by heating at ∼200 ◦ C. The mate-
rials provided heat by combustion during pyrolysis and facilitated
the reduction of the external temperatures required for the desired
phase formation. Thermal analysis [differential thermal analysis
(DTA) and thermogravimetric analysis (TGA) (Model DT-40, Shi-
madzu Co, Japan)] of the voluminous mass was completed in order
to optimize the calcination temperature in static air at a heating
rate of 10 ◦ C/min up to 1000 ◦ C using alumina crucible. The volu-
minous fluffy black carbonaceous mass, which was ground to fine
powder and was calcined at 600 ◦ C for 2 h to get the nanosized BTLM
powder and thus the formation of single-phase compound was
confirmed by X-ray diffraction (XRD) (Philips, model: PW 1710)
using Cu K␣ target ( = 1.5418 Å) in a wide range of Bragg angles
2 (20◦ ≤ 2 ≤ 70◦ ) at a scanning rate of 2◦ (2)/min. The XRD spec-
trum of Si crystal was used as a standard to calibrate the scanning
angles. Transmission electron microscope (TEM) micrograph of the
calcined powder was taken by Hitachi H-600 in order to observe the
shape and size of the particles. The powder sample was dispersed
in acetone through sonication and then placed on a carbon-coated
copper grid with a mesh size of 200.
The calcined fine powder was used to make cylindrical pellets
of diameter 10 mm and thickness 2 mm using a hydraulic press at
a pressure of 190 MPa/cm2 . Polyvinyl alcohol (PVA) was used as a
binder to prepare the pellets. The pellets were sintered at 900 ◦ C
for 4 h in static air atmosphere. The flat clean surfaces of the sin-
tered pellets were thermally etched and then gold coated (thickness
40 Å) by sputtering technique to check the surface morphology by
a scanning electron microscope (JEOLJSM5800) at 20 kV at room
temperature. In order to study the electrical properties, both the
flat surfaces of the sample were polished and electroded with high
purity silver paint. The silver painted sample was dried at 300 ◦ C
for 2 h to remove the moisture, if any. The electrical properties of
the sample pellet were observed by the dielectric measurement
using a computer-controlled HIOKI 3532-50 LCR HiTESTER at an ac
signal of 1.0 V up to a temperature of 600 ◦ C starting from room
temperature.
3. Results and discussion
3.1. DTA and TGA analysis
Thermal characterization technique was used to find the
optimum formation temperature for the compound. The thermo-
gravimetric (TG) data and the corresponding differential thermal
analysis (DTA) curve for a representative precursor samples is
shown from 25 to 1000 ◦ C at the heating rate of 10 ◦ C/min in Fig. 2.
 P. Dhak et al. / Materials Science and Engineering B 164 (2009) 165–171
Fig. 3. Room temperature XRD and EDX (inset) of BTLM ceramics precursor powder
heat treated at 600 ◦ C, for 2 h in static air.
BTLM precursors showed a slow rate of water loss up to about
380 ◦ C. The first exothermic process occurring near 380 ◦ C may
be associated to the departure of water molecules during ther-
mal decomposition of the precursor (tartarate complex). In the
range between 400 and 550 ◦ C, a large exothermic peak appeared at
510 ◦ C in DTA graph due to the thermal effect for precursor decom-
position and the maximum mass loss (m/m) occurred at this stage.
So, this temperature (510 ◦ C) is expected to be the crystallization
temperature (Tc ) of the material. The exothermic peak at 500 ◦ C
could be assigned to the oxidation of carbonaceous remains from
the decomposed metal-complexes and TEA. For this reason this
stage showed the major decomposition of the precursor materi-
als in the TG curves shown in Fig. 2. The sample got free from all
type of organic contaminants at ∼580 ◦ C. The entire thermal effect
was accompanied by the evolution of various gases (such as CO,
CO2 , NH3 , water vapor, etc.), which was manifested by a single step
weight loss, shown in the TG curves. Above 580 ◦ C, there were no
significant thermal effect observed in DTA curves and the corre-
sponding TG curves showed no weight loss, implying the complete
volatilization of carbon compounds.
3.2. Structure and microstructure
Room temperature XRD studies have been carried out to confirm
the formation and phase formation of the BTLM compound in the 2
Fig. 4. (a) Bright field (BF) TEM and (b) particle-size distribution pattern of BTLM compound.
167
range of 20–70◦ . The single-phase formation of the compound was
confirmed by the careful analyses of the X-ray data shown in Fig. 3.
The XRD pattern as observed from Fig. 3 is sharp and quite differ-
ent from those of the oxides which confirm the formation of a new
and single-phase compound. All peaks were indexed and the lattice
parameters were determined in various crystal systems and config-
uration using a JCPDS data file. On the basis of the best agreement
between observed and calculated d, i.e., dobs − dcal = minimum,
a tetragonal system was selected with JCPDS data file No. 83-1880.
Fig. 3 (inset) shows the EDX (energy dispersive X-ray) spectrum
of the synthesized BTLM compound at room temperature. An ele-
mental analysis of the compound using EDX spectrum confirmed
the formation of the desired compound in which Ba or Ti: 19.4%, La:
0.4%, Mn: 0.8% and O: ∼60% were observed. The crystallite size was
calculated using Scherrer’s equation, D = 0.9/ˇ1/2 cos  [24] where,
ˇ1/2 = half-peak width. In the calculation of the crystallite size, some
errors arise due to strain effect and instrumental error. The instru-
mental errors have been minimized by making the correction in the
half-peak width (ˇ) term [ˇ2 = ˇ2 (material) − ˇ2 (standard sam-
ple)]. The corrected average crystallite size calculated from the XRD
peak of BTLM compound was 27 nm.
A representative bright field TEM for BTLM was taken after calci-
nation of the precursor powder at the phase formation temperature
of 600 ◦ C. The bright field TEM micrograph represented the basic
powder morphology in the sample, where the smallest visible iso-
lated spot can be identified with particle/crystallite agglomerates
as shown in Fig. 4(a). From the TEM study of the BTLM powder,
it was observed that the particles have an almost-spherical mor-
phology with broad particle-size distribution [Fig. 4(b)] between
15 and 45 nm with a mean average particle size 33 ± 1 nm, which
is in close agreement with the crystallite size obtained from XRD
after corrections.
Fig. 5 shows the typical SEM micrograph of the sintered pel-
let. The sintering was done at 900 ◦ C for 4 h. The grain growth
takes place for both porous and crystalline solids during sinter-
ing at higher temperature. Usually the grain growth is inhibited in
nanomaterials due to open porosity, grain growth inhibitors, and
grain boundary segregation. Thus during sintering the size of the
particle does not increase much [25]. But in this case well defined
grains with visible grain boundaries are observed (Fig. 5) which is
in agreement with the impedance analysis.
3.3. Complex impedance analysis
In general, for the electrode/ceramic/electrode, the values of
resistance R and capacitance C can be analyzed by an equivalent
circuit of one parallel resistance–capacitance (RC) element. The
168 P. Dhak et al. / Materials Science and Engineering B 164 (2009) 165–171

Table 1
(a) Variation of electrical parameters (bulk) as a function of temperature. (b) Varia-
tion of electrical parameters (grain boundary) as a function of temperature.

(a) Temperature (◦ C) fmax (kHz) Rb (k) Cb (pF)

350 45 34.3 103

400 95 18.3 91
450 250 9.2 68
500 400 5.4 73
550 700 3.3 68
600 950 1.9 87

(b) Temperature (◦ C) fmax (Hz) Rgb (k) Cgb (pF)

350 700 7.7 29

400 800 2.0 98
450 950 0.4 377
500 1000 0.2 714

Fig. 5. SEM micrograph of BTLM compound.
complex impedance spectrum (Nyquist plot) i.e., the variation of
real and imaginary part of impedance, measured at different tem-
peratures, is shown in Fig. 6(a)–(d). The impedance spectroscopy
is characterized by the appearance of the semicircular arcs, whose
pattern of evolution changes with rise in temperature. The tem-
perature effect on impedance behavior is more important because
with increase in temperature, the semicircular nature of the arcs
increases and the arcs shift to the center of the arc towards the
origin of the complex plain plot. In Fig. 6(a) and (d), the entire
plots show single arc, which indicates that the electrical pro-
cess contribution is from bulk materials (grain interior), which
can be modeled as an equivalent circuit comprising of a parallel
combination of bulk resistance and bulk capacitance [26]. Appear-
ance of another semicircle arc at 350 ◦ C clearly indicates the
beginning of the intergranular activities (grain boundary effect)
within the sample with definite contributions from both bulk (grain
interior) and grain boundary effects [Fig. 6(b)–(d)]. The values of
circuit elements obviously depend on the volume fraction of the
individual components (i.e., grain and grain boundary effect), which
is related to the microstructure of the compound. In order to estab-
lish a connection between the microstructure and the electrical
properties, several microstructural models [27] are discussed in the
literature, which usually fall into two types: the layer models and
the effective medium models. In ceramics, which are used because
of their high dielectric permittivities, grain boundaries are often
electronically active due to depletion effects and act as barriers to
the cross transport of charge carriers. The electrical phenomena can

Fig. 6. Variation of real and imaginary parts of impedance at different temperatures for BTLM compound.
 P. Dhak et al. / Materials Science and Engineering B 164 (2009) 165–171
be expressed in terms of a bricklayer model [28], where the con-
duction through the grain and grain boundaries dominates, with
electrical circuit having different values of capacitance and resis-
tance as shown in Table 1 in the temperature range from 350 to
500 ◦ C. The resistance value was evaluated from the impedance
spectrum using the equivalent circuit (EQUIVCRT) software pro-
gram [29], whereas the capacitance can be calculated using the
following relation:
(2f )(Rb Cb ) = 1,
1 of the presence of the space charge polarization effect at lower
Cb = , (2)
2fRb
where Rb and Cb refer to bulk resistance and capacitance; f is the
relaxation frequency. This relation is also valid for grain boundary
effects.
The absence of third semicircle suggests that the contribution
of the electrode–materials interface to impedance is negligible.
The analysis of the curves shows that the semicircle exhibits some
depression degree instead of a semicircle centered on the abscissa
axis. This decentralization reflects the non-Debye-type relaxation.
3.3.1. Variation of the real part of the impedance with frequency
Fig. 7(a) shows the variation of real part of impedance (Z ) with
frequency at different temperatures of the BTLM compound. On
increasing temperature the Z value decreased which indicates the
increase in ac conductivity as shown in Fig. 9. At higher frequency,
the Z value merges for all the temperatures, which clearly indi-
cates the presence of space charge polarization [30]. The higher
impedance value at lower frequency is also an indication of the
space charge polarization of the materials.
3.3.2. Variation of the imaginary part of the impedance with
frequency
Fig. 7(b) shows the variation of imaginary part of impedance
(i.e., loss spectrum) with frequency at different temperatures. The
loss spectrum (Z ) increased with increase in frequency in all
the temperature ranges studied here and exhibited a maximum
before starts decreasing rapidly. The existence of a temperature
dependent electrical relaxation phenomenon is suggested by this
maximum shifts to higher frequency with an increase in temper-
ature. The Z peak shifts to higher frequencies with increasing
temperature [as shown by the arrow, Fig. 7(b)], which indicates
the presence of temperature dependent electrical relaxation phe-
nomenon in the system. The asymmetric broadening of the peaks
suggested the presence of electrical processes in the material with
Fig. 7. Variation of real part (a) and imaginary part (b) of impedance with frequency at different temperatures and relaxation time with inverse of temperature (b) (inset)
for BTLM compound.
169
a spread of relaxation time [31]. The relaxation phenomenon in the
material may be due to the presence of immobile species/electron
at low temperature and defects/vacancies at higher temperature.
For the dielectric materials, the localized relaxation (i.e., defect
relaxation) dominates [32] because of the low dielectric ratio r
(r = εs /ε˛ , εs and ε˛ are the dielectric constants at low and high
frequencies respectively). As shown in Fig. 7(b), there was a clear
dispersion of the resultant curves in the low frequency region at
different temperatures and appears to be merging at higher fre-
(1)
quency irrespective of temperature. This behavior may be because
frequencies, which is eliminated at higher frequencies [33].
The impedance data were used to evaluate the relaxation time
( ) of the electrical phenomena using the relation ω = 1, where
ω = 2f is the angular frequency. The nature of the variation of
with 103 T−1 of the compound as shown in Fig. 7(b) (inset), follows
the Arrhenius relation [34]. The activation energy evaluated from
the slope of log ( ) against 103 T−1 curve of BTLM compound is
0.98 eV.
3.4. Electrical conductivity study
3.4.1. dc conductivity
Electrical conduction in dielectric material is a thermally acti-
vation process and is due to the ordered motion of weakly bound
charged particles under the influence of an electric field. It depends
on the nature of the charge carriers that dominate the conduc-
tion process like electrons/holes or cations/anions and follow the
Arrhenius low. The bulk conductivity ( rb ) of the compound can be
evaluated from the impedance data using the relation,  dc = t/Rb A
where Rb is the bulk resistance, t is the thickness, and A is the area
of the electrode deposited on the sample. Rb is obtained from the
value of low frequency intercept of the semicircle on the real axis
(Z ) in the complex impedance plot.
Fig. 8 shows the variation of bulk conductivity ( rb ) and grain
boundary conductivity ( gb ) as a function of temperature of the
BTLM compound. Using this Arrhenius plot of dc conductivity, the
corresponding activation energy for both bulk and grain boundary
were calculated from the slope of the linear portion of the plot and
were found to be 0.96 and 0.94 eV. The activation energy calculated
from  rb vs 103 T−1 plot (Fig. 8) is almost similar with that of the
activation energy estimated from the relaxation time plot (Fig. 7(b)
(inset)). The close resemblance of the two values indicates that the
relaxation and the conduction processes may be attributed to the
same type of charge carriers. The value of conductivity at 500 ◦ C is
4.02 × 10−4 S/cm.
170 P. Dhak et al. / Materials Science and Engineering B 164 (2009) 165–171

Fig. 8. Variation of bulk and grain boundary conductivity with inverse of tempera- Fig. 9. Variation of ac conductivity with frequency of BTLM compound.
ture of BTLM compound.

the behavior of ac conductivity using the following universal power

The variation of grain boundary conductivity with tempera- law [41]:
ture exhibits Arrhenius behavior, which is an indication of the
thermally activated nature of grain boundary conduction. The (ω) = (0) + Aωn . (3)
activation energies for grain and grain boundary conductivities
where (0) is the “dc” or frequency independent part, which is
reported here showed good correlation with the earlier reported
related to dc conductivity and the second term is of constant phase
activation energy values observed in perovskite as well as bilayered
element (CPE) type; n is a frequency exponent in the range of
ferroelectric ceramics [35–38]. By comparing the grain boundary
0 ≤ n ≤ 1.
conductivity with that of the grain of the corresponding sample,
The ac conductivity is calculated using the relation
the former is slightly higher than that of the later.
 ac = ωεε0 tan ı. The curve in Fig. 9 shows the dispersion, which
The value of the activation energy for conduction clearly sug-
shifts to the higher frequency side with a rise in temperature. The
gested a possibility that the conduction in the higher temperature
increasing trend of ac conductivity may be due to the presence of
range for ionic charge carriers may be oxygen vacancies. In per-
disordered cations between the neighboring sites and the presence
ovskite ferroelectric materials, oxygen vacancies are considered as
of space charges that vanish at higher temperature and frequency
one of the mobile charge carriers [39] and mostly in titanates, ion-
[33]. The change in slope takes place at a particular frequency
ization of oxygen vacancies creates conduction electrons, a process
known as the “hopping frequency ωp ” which obeys the relation
which is defined by the Kroger–Vink notation as [40].
[42]:
Ox0 → 1
O
2 2
(g) + Vx0   n
ω
(ω) = kωp 1 + , (4)
ωp
Vx0 → V∗ + e
Fig. 9 shows the frequency dependent conductivity from
V∗0 ↔ V∗∗
0 +e

≥350 ◦ C; the hopping frequencies are estimated to be 3, 7, 20, 30,
44.5 and 90 kHz at 350, 400, 450, 500, 550 and 600 ◦ C respectively.
Thus excess electrons and oxygen vacancies are formed in the
At higher frequency the conductivity becomes more or less tem-
reduction reaction
perature dependent as shown in Fig. 9. The increasing trend of 
Ox0 → 1
O
2 2
(g) + V∗∗
0 + 2e
in the low frequency range up to 50 kHz as shown in Fig. 9 may
be due to the disordering of cations between the neighboring sites
And they may bond to Ti4+ and Mn3+ in the form and the presence of space charge that vanish at higher temperature
Ti4+ + e ↔ Ti3+ and frequency. The ac activation energy was estimated to be 1.01 eV
which is greater than that of dc activation energy as ac conductivity
is both temperature and frequency dependent [43].
Mn3+ + e ↔ Mn2+

These electrons trapped by Ti4+ or Mn3+ ions or oxygen vacan- 4. Conclusion

cies can be thermally activated, thus enhancing the conduction
process. Doubly charged oxygen vacancies are considered to be
the most mobile charges in perovskite ferroelectrics and play an
important role in conduction [16].
3.4.2. ac conductivity
According to Jonscher, the origin of the frequency dependence
of conductivity was due to the relaxation of ionic atmosphere after
the movement of the particle. The variation of ac conductivity as
a function of frequency (conductivity spectrum) at different tem-
peratures is shown in Fig. 9. Jonscher made an attempt to explain
The present work reports the results of our investigation on the
electrical properties of BTLM compound prepared by a chemical
route using CIS technique. The electrical properties indicated that
the material exhibit (a) bulk conduction up to a temperature of
300 ◦ C, (b) grain boundary conduction at higher temperature up
to 500 ◦ C, and temperature dependent relaxation phenomena. The
activation energies calculated from the conductivity pattern and
the relaxation time pattern are almost the same, 0.96 and 0.98 eV
respectively. The value ac activation energy, 1.01 eV was greater
than the dc activation energy, 0.96 eV as ac conductivity is both
 P. Dhak et al. / Materials Science and Engineering B 164 (2009) 165–171
temperature and frequency dependent. The electrical conduction
in the grain boundary may be due to the mobility of the oxide (O2− )
vacancies at higher temperatures.
Acknowledgement
The authors thank the Council of Scientific and Industrial
Research, India, for financial support.
References
[1] J.R. Macdonald, Impedance Spectroscopy: Emphasizing Solid State Materials
and Systems, Wiley, New York, 1987, Chapters 2 and 4.
[2] D. Dhak, P. Dhak, P. Pramanik, Appl. Surf. Sci. 254 (2008) 3078.
[3] H. Ihrig, J. Am. Ceram. Soc. 64 (1981) 617.
[4] C.J. Ting, C.J. Peng, H.Y. Lu, S.T. Wu, J. Am. Ceram. Soc. 73 (1990) 329.
[5] H.-I. Hsiang, F.-S. Yen, Y.-H. Chang, J. Mater. Sci. 31 (1996) 2417.
[6] M. Mahesh Kumar, V.R. Palkar, K. Srinivas, Appl. Phys. Lett. 76 (2000)
2764.
[7] N.G. Kim, Y.S. Koo, C.J. Won, N. Hur, J.H. Jung, J. Yoon, Y. Jo, M.H. Jung, J. Appl.
Phys. 102 (2007) 014107.
[8] X.-H. Liu, Z. Xu, S.-B. Qu, X.-Y. Wei, J.-L. Chen, Ceram. Int. 34 (2008) 797.
[9] N. Sdiri, R. Jemai, M. Bejar, M. Hussein, K. Khirouni, E. Dhahri, S. Mazen, Solid
State Commun. 148 (2008) 577.
[10] B. Tang, H.F. Shanming, L. Liu, Mater. Sci. Eng. B 138 (2007) 205.
[11] D.D. Gulwade, S.M. Bobade, A.R. Kulkarni, P. Gopalan, J. Appl. Phys. 97 (2005)
074106.
[12] M. Lj Zivkovic, V.V. Paunovic, N. Lj Stamenkov, M.M. Miljkovic, Sci. Sinter. 38
(3) (2006) 273.
[13] Y.C. Chen, G.M. Lo, M.Y. Su, Jpn. J. Appl. Phys. Part 1: Regular Papers, Short Notes
& Review Papers 35 (1996) 2745.
[14] J. Zhi, A. Chen, Y. Zhi, P.M. Vilainho, J.L. Baptista, J. Am. Ceram. Soc. 82 (1999)
1345.
[15] B.V.B. Saradhi, K. Srinivas, G. Prasad, S.V. Suryanaryan, T. Bhimasankaram,
Mater. Sci. Eng. B 98 (2003) 10.
[16] N. Hirose, A.R. West, J. Am. Ceram. Soc. 79 (1996) 1633.
[17] D. Dhak, P. Dhak, T. Ghorai, P. Pramanik, J. Appl. Phys. 102 (2007) 074117.
171
[18] M. Dong, J.M. Reau, J. Ravez, Solid State Ionics 91 (1996) 183.
[19] P. Dhak, D. Dhak, K. Pramanik, P. Pramanik, Solid State Sci. 10 (2008)
1936.
[20] D. Dhak, P. Dhak, T. Ghorai, S.K. Biswas, P. Pramanik, J. Mater. Sci.: Mater. El. 19
(2008) 448.
[21] T.K. Ghorai, D. Dhak, S. Dalai, P. Pramanik, J. Alloys Compd. 463 (2008) 390.
[22] D. Dhak, P. Pramanik, J. Am. Ceram. Soc. 89 (2006) 1014.
[23] R.N. Das, P. Pramanik, Mater. Lett. 46 (2000) 7.
[24] B.D. Cullity, S.R. Stock, Elements of X-ray Diffraction, 3rd ed., Pearson Education
International, 2001, p. 170.
[25] M.N. Rahaman, Ceramic Processing and Sintering, Dekker, New York, 1995, p.
465.
[26] E. Barsoukov, J. Ross Macdonald, Impedance Spectroscopy Theory, Experiment
and Applications, 2nd ed., Wiley Interscience, New York, 2005, p. 14.
[27] J.R. Mac Donald, Impedance Spectroscopy Emphasizing Solid Materials and
System, John Wiley & Sons, New York, 1987, p. 191.
[28] J.R. Macdonald, Impedance Spectroscopy, John Wiley & Sons, New York, 1987,
p. 13, 14 and 205.
[29] B.A. Boukamp, Equivalent Circuit-EQUIVCRT Program Users Manual, vol. 3, Uni-
versity of Twente, The Netherlands, 1989, p. 47.
[30] J. Suchanicz, Mater. Sci. Eng. B 55 (1998) 114.
[31] A.K. Jonscher, Nature 267 (1977) 673.
[32] M.A.L. Nobre, S. Lanfredi, J. Phys. Chem. Solids 64 (2003) 2457.
[33] S. Sen, R.N.P. Chowdhary, A. Tarafdar, P. Pramanik, J. Appl. Phys. 99 (2006)
124114.
[34] A.J. Moulson, J.M. Herbert, Electroceramics, Chapman & Hall, London, UK, 1990.
[35] K. Pravakar, S.P. Mallikarjun Rao, J. Alloys Compd. 437 (2007) 302.
[36] S. Saha, S.B. Krupanidhi, J. Appl. Phys. 87 (2000) 849.
[37] S. Bhattacharya, S.S. Bharadwaja, S.B. Krupanidhi, J. Appl. Phys. 88 (2000) 4294.
[38] G.Y. Yang, E.C. Dicky, C.A. Randall, D.E. Barber, P. Pinceloup, M.A. Henderson,
R.A. Hill, J.J. Beeson, D.J. Skamser, J. Appl. Phys. 96 (2004) 7492.
[39] A. Munpakdee, K. Pengpat, J. Tontrakoon, T. Tunkasiri, Smart Mater. Struct. 15
(2006) 1255.
[40] S.P.S. Badwal, Processing of the International Seminar on Solid State Ionic
Devices, World Scientific Publishing, Singapore, 1988, p. 165.
[41] M. Vijayakumar, S. Selvasekarapandian, M.S. Bhuvaneswari, G. Hirankumar, G.
Ramprasad, R. Subramanian, P.C. Angelo, Physica B 334 (2003) 390.
[42] D.P. Almond, G.K. Duncan, A.R. West, Solid State Ionics 8 (1983) 159.
[43] E. Barsoukov, J. Ross Macdonald, Impedance Spectroscopy Theory, Experiment
and Applications, 2nd ed., Wiley Interscience, New York, 2005, p. 47.