1 s2.0 S0921510709003894 Main
1 s2.0 S0921510709003894 Main
1 s2.0 S0921510709003894 Main
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.
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. 4. (a) Bright field (BF) TEM and (b) particle-size distribution pattern of BTLM compound.
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.
Fig. 5. SEM micrograph of BTLM compound. 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)
complex impedance spectrum (Nyquist plot) i.e., the variation of within the sample with definite contributions from both bulk (grain
real and imaginary part of impedance, measured at different tem- interior) and grain boundary effects [Fig. 6(b)–(d)]. The values of
peratures, is shown in Fig. 6(a)–(d). The impedance spectroscopy circuit elements obviously depend on the volume fraction of the
is characterized by the appearance of the semicircular arcs, whose individual components (i.e., grain and grain boundary effect), which
pattern of evolution changes with rise in temperature. The tem- is related to the microstructure of the compound. In order to estab-
perature effect on impedance behavior is more important because lish a connection between the microstructure and the electrical
with increase in temperature, the semicircular nature of the arcs properties, several microstructural models [27] are discussed in the
increases and the arcs shift to the center of the arc towards the literature, which usually fall into two types: the layer models and
origin of the complex plain plot. In Fig. 6(a) and (d), the entire the effective medium models. In ceramics, which are used because
plots show single arc, which indicates that the electrical pro- of their high dielectric permittivities, grain boundaries are often
cess contribution is from bulk materials (grain interior), which electronically active due to depletion effects and act as barriers to
can be modeled as an equivalent circuit comprising of a parallel 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) 165–171 169
be expressed in terms of a bricklayer model [28], where the con- a spread of relaxation time [31]. The relaxation phenomenon in the
duction through the grain and grain boundaries dominates, with material may be due to the presence of immobile species/electron
electrical circuit having different values of capacitance and resis- at low temperature and defects/vacancies at higher temperature.
tance as shown in Table 1 in the temperature range from 350 to For the dielectric materials, the localized relaxation (i.e., defect
500 ◦ C. The resistance value was evaluated from the impedance relaxation) dominates [32] because of the low dielectric ratio r
spectrum using the equivalent circuit (EQUIVCRT) software pro- (r = εs /ε˛ , εs and ε˛ are the dielectric constants at low and high
gram [29], whereas the capacitance can be calculated using the frequencies respectively). As shown in Fig. 7(b), there was a clear
following relation: dispersion of the resultant curves in the low frequency region at
different temperatures and appears to be merging at higher fre-
(2f )(Rb Cb ) = 1, (1)
quency irrespective of temperature. This behavior may be because
1 of the presence of the space charge polarization effect at lower
Cb = , (2)
2fRb frequencies, which is eliminated at higher frequencies [33].
The impedance data were used to evaluate the relaxation time
where Rb and Cb refer to bulk resistance and capacitance; f is the
( ) of the electrical phenomena using the relation ω = 1, where
relaxation frequency. This relation is also valid for grain boundary
ω = 2f is the angular frequency. The nature of the variation of
effects.
with 103 T−1 of the compound as shown in Fig. 7(b) (inset), follows
The absence of third semicircle suggests that the contribution
the Arrhenius relation [34]. The activation energy evaluated from
of the electrode–materials interface to impedance is negligible.
the slope of log ( ) against 103 T−1 curve of BTLM compound is
The analysis of the curves shows that the semicircle exhibits some
0.98 eV.
depression degree instead of a semicircle centered on the abscissa
axis. This decentralization reflects the non-Debye-type relaxation. 3.4. Electrical conductivity study
3.3.1. Variation of the real part of the impedance with frequency 3.4.1. dc conductivity
Fig. 7(a) shows the variation of real part of impedance (Z ) with Electrical conduction in dielectric material is a thermally acti-
frequency at different temperatures of the BTLM compound. On vation process and is due to the ordered motion of weakly bound
increasing temperature the Z value decreased which indicates the charged particles under the influence of an electric field. It depends
increase in ac conductivity as shown in Fig. 9. At higher frequency, on the nature of the charge carriers that dominate the conduc-
the Z value merges for all the temperatures, which clearly indi- tion process like electrons/holes or cations/anions and follow the
cates the presence of space charge polarization [30]. The higher Arrhenius low. The bulk conductivity ( rb ) of the compound can be
impedance value at lower frequency is also an indication of the evaluated from the impedance data using the relation, dc = t/Rb A
space charge polarization of the materials. 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
3.3.2. Variation of the imaginary part of the impedance with value of low frequency intercept of the semicircle on the real axis
frequency (Z ) in the complex impedance plot.
Fig. 7(b) shows the variation of imaginary part of impedance Fig. 8 shows the variation of bulk conductivity ( rb ) and grain
(i.e., loss spectrum) with frequency at different temperatures. The boundary conductivity ( gb ) as a function of temperature of the
loss spectrum (Z ) increased with increase in frequency in all BTLM compound. Using this Arrhenius plot of dc conductivity, the
the temperature ranges studied here and exhibited a maximum corresponding activation energy for both bulk and grain boundary
before starts decreasing rapidly. The existence of a temperature were calculated from the slope of the linear portion of the plot and
dependent electrical relaxation phenomenon is suggested by this were found to be 0.96 and 0.94 eV. The activation energy calculated
maximum shifts to higher frequency with an increase in temper- from rb vs 103 T−1 plot (Fig. 8) is almost similar with that of the
ature. The Z peak shifts to higher frequencies with increasing activation energy estimated from the relaxation time plot (Fig. 7(b)
temperature [as shown by the arrow, Fig. 7(b)], which indicates (inset)). The close resemblance of the two values indicates that the
the presence of temperature dependent electrical relaxation phe- relaxation and the conduction processes may be attributed to the
nomenon in the system. The asymmetric broadening of the peaks same type of charge carriers. The value of conductivity at 500 ◦ C is
suggested the presence of electrical processes in the material with 4.02 × 10−4 S/cm.
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.
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.
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[22] D. Dhak, P. Pramanik, J. Am. Ceram. Soc. 89 (2006) 1014.
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