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Dielectric and Impedance Studies of Ce-

Doped Ba(Zr0.52Ti0.48)O3
a a a
Raghavendra Sagar , Shivanand Madolappa & R. L. Raibagkar
a
Department of Post Graduate Studies and Research in Materials
Science, Gulbarga University, Gulbarga, 585 106, Karnataka state,
INDIA
Published online: 14 Dec 2011.

To cite this article: Raghavendra Sagar , Shivanand Madolappa & R. L. Raibagkar (2011): Dielectric
and Impedance Studies of Ce-Doped Ba(Zr0.52Ti0.48)O3 , Integrated Ferroelectrics: An International
Journal, 130:1, 21-26

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 Integrated Ferroelectrics, 130:21–26, 2011
Copyright © Taylor & Francis Group, LLC
ISSN: 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584587.2011.621753

Dielectric and Impedance Studies of Ce-Doped

Ba(Zr0.52 Ti0.48 )O3

RAGHAVENDRA SAGAR, SHIVANAND MADOLAPPA,

AND R. L. RAIBAGKAR∗
Department of Post Graduate Studies and Research in Materials Science,
Gulbarga University, Gulbarga-585 106, Karnataka state, INDIA
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Cerium (Ce) doped Ba(Zr0.52 Ti0.48 )O3 were prepared by conventional solid state reac-
tion method. The frequency dependence dielectric behaviors were studied from 50◦ C
temperatures to 400◦ C. Dielectric properties showed the low loss (tan δ) behavior.
The frequency dependent dielectric constant (ε ) exhibited moderate values. Impedance
studies (Z ) showed superior electrical behavior within the samples.

Keywords Ce-doping; low loss; dielectric constant; impedance measurement

Introduction
Now a day, low dielectric loss materials are attracting much interest due to their extraor-
dinary dielectric behavior in the field of wireless communication and microwave devices
[1–3]. The environment friendly lead-free perovskite-structured, BaTiO3 based materials
are one among them with high dielectric non-linearity, has become the potential candidate
for use in practical applications, including tunable microwave devices such as frequency-
agile filters, voltage-controlled oscillators, phase shifters, and antennas [4–5]. Isovalent
dopants, such as zirconium substituted in B–site in the form of Ba(Zr1-x Tix )O3 (BZT) are
the materials of immense interest due to their high dielectric constant, high voltage resis-
tance and better temperature stability [6–8]. Barium strontium titanate is possible alternative
to BST in the microwave dielectrics because Zr4+ is chemically more stable. However, ex-
tensive work has been reported on the structural and electrical behavior of BZT ceramics
[9]. Literature review suggests that the dielectric properties of the BZT ceramics strongly
depend on the Zr/Ti ratio [10].
Many researchers have reported that, better dielectric properties of BZT ceramics can
be obtained by doping rare earth ions, (e.g., La, Nd, Sm, Eu, Dy) of different ionic radius
[11–13]. Rare earth ions doping in barium based solid solutions exhibit semiconducting or
highly insulating behavior on the basis of doping concentration [14]. In this paper, on the
basis of Ti-vacancy defect composition model, Ce-ions with ionic radii less than barium
are introduced at Ba2+-site in the Ba(Zr0.52 Ti0.48 )O3 ceramic compound, according to the
composition formula (Ba1-x Cex )(Zr0.52 Ti0.48 )O3 (BCZT) where x = 0.1 and 0.2. Dielectric
properties of BCZT ceramics were investigated. The main focus is set on the effect of
Cerium–ion on the dielectric properties of the BCZT ceramics.

Received in final form October 10, 2010.

∗
Corresponding author. E-mail: rlraibagkar@rediffmail.com
21
 22 R. Sagar et al.

The main objective of this research is to seek a suitable material with low dielectric
loss and moderate dielectric constant for microwave device applications.

2 Experimental Procedure
(Ba1-x Cex )(Zr0.52 Ti0.48 )O3 at x = 0.1 and 0.2.powders were prepared by the conventional
solid state reaction method. The highly pure oxides and carbonate powder such as BaCO3
(Aldrich 99.9), ZrO2 (Aldrich 99.9), TiO2 Aldrich, 99.9), Gd2 O3 (Aldrich 99.9), were used
as the starting materials, which were weighed and mixed accordingly in the compositional
form of (Ba1-x Cex )(Zr0.52 Ti0.48 )O3 . The weighed mixtures were mixed by hand grinding
for 4 h by using agate mortar and pestle. The mixed powder was calcined in alumina
crucible at 900◦ C for 8 h in air with programmed rate of heating. The obtained powder
was hand grinded for 1 h and then subjected to pre-sintering for 950◦ C for 8 h in air. The
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product obtained from pre-sintering was again ground for 1 h and pressed into disc-shaped
pellets at 100 Mpa by adding 5 wt.% PVA binder. The pellets of pure and Ce ions doped
Ba(Zr0.52 Ti0.48 )O3 were sintered at 1400◦ C for 8 h in air.
The structural studies were evaluated from X-ray diffractometer (Philips, PANalytical
PRO) using Cu Kα radiation. The surface morphology of the obtained ceramic sample
was characterized by scanning electron microscopy. The grain sizes of the samples were
evaluated from line intercept method. The dielectric properties of the samples were studied

Figure 1. Frequency dependent tan δ plots of BCZT10 and BCZT20 ceramics.

 Dielectric and Impedance Studies of Ce-Doped Ba(Zr0.52 Ti0.48 )O3 23

using impedance analyzer (WAYNE KERR, 43100) from which measurement of capaci-
tance (C), at various temperature range of 50◦ C to 400◦ C were studied in order to calculate
various related dielectric parameters.

3 Results and Discussion

Dielectric Studies
Figure 1 exhibits a typical behavior of change in tan δ with frequency at different temper-
atures. The value of tan δ was observed to be higher for both the samples at 100 oC. It is
well known that at lower frequencies i.e. around 10 kHz, the value of tan δ is high because
of low frequency dipolar polarization, mainly observed due to the stronger influence of
composition and structural behavior [15–16]. However, tan δ in higher frequency ranges
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Figure 2. Frequency dependent ε patterns of BCZT10 and BCZT20 ceramics.

 24 R. Sagar et al.

is small due to the in low frequency dipolar polarization. The observed tan δ at various
temperature ranges is very less, i.e., in between 0.16 to 0.005. This low loss of the samples
signify a good quality of low loss materials and further same value of tan δ at microwave
frequency regime may shows potential use in dielectric ceramic applications including
resonators, radars and detectors [17].
The frequency dependence of dielectric constant (ε ) of the BCZT samples at various
temperatures is shown in Fig. 2. At lower frequencies (≤104 Hz) and temperature at 50 oC,
ε has very high value for both the samples and anomalous decrease in the value of ε was
observed at different temperatures. However, the value of ε decreased after the substitution
of Ce (x = 0.2) in the sample. Generally, for all the samples, ε value is almost same on
increasing frequency. This is very much consistent for non-linear dielectrics because at
lower frequencies all the polarizations (i.e., interfacial, dipole, ionic, atomic and electronic)
are present in the samples. The magnitude of ε is of the order of 103 for the entire sample at
various temperatures. However, the small decrease in the value of ε for both temperature and
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Figure 3. Frequency dependent Z plots of BCZT10 and BCZT20 ceramics.

 Dielectric and Impedance Studies of Ce-Doped Ba(Zr0.52 Ti0.48 )O3 25

frequency was observed. The anomalous change in the value of ε is attributed to influence
of zirconium in the microstructure of BCZT. In the sample due to Zr-rich concentration the
grain size of the sample reduces, which tends polarizability in atoms of the structure, and
the difference in the conductivity of grain and grain boundaries, which in turn gives rise to
dipolar polarization. However, this decrease in ε is of very small magnitude.

Impedance Studies
The frequency dependence impedance spectra of the samples are shown in Fig. 3. Both
BCZT10 and BCZT20 sample indicates frequency dependent decrease of Z’ up to 200 kHz
and 20 kHz, respectively and later remains constant up to 1 MHz, clearly indicating effect
of Ce on impedance spectra. The larger value of Z in lower frequency (10 KHz) range
is mainly due to the low frequency dipolar polarization mechanism i.e., barrier potential
decreases due to the release of charges which in turn increases the σ ac of the materials [18].
However, the effect of temperature is also not as influential in higher frequencies for both
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the samples as seen from Fig. 3.

Conclusion
Solid solutions of (Ba1-x Cex )(Zr0.52 Ti0.48 )O3 was prepared with solid state reaction tech-
nique with x = 0.1 and x = 0.2. The frequency dependent tan δ study shows the non-linear
dielectric property change with different concentration of Ce. Relative permittivity shows
the moderate values in all studied temperature range. Impedance measurement proves
excellent electrical behaviour of the samples.

Acknowledgements
Two of the Authors (RS and SM) acknowledge University Grants Commission (UGC) New
Delhi, India, for granting RFSMS Fellowship No. F. 4-1/2006(BSR)/11-129/2009 (BSR).

References
1. P. Petkov, I. Ilieva, T. Petkovab, and V. Vassileva, New complex ceramic materials for microwave
resonators. J. Optoelectron and Adv Mater. 5(2), 521–524 (2003).
2. S. Sreekantan, C. T. Shin, and A. F. M. Noor, Structural and dielectric properties of the Mn-Doped
BaO-Nd2 O3 -4TiO2 system. J. Phy. Sci. 20(2), 13–22 (2009).
3. H. Sreemoolanadhana, M. T. Sebastiana, R. Ratheeshb, R. Blachnikb, M. Woehleckec, B. Schnei-
derc, M. Neumannc, and P. Mohanan, Microwave dielectric properties of BaO2 -CeO2 -nTiO2
ceramics. J. Solid State Chem. 177, 3995–4000 (2004).
4. S. Bahel and S. B. Narang, Dielectric and structural characteristics of Sm doped Ba4 La9.33 Ti18 O54
ceramics. Materials Science-Poland 26(3), 555–561 (2008).
5. Y. Kuga, S. Lee, M. Taya, A. Almajid, S. Lee, J. Li, and R. Watanabe, Experimental and numerical
studies of dielectric properties of BaTiO3 -platinum composites at microwave frequencies. IEEE
Transactions on Dielectrics and Electrical Insulation 12(4), 827–824 (2005).
6. U. Weber, G. Greuel, U. Botteger, S. Weber, D. Hennings, and R. Waser, Dielectric Properties of
Ba(Zr,Ti)O3 –Based Ferroelectrics for Capacitor Applications. J. Am. Ceram. Soc. 84(4), 759–766
(2001).
7. D. Hennings and A. Schnell, Diffuse ferroelectric phase transitions in Ba(Ti1-y Zry )O3 ceramics.
J. Am. Ceram. Soc. 65, 539–544 (1982).
8. D. Hennings, B. Schrchreinemacher, and H. Schreinemacher, High-permittivity dielectric ce-
ramics with high endurance. J. Eur. Ceram. Soc. 13, 81–85 (1994).
 26 R. Sagar et al.

9. S. M. Neirman, The curie point temperature of Ba(Ti1-X Zrx )O3 solid solutions. J. Mater. Sci. 23,
3973–80 (1988).
10. A. Dixit, S. B. Mujumdar, A. S. Savvinov, R. S. Katiyar, R. Guo, and A. S. Bhalla, Investigations
on the sol-gel-derived barium zirconium titanate thin films. Mat. Lett. 56, 933–940 (2002).
11. X. Chou, J. Zhai, H. Jiang, and X. Yao, Dielectric properties and relaxor behavior of rare-
earth (La, Sm, Eu, Dy, Y) substituted barium zirconium titanate ceramics. J. Appl. Phys. 102,
084106-1-6 (2007).
12. C. Ostos, L. Metres, M. L. Martinaz-Sarrion, J. E. Garcia, A. Albarda, and R. Perez, Synthesis and
charecterization of A-site deficient rare-earth doped BaZrx Ti1-x O3 . Solid Stat. Sci. 11, 1016–1022
(2009).
13. E. Delgado, C. Ostos, M. L. Martinz-Sarrion, L. Mestres, and P. Prieto, Characterization and
electrical properties of new perovskite films of Ba(Ti,Zr)O3 type doped with lanthanum (BLZT).
Phys. Stat. Sol.(C) 4. 11, 4099–406 (2007).
14. E. Antonelli, M. Letonturier, J. C. M’peko, and A. C. Hernands, Microstructural, structural and
dielectric properties of Er3+ -modified BaTi0.85 Zr0.15 O3 . J. Euro. Ceram. Soc. 29, 1449–1455
(2009).
Downloaded by [Gulbarga University ] at 00:29 17 June 2013

15. M. C. Gust, L. A. Momada, N. D. Evans, and M. L. Mecartney, Crystallization of Sol–Gel-

Derived Barium Strontium Titanate Thin Films. J. Am. Ceram. Soc. 84(5), 1087–92 (2001).
16. R. R. Das, P. Bhattacharya, and R. S. Kattiyar, Enhanced ferroelectric properties in laser-ablated
SrBi2 Nb2 O9 thin films on platinized silicon substrate. Appl. Phys. Lett. 81(9), 1672 (2002).
17. V. M. Ferreira and J. L. Baptista, Preparation and microwave dielectric properties of pure and
doped magnesium titanate ceramics. Mater. Res. Bull. 29(10), 1017–1023 (1994).
18. K. S. Rao, D. M. Prasad, P. M. Krishna, B. H. Bindu, and K. Suneetha, frequency and temperature
dependence of electrical properties of barium and gadolinium substituted SrBi2 Nb2 O9 ceramics.
J. Mater. Sci. 42, 7363–7374 (2007).