Phase transitions and dielectric properties in Bi(Zn1/2Ti1/2)O3−BaTiO3

perovskite solid solutions

Chien-Chih Huang and David P. Cann

Citation: J. Appl. Phys. 104, 024117 (2008); doi: 10.1063/1.2960469

View online: http://dx.doi.org/10.1063/1.2960469
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Published by the American Institute of Physics.

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 JOURNAL OF APPLIED PHYSICS 104, 024117 共2008兲

Phase transitions and dielectric properties in Bi„Zn1/2Ti1/2…O3 − BaTiO3

perovskite solid solutions
Chien-Chih Huanga兲 and David P. Cann
Materials Science, Department of Mechanical Engineering, Oregon State University,
Corvallis, Oregon 97331, USA
共Received 13 February 2008; accepted 31 May 2008; published online 30 July 2008兲
共1 − x兲Bi共Zn1/2Ti1/2兲O3 − xBaTiO3 polycrystalline ceramics were obtained via solid state processing
techniques. The perovskite structure was found to be stable for compositions containing x = 0.66 or
greater. Based on x-ray diffraction data, a morphotropic phase boundary between tetragonal and
rhombohedral perovskite phases was observed at x ⬇ 0.9. For compositions rich in BaTiO3, the
symmetry of the perovskite phase was tetragonal but with increased Bi共Zn1/2Ti1/2兲O3 content, the
rhombohedral phase appeared. Dielectric characterization revealed that as Bi共Zn1/2Ti1/2兲O3 content
increased, the transition temperature decreased and the transition peak became very diffused. A
comparison of the dielectric behavior with other Bi共Zn1/2Ti1/2兲O3-based solid solutions is also
discussed. © 2008 American Institute of Physics. 关DOI: 10.1063/1.2960469兴

I. INTRODUCTION 共BZT-BT兲 system. The dielectric properties of the BiScO3

Solid solutions of Bi共Me兲O3 − PbTiO3 perovskites have
been widely investigated due to their high Curie transition
temperature 共TC兲 and excellent piezoelectric properties.1,2 In
Bi共Me兲O3 compounds, Me can either be a single trivalent
cation or two cations with an average of +3 valence which
occupy the octahedral sites. Recently, Eitel et al.2,3 reported a
new piezoelectric material based on BiScO3 − PbTiO3 共BS-
PT兲 which showed high piezoelectric properties and a high
transition temperature 共TC ⬇ 450 ° C兲 at the morphotropic
phase boundary 共MPB兲. Instead of decreasing tetragonality
with increasing Bi共Me兲O3 content, Suchomel and Davies4,5
demonstrated an enhanced tetragonality in Bi共Zn1/2Ti1/2兲O3
− PbTiO3 共BZT-PT兲 solid solutions. In this system, the MPB
did not appear and the tetragonal phase persisted over all
compositions studied until a second phase formed.
Due to environmental concerns, the replacement of toxic
Pb in piezoelectric materials is a high priority. Thus, there is
a great need for a Pb-free piezoelectric material that shows
comparable electric properties to Pb-based piezoelectrics. Bi-
based perovskites are a good candidate due to their similar
electronic structure with Pb.6,7 However, the smaller size of
the Bi cation severely limits the stability of the perovskite
structure. Therefore, one approach is to utilize a solid solu-
tion with a stable perovskite end member. Thus, BaTiO3 is a
good candidate due to its high degree of solid solution on
other perovskite phases and its stable tetragonal crystal struc-
ture at room temperature.
In a previous work, solid solutions within the ternary
perovskite system Bi共Zn1/2Ti1/2兲O3 − BiScO3 − BaTiO3 were
investigated.7,8 The phase equilibria and dielectric data
showed a transition from the pseudocubic relaxor behavior to
tetragonal normal ferroelectric behavior. The object of this
research is focused on the transition temperature and ferro-
electric properties of the binary Bi共Zn1/2Ti1/2兲O3 − BaTiO3
a兲
Electronic mail: huangch@onid.orst.edu.
− BaTiO3 system will be also discussed as a comparison.
II. EXPERIMENT
Ceramics of a composition 共1 − x兲Bi共Zn1/2Ti1/2兲O3
− xBaTiO3 where x = 0.66– 1 were synthesized by conven-
tional solid state reaction methods. Reagent grade oxide
powders of Bi2O3共ⱖ99.9%兲, ZnO共ⱖ99%兲, TiO2共ⱖ99.9%兲,
and BaCO3共ⱖ99.5%兲 were batched in stoichiometric
amounts and vibratory milled with ethanol and yttrium-
stabilized zirconia media for 6 h. The dried powders were
calcined in crucibles at 950 ° C for 12 h followed by addi-
tional milling and drying. The calcined powders were mixed
with a 3 wt % polyvinyl butyral binder and then uniaxially
cold pressed at 150 MPa into 12.7 mm diameter pellets. Fol-
lowing binder burnout at 400 ° C, the pellets were sintered in
sealed crucibles between 1100 and 1300 ° C for 2 h. For
phase determination, x-ray diffraction 共XRD兲 共Bruker-AXS
D8兲 was utilized in the 2␪ scan range of 10° – 80° using
sintered ceramics.9
Prior to making dielectric measurements, the samples
were polished to obtain smooth and parallel surfaces. After
polishing, a silver electrode paste 共Heraeus C1000兲 was ap-
plied and then fired at 650 ° C for 30 min. Polarization hys-
teresis measurements 共P-E兲 were obtained at a frequency of
10 Hz using a ferroelectric test system 共Radiant兲. The strain
as a function of the applied electric field was determined by
using an optical displacement sensor 共MTI-2100兲. An Agi-
lent 4284A LCR meter was then used to measure the dielec-
tric properties over a wide temperature range.
III. RESULTS AND DISCUSSION
A. Crystal structure of BZT-BT solid solutions
Figure 1 shows XRD patterns of sintered 共1
− x兲BZT-xBT ceramics at room temperature. Single-phase
perovskite was obtained for compositions containing up to
33 mol % of BZT. Higher concentrations of BZT resulted in

0021-8979/2008/104共2兲/024117/4/$23.00 104, 024117-1 © 2008 American Institute of Physics

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024117-2 C.-C. Huang and D. P. Cann J. Appl. Phys. 104, 024117 共2008兲

FIG. 1. 共Color online兲 XRD patterns of sintered 共1 − x兲共BZT兲-xBT ceramics.

the formation of secondary phases. According to the peak

splitting of the 兵200其 reflection, the samples exhibited tetrag-
onal symmetry 共P4mm兲 between 1 ⱕ x ⱕ 0.95. The tetrago-
nality 共or c / a ratio兲 decreased as the BZT content increased FIG. 2. 共Color online兲 Dielectric constant as a function of temperature for
共1 − x兲BZT-xBT at a measurement frequency of 10 KHz.
as observed by the merging of the 兵200其 peaks as shown in
Fig. 1共b兲. For compositions between 0.8ⱕ x ⱕ 0.66, the struc-
ture was stabilized into pseudocubic or rhombohedral sym- ⬘
␧m 关T − Tm共f兲兴␥
metry. According to XRD data, a MPB between the tetrago- =1+ 共1 ⱕ ␥ ⱕ 2兲. 共1兲
␧⬘共f,T兲 2␦␥2
nal and rhombohedral phases was observed at a composition
close to x = 0.9. However the exact MPB composition is dif- It was observed that the diffuseness increased with increas-
ficult to determine. ing BZT content. However the transition temperature Tm was
exhibited at a minimum of x = 0.9. Within the tetragonal re-
gion, Tm decreased dramatically with increasing BZT content
indicating a destabilization of the ferroelectric phase. Within
the rhombohedral phase field, the transition temperature in-
B. Dielectric properties of BZT-BT solid solutions
creased linearly with BZT content. This phenomenon is very
In Fig. 2, the dielectric constant as a function of tem-
perature was plotted for the 共1 − x兲Bi共Zn1/2Ti1/2兲O3
− xBaTiO3 ceramic solid solutions. According to Fig. 2, pure
BaTiO3 ceramic showed three distinct transition tempera-
tures at approximately −90, 0, and 130 ° C. However, with
the addition of only 5% BZT, the transition peaks at 0 and
−90 ° C vanished and a single phase transition was observed.
The dielectric data for the x = 0.9 composition shows that the
transition temperature is in the vicinity of room temperature.
This is consistent with the relatively broad peaks observed in
the XRD data 共Fig. 1兲.
Figure 3 illustrates the diffuseness of the phase transition
in terms of the parameter ␦r and the temperature at which the
maximum permittivity was observed 共Tm兲 as a function of
composition. The degree of diffuseness 共␦r兲 can be obtained
from the following expression:10 FIG. 3. 共Color online兲 Tm and diffuseness ␦ as a function of BaTiO3 content.

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024117-3 C.-C. Huang and D. P. Cann
FIG. 4. 共Color online兲 Lattice parameter of 共1 − x兲BZT-xBT.
similar to previous results in the BiScO3 − Bi共Zn1/2Ti1/2兲O3
− BaTiO3 ternary system.
The effects of composition on the unit cell parameters
and volume is shown in Fig. 4. While the volume decreases
as the mole percent of BZT increases, there is an anomalous
peak close to the MPB composition at x = 0.9. This could be
attributed to the coexistence of the rhombohedral and tetrag-
onal phases due to the fact that at this composition the phase
transition is very close to room temperature 共Tm ⬇ 30 ° C兲. It
could also be related to the structural disorder in the B-cation
sublattice due to the limited processing temperatures.
The dielectric properties as a function of frequency for
the 0.2BZT-0.8BT composition are shown in Fig. 5. The fre-
quency dependence of the transition peaks indicates a strong
relaxor behavior for this composition. Moreover, these com-
positions exhibit a stable dielectric constant and low loss
tangent 共tan␦ ⬍ 0.01兲 up to high temperatures 共T ⬍ 400 ° C兲.
It may have potential for high temperature applications.
The polarization hysteresis data at room temperature for
共1 − x兲BZT-xBT are shown in Fig. 6. The remnant polariza-
FIG. 5. 共Color online兲 Dielectric constant and tan ␦ of 0.2BZT-0.8BT as a
function of temperature.
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J. Appl. Phys. 104, 024117 共2008兲
FIG. 6. 共Color online兲 P-E hysteresis measurements on 共1 − x兲BZT-xBT
ceramics obtained at room temperature.
tion 共Pr兲 and coercive field 共Ec兲 were increased to
10.2 ␮m C / cm and 11.3 kV/cm for 0.05BZT-0.95BT com-
pared to pure BaTiO3. However, when more BZT was added,
the area of hysteresis loops decreased dramatically. The ab-
sence of clear hysteresis behavior for higher BZT contents
can be related to a decreased Tm, as shown in Fig. 2. Al-
though Tm increased by x ⬎ 0.1, the relaxor behavior due to
rhombohedral symmetry and possibly the degree of higher
disorder in the structure resulted in the disappearance of hys-
teresis loops.
Figure 7 shows the strain behavior at room temperature
under a bipolar driving electric field from 0 to 60 kV/cm.
The slope of the strain-electric field loop decreased when the
BZT content increased. This may be due to the loss of nor-
mal ferroelectric behavior revealed in Fig. 6.
C. Dielectric properties for BS-BT and BZT-BT
ceramics
The dielectric constant and loss versus temperature for
0.2关xBi共Zn1/2Ti1/2兲O3 − 共1 − x兲BiScO3兴 − 0.8BaTiO3 ceramics
FIG. 7. 共Color online兲 Strain-electric field measurements on 共1
− x兲BZT-xBT ceramics obtained at room temperature.
024117-4 C.-C. Huang and D. P. Cann J. Appl. Phys. 104, 024117 共2008兲

sized via conventional solid state processing techniques. A

phase boundary between ferroelectric tetragonal and rhom-
bohedral phases was observed close to x = 0.99. The tetrago-
nality decreased and the diffuseness of the phase transition
increased with increasing BZT content. Measurement of the
unit cell volume as a function of composition showed a lin-
ear dependence except for a peak near the MPB which can
be attributed to the coexistence of the rhombohedral and te-
tragonal phases. The hysteresis measurements revealed an
improved Pr and Ec for x = 0.95 compared to pure BaTiO3.
Due to the diffuseness of the phase transition, the dielectric
constant remains stable and loss tangents remained small
共tan ␦ ⬍ 0.01兲 over a wide range of temperatures 共T
⬍ 400 ° C兲.
FIG. 8. 共Color online兲 Dielectric constant and tan ␦ vs temperature for
0.2关xBi共Zn1/2Ti1/2兲O3 − 共1 − x兲BiScO3兴 − 0.8BaTiO3 at 10 KHz. 1
C. J. Stringer, T. R. Shrout, and C. A. Randall, J. Appl. Phys. 99, 024106
共2006兲.
are shown in Fig. 8. The transition peak in BS-BT is clearly 2
R. E. Eitel, C. A. Randall, T. R. Shrout, P. W. Rehrig, W. Hackenberger,
more diffused than the BZT-BT system. This may indicate and S.-E. Park, Jpn. J. Appl. Phys., Part 1 40, 5999 共2001兲.
3
that the source of the relaxor behavior is more closely tied to R. E. Eitel, C. A. Randall, T. R. Shrout, and S.-E. Park, Jpn. J. Appl. Phys.,
disorder on the B-site. Moreover, though Sc3+ is bigger than Part 1 41, 2099 共2002兲.
4
the average of Zn2+ and Ti4+, the transition temperature is the M. R. Suchomel and P. K. Davies, J. Appl. Phys. 96, 1489 共2004兲.
5
M. R. Suchomel and P. K. Davies, Appl. Phys. Lett. 86, 262905 共2005兲.
same for BZT-BT and BS-BT. This result is quite different 6
G. A. Smolenskii, V. A. Isupov, A. I. Agranovskaya, and N. N. Krainik,
from other BiMeO3 − PbTiO3 systems in which the transition Sov. Phys. Solid State 2, 2651 共1961兲.
temperature is highly dependent on the size of the B-site 7
R. E. Cohen, Nature 共London兲 358, 136 共1992兲.
cations.1 8
C.-C. Huang, D. P. Cann, X. Tan, and N. Vittayakorn, J. Appl. Phys. 102,
044103 共2007兲.
IV. CONCLUSIONS 9
O. Bidault, P. Goux, M. Kchikech, M. Belkaoumi, and M. Maglione, Phys.
Perovskite solid solutions based on 共1 Rev. B 49, 7868 共1994兲.
10
K. Uchino and S. Nomura, Ferroelectr., Lett. Sect. 44, 55 共1982兲.
− x兲Bi共Zn1/2Ti1/2兲O3 − xBaTiO3 with x ⱖ 0.66 were synthe-

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