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High piezoelectric performance in a new Bibased perovskite of (1-x)Bi(Ni12Hf12)O3-xPbTiO3

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JOURNAL OF APPLIED PHYSICS 112, 114120 (2012)

High piezoelectric performance in a new Bi-based perovskite

of (12x)Bi(Ni1/2Hf1/2)O32xPbTiO3
Zhao Pan,1 Jun Chen,1,a) Longlong Fan,1 Laijun Liu,2 Liang Fang,2 and Xianran Xing1,3,a)
1

Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China
Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, Ministry of Education,
Guilin University of Technology, Guilin 541004, China
3
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing,
Beijing 100083, China
2

(Received 6 September 2012; accepted 12 November 2012; published online 13 December 2012)
Preparation, piezoelectric, and dielectric properties were investigated in a new Bi-based
piezoelectric material of (1x)Bi(Ni1/2Hf1/2)O3-xPbTiO3. The system can form a pure perovskite
structure with the morphotropic phase boundary locating at x 0.62, separating the rhombohedral
and tetragonal phases. It is interesting to observe that the morphotropic phase boundary
composition shows a very high piezoelectric coefficient of d33 (446 pC/N), which is comparable to
BiScO3-PbTiO3 (460 pC/N). The Curie temperature of the morphotropic phase boundary is around
290  C. Furthermore, the system has a relatively low coercive field, which makes the poling easily.
Temperature dependence of dielectric properties also shows that the Bi(Ni1/2Hf1/2)O3-PbTiO3
system has a strong relaxor feature. Present new Bi-based perovskite of Bi(Ni1/2Hf1/2)O3-PbTiO3 is
C 2012 American
a competitive piezoelectric material with high piezoelectric performance. V
Institute of Physics. [http://dx.doi.org/10.1063/1.4769405]

I. INTRODUCTION

Many attempts have been carried out to obtain high piezoelectric performance ceramics for the increasing demand
of piezoelectric materials in industrial applications.13
Recently, investigations have been focused on BiMeO3PbTiO3 solid solutions, where Me can be a single cation of
valence 3 or a mixture of cations with an average valence
of 3. Studies have shown that the Bi substitution in the
BiMeO3-PbTiO3 systems plays an important role in enhancing both tetragonality (c/a) and Curie temperature (TC).46 In
previous studies of the Bi-based systems, BiScO3-PbTiO3
(BS-PT) exhibits excellent piezoelectric properties in the
morphotropic phase boundary (MPB, d33 460 pC/N and
TC 450  C),1 which is even superior to the conventional
piezoelectric ceramics based on Pb(Zr1xTix)O3 (PZT).
However, the highest d33 in the other Bi-based systems
reaches approximately 300 pC/N of Bi(Sc1/2Fe1/2)O3-PbTiO3
(d33 298 pC/N),4 which is much lower than that of BS-PT.
Furthermore, it is generally known that only a few BiMeO3PbTiO3 systems can form the MPB where the piezoelectric
properties are optimized.79 The initial work is to find new
Bi-based materials with high piezoelectric performance in
the MPB.
Compared to PZT, PbHfO3-PbTiO3 (PHT) shows a sim ) is
ilar behavior, due to the cation radius of Hf4 (0.71 A
),10,11 thus they possess similar
very close to Zr4 (0.72 A
ionic polarizations. Jaffe et al. has determined the binary
phase diagram of the isomorphic PHT series, where the
rhombohedral Hf-rich phase is separated from the tetragonal
Ti-rich phase by a MPB at 50%PT, with dielectric constant
a)

Authors to whom correspondence should be addressed. Electronic

addresses: junchen@ustb.edu.cn and xing@ustb.edu.cn.

0021-8979/2012/112(11)/114120/4/$30.00

and radial coupling factor reaching maximum values.12,13

That means Hf may be a possible important element to
improve electrical properties of the piezoelectric ceramic
materials. Furthermore, considering the facts that the cation
) is also close to Sc3 (0.745 A
) in the
radius of Hf4 (0.71 A
BS-PT which presents excellent piezoelectric properties, and
) is in Bi(Ni1/2Ti1/2)O3the effective cation of Ni2 (0.69 A
PbTiO3 showing good piezoelectric property,11,14 high performance of piezoelectric properties could exist in the new
type Bi-based perovskite of Bi(Ni1/2Hf1/2)O3-PbTiO3 (BNHPT). Therefore, in the present study, preparation, piezoelectric, and dielectric properties were carried out in the
BNH-PT binary. Excellent piezoelectric performance was
observed in the BNH-PT, which could be comparable to the
BiScO3-PbTiO3 system.
II. EXPERIMENT

(1x)Bi(Ni1/2Hf1/2)O3-xPbTiO3 (abbreviated as (1x)

BNH-xPT) ceramics were prepared by the conventional solid
state method. Samples in the solution series were fabricated
with reagent grade oxide powders, PbO, TiO2, Bi2O3, NiO,
and HfO2, with the purity >99%. Powders were stoichiometrically weighed and mixed using hand milling in an agate
mortar, ensuring the powders were as homogeneous as possible. Calcination of these mixed powders was performed at
850  C for 6 h. After calcination, the powders were ground in
mortar and pressed into pellets with a diameter of 10 mm and
thickness of 1 mm, and then the pellets were sintered at
1180  C for 2 h in a closed crucible.
Powder X-ray diffraction (XRD, Xpert PRO, PANalytical) patterns at room temperature of the BNH-PT
(x 0.570.90) system were recorded in the 2h scan range
of 20 60 . The surface morphology of the ceramics was

112, 114120-1

C 2012 American Institute of Physics

V

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114120-2

Pan et al.

studied by the scanning electron microscope (SEM, LEO

1530, Germany). For electrical measurements, the sintered
pellets were polished to a thickness of 0.6 mm. Silver paste
on both sides of the samples as the electrodes was fired on at
500  C for 30 min. A triangular wave form at a frequency of
1 Hz was used to monitor the temperature dependence of
polarization (P) and field-induced longitudinal strain (S)
curves in a silicone oil bath (Model aixACCT, TF Analyzer
1000, Germany). For the measurement of the small-signal
piezoelectric coefficient d33, samples were poled at room
temperature under an electric field of 5 kV/mm for 15 min
and then measured using a quasi-static d33 meter (China
Academy of Acoustics, ZJ-3). Dielectric properties were
investigated as a function of frequency and temperature
using an impedance analyzer (HP4192A, Hewlett-Packard,
Palo Alto, CA).
III. RESULTS AND DISCUSSION

The BNH-PT piezoelectric ceramic was determined to

be tetragonal for x  0.64, and the MPB region between the
ferroelectric tetragonal and the rhombohedral was determined to be at approximately 0.61  x  0.63. When
x  0.61, the split of diffraction profile, such as {200}, disappears, and merges into a singlet profile. It implies that the tetragonal phase features disappear, and the sample completely
transforms into rhombohedral phase structure. It needs to
note that the diffraction profile of rhombohedral compositions shows a broad character and no apparent splitting character can be observed, which means a very small lattice
distortion. The small lattice distortion could imply a good
piezoelectric property due to the easy domain wall motion.
The c/a ratio changes from 1.05 to 1.01 as a function of
BNH concentration (supplementary material).15 The composition of x 0.64 near the MPB has a very small value of c/a
ratio (1.01), which is the lowest except the Bi(Mg3/4W1/
9
4)O3-PbTiO3 (c/a 1.002 at the MPB). This reveals that the
BNH-PT has a really small c/a ratio, and it could have a
great influence on its properties. The detailed structural
results of the BNH-PT solid solutions are listed in the supplementary material.15
The evolution of polarization loops of BNH-PT
(x 0.64, 0.62, 0.60, and 0.58) at room temperature is presented in Fig. 1. The polarization loops are rectangular and
fully saturated, and the remnant polarization (Pr) and coercive field (EC) as a function of BNH content can be obtained.
Pr increases with increasing BNH content, and reaches maximum values at the MPB composition (x 0.62), then
decreases in the rhombohedral phase. Due to the coexistence
of tetragonal and rhombohedral phases in the MPB, the
highest Pr value is expected owing to the summation of the
possible crystallographic orientations, with eight h111i spontaneous polarization directions in the rhombohedral phase
and six h001i directions in the tetragonal phase.16 EC is
observed to decrease with increasing BNH content, indicating that the domain switching becomes easier and easier.
This is attributed to the decrease in the c/a ratio of the tetragonal phase and the smaller lattice distortion in the rhombohedral phase. With a similar c/a ratio near the MPB to the

J. Appl. Phys. 112, 114120 (2012)

FIG. 1. P(E) hysteresis loops at room temperature of (1x)Bi(Ni1/2Hf1/2)O3-x

PbTiO3 for x 0.64, 0.62, 0.60, and 0.58.

BiMeO3-PbTiO3 systems, 0.38BNH-0.62PT has a EC of

2.1 kV/mm (Fig. 1), which is comparable to that of
0.36BiScO3-0.64PbTiO3 (2.0 kV/mm),2 and lower than any
other BiMeO3-PbTiO3 systems, such as the reported
0.51Bi(Ni1/2Ti1/2)O3-0.49PbTiO3 (3.8 kV/mm),14 0.4Bi(Sc3/4
Ga1/4)O3-0.6PbTiO3 (3.9 kV/mm),17 and 0.63Bi(Mg1/2Ti1/2)
O3-0.37PbTiO3 (5.0 kV/mm).8 Actually, a low EC makes the
BNH-PT system poling much easier.
The electric field induced unipolar strain curves measured at electric field of 5 kV/mm for the BNH-PT are shown
in Fig. 2(a). The strain is found first to increase and then
decrease through the transformation of tetragonal to rhombohedral, and reaches the maximum value at the MPB

FIG. 2. (a) Unipolar S(E) curves at room temperature, and (b) piezoelectric
coefficient d33 of (1x)Bi(Ni1/2Hf1/2)O3-xPbTiO3 for x 0.64, 0.62, 0.60,
and 0.58.

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114120-3

Pan et al.

(x 0.62). While for compositions with higher content of

rhombohedral phrase, 0.42BNH-0.58PT, the strain suddenly
increases even larger than that of 0.38BNH-0.62PT at the
MPB. For ferroelectric materials, the strain response is produced by two separate contributions, an extrinsic contribution due to ferroelectric non-180 domain switching and an
intrinsic contribution due to the lattice distortion.18 Due to
the strain hysteresis under unipolar cycling, strain shows significant differences between materials on the tetragonal and
rhombohedral side of the MPB. For the 0.36BNH-0.64PT
content, strain increases more than proportional to the electric field, resulting in upward bending S-E curves. Compositions in the tetragonal side of the MPB exhibit an increase of
the increment in strain with electric field up to approximate
2.5 kV/mm, and the strain increment decreases for higher
fields, thus presenting an S-shaped S-E curve. For higher
rhombohedral phase content, i.e., 0.40BNH-0.60PT, the
increase in strain is less than proportional to the increase in
electric field. The corresponding S-E curve increases but
bends downward with increasing electric field.19 This supports the previous assumption that the large lattice distortion
is responsible for the limited contribution from domain
switching, since the lattice distortion is smaller in the rhombohedral phase in the BNH-PT. A reduced lattice distortion
then prompts increased levels of domain switching and
increased hysteresis of unipolar strain, thus the 0.42BNH0.58PT content produced a larger strain level, which suggests that the extrinsic contribution to the electric field
induced strain plays a key role in enhancing the total strain
level in the rhombohedral side.
It is well known that proper sintering temperature plays
a crucial role in piezoelectric properties. The best sintering
temperature for the BNH-PT system is between 1180 and
1210  C for reaching the maximum value of small-signal d33,
such as the MPB at x 0.62 has d33 446 pC/N. Figure 2(b)
presents the small and large-signal d33 values measured at
room temperature. The large-signal d33 (Smax/Emax) could be
obtained, where the maximum strain (Smax) is achieved
under the maximum polarization electric field (Emax). The
large-signal d33 is about 10%30% larger than the smallsignal d33 for the compositions of x 0.60, 0.62, and 0.64,
which can be compared to Bi(Mg1/2Ti1/2)O3-PbTiO3, where
the value is about 20%40%.4 It is interesting to observe that
the small-signal d33 (446 pC/N) of BNH-PT is comparable to
BiScO3-PbTiO3 (460 pC/N), and larger than the other
BiMeO3-PbTiO3 systems, such as Bi(Mg1/2 Ti1/2)O3-PbTiO3
(225 pC/N) and Bi(Ni1/2Ti1/2)O3-PbTiO3 (260 pC/N).4,14
Obviously, the BNH-PT system has a superior piezoelectric
performance.
In order to determine the TC, temperature dependence
of dielectric data was performed at 1 MHz on the unpoled
BNH-PT ceramics (Fig. 3). The TC of BNH-PT decreases
with increasing BNH content. The TC in the MPB region
is around 290  C, and lower than that of PbTiO3
(TC 490  C).20 It is common sense that the TC of tetragonal
ABO3 family perovskites is generally correlated to the c/a
ratio.5 This could be explained as follows. High c/a ratio,
meaning large distorted lattice symmetry, requires high temperature to remove the crystalline distortion. For example,

J. Appl. Phys. 112, 114120 (2012)

FIG. 3. Dielectric constant (er) and dielectric loss (tand) as a function of

temperature at 1 MHz.

piezoelectric ceramics of 0.63Bi(Mg1/2Ti1/2)O3-0.37PbTiO3

(c/a 1.034), 0.36BiScO3-0.64PbTiO3 (c/a 1.023), 0.38Bi
(Mg3/4W1/4)O3-0.62PbTiO3 (c/a 1.002) in the MPB region,
respectively, produced TC of 478  C, 450  C, 220  C.2,4,9
This is consistent with the mentioned before. In the present
study, the c/a ratio of BNH-PT near the MPB (c/a 1.01)15
is much lower than previous mentioned analogous compositions, thus it exhibits a relatively lower TC.
Additionally, it is obvious to see that the peak height
decreases and the width increases, respectively (Fig. 3). It is
very interesting to observe a relaxor phase transformation
rather than a normal ferroelectric behavior according to the
frequency dependence of dielectric measurement. The maximum dielectric constant is corresponding temperature with
the increase of the frequency to the higher temperature direction.15 It has been reported that in the mixed B-site cation
family, the relaxor behavior in ferroelectric materials is
resulted from the local heterogeneity due to the presence of
different ions possessing fluctuating valence states at the B
site.21 A modified Curie-Weiss law can be used to account
for the degree of diffuseness in peaks at a constant
frequence22
1
1
T  Tm c
;


C
er er; max
where er,max is the maximum value of the dielectric constant
er at the transition temperature Tm, C is a constant, and c
(1  c  2) is the diffuse exponent. Generally, c 1 corresponds to a normal ferroelectric while c 2 to an ideal
relaxor ferroelectric. The plots of ln(1/er  1/er,max) versus
ln(T  Tm) of 0.38BNH-0.62PT exhibit a highly linear relation with an ultrahigh relaxor degree of 1.72 at 1 MHz.15 It is
significantly higher than the other reported Bi-based systems,
such as BiMnO3-PbTiO3,23 BiScO3-PbTiO3,24 and the Codoped in BiScO3-PbTiO3 piezoelectric ceramics.25 The
above suggest that the BNH-PT can be a potential electronic
ceramic material for its strong relaxor feature.
Piezoelectric materials, which can tolerate high temperature, usually have a wide application, so the temperature dependence electric-field induced unipolar strain investigation
is essential. Temperature dependence of large-signal d33 is
presented in Fig. 4. All three compositions show a rapid

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114120-4

Pan et al.

J. Appl. Phys. 112, 114120 (2012)

in University (NCET-11-0573), and Fok Ying Tung Education Foundation (131047).

1

FIG. 4. Temperature dependence of large-signal d33 of (1x)Bi(Ni1/2Hf1/2)

O3-xPbTiO3 with x 0.64, 0.62, and 0.60.

growth in the large-signal d33. The piezoelectric behavior of

0.38BNH-0.62PT exhibits a large-signal d33 as high as
1000 pm/V at 175  C. It is two times of 0.37Bi(Mg1/2Ti1/2)
O3-0.63PbTiO3 whose MPB composition has a large-signal
d33 of 500 pm/V at 175  C.4 All above indicate that the
BNH-PT system is a new promising composition for the
application of piezoelectric devices.
IV. CONCLUSION

A new perovskite structure solid-solution system based

on (1x)Bi(Ni1/2Hf1/2)O3-xPbTiO3 has been investigated. A
relatively low c/a ratio of 1.01 is observed in the MPB
(x 0.62) with a TC of 290  C. High piezoelectric coefficient
(d33 446 pC/N) is obtained, which is comparable to
BiScO3-PbTiO3 (d33 460 pC/N). Present system of BNHPT also exhibits a strong relaxor feature, and has a large
strain response. The BNH-PT is a promising piezoelectric
material for future application.
ACKNOWLEDGMENTS

This work was supported by National Natural Science

Foundation of China (Grant Nos. 91022016, 21031005, and
21231001), the Fundamental Research Funds for the Central
Universities, China (FRF-TP-09-004B), the Foundation for
the Author of National Excellent Doctoral Dissertation of PR
China (201039), Program for New Century Excellent Talents

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