Large strain under a low electric field in lead-free bismuth-based

piezoelectrics
Aman Ullah, Chang Won Ahn, Amir Ullah, and Ill Won Kim

Citation: Appl. Phys. Lett. 103, 022906 (2013); doi: 10.1063/1.4813420

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 APPLIED PHYSICS LETTERS 103, 022906 (2013)

Large strain under a low electric field in lead-free bismuth-based

piezoelectrics
Aman Ullah,1,2 Chang Won Ahn,1 Amir Ullah,1 and Ill Won Kim1,a)
1
Department of Physics and EHSRC, University of Ulsan, Ulsan 680-749, South Korea
2
Department of Physics, University of Science and Technology, Bannu, Khyber Pakhtunkhwa, Pakistan
(Received 22 April 2013; accepted 24 June 2013; published online 10 July 2013)
In this letter, the composition and electric field dependent strain behavior of (1  x)Bi0.5
(Na0.78K0.22)0.5TiO3-xBi(Mg0.5Ti0.5)O3 (BNKT-BMT) were investigated to develop lead-free
piezoelectric materials with a large strain response at a low driving field for actuator applications.
A large strain of 0.35% (Smax/Emax ¼ 636 pm/V) at an applied field of 55 kV/cm was obtained with
a composition of 4 mol. % BMT. In particular, the electric field required to deliver large strains was
reduced to a level that revealed not only a large Smax/Emax of 542 pm/V at a driving field as low as
35 kV/cm, but also remarkably suppressed the large hysteresis. V C 2013 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4813420]

Lead-based piezoelectric ceramics such as Pb(Zr,Ti)O3
(PZT) possess a large strain response at a low applied field
and have dominated the piezoelectric actuators market.1,2
However, based on lead oxide toxicity and growing demands
for global environmental protection, worldwide research has
been focused on the development of lead-free piezoelectric
ceramics with a large strain response that can eventually
replace lead-based ceramics in actuator applications.
In recent years, the predominantly investigated systems
to obtain a giant electric field induced strain for actuator appli-
cations are Bi0.5Na0.5TiO3 (BNT)-based solid solutions.3–17
For example, Zhang et al. published results of BNT-BaTiO3-
K0.5Na0.5NbO3 (BNT-BT-KNN) ternary solid solutions with a
large normalized strain, Smax/Emax, of 560 pm/V.3,4 Since
then, Seifert et al. introduced Bi0.5K0.5TiO3 in place of BT in
the BNT-BKT-KNN system and reported a large Smax/Emax of
600 pm/V.5 The BNT-BKT-KNN system was also investi-
gated by Sing et al., who observed a similar large strain.6
Lee and his coworkers found significant enhancements of
the strain response by doping Y and Nb on Ti sites in
Bi0.5(Na0.82K0.18)0.5TiO3 (BNKT) ceramics.7,8 The effect of
Zr and Hf substitutions on BNKT ceramics was investigated
by Hussain et al., who reported Smax/Emax values of 614 and
475 pm/V, respectively.9,10 Bai et al. observed high Smax/Emax
of 448 pm/V in BNT- Ba(Al0.5Ta0.5)O3 ceramics attributed to
the degradation of remnant polarization, piezoelectric con-
stant, and coercive field.13 Based on the literature, such a large
strain is possible only in materials with a nearly nonpolar
phase at a zero field and can be evolved into a long-range fer-
roelectric phase upon application of an electric field.3–12 A
comprehensive review on this topic is available.1 It should be
noted that in these developed systems, the required electric
field for phase transition to achieve a large strain is as high as
70–80 kV/cm, which is about two times greater than strain
saturations in soft PZT and may limit their use in practical
applications.4,11 Recently, we reduced the applied field to
60 kV/cm and observed a large strain in BiAlO3-modified
a)
Author to whom correspondence should be addressed. Electronic mail:
kimiw@mail.ulsan.ac.kr
BNKT (BNKT-BA) ceramics.12 To further reduce the applied
field, Lee et al. proposed a method in which BNT single par-
ticles were added to BNKT-BA ceramics, resulting in a high
strain of 0.29% at a low applied field of 40 kV/cm.11 Wang
et al. also reported large Smax/Emax of 600 pm/V at a relatively
low applied field of 60 kV/cm by adding 5 mol. % of SrTiO3
in BNT-BKT solid solution.14
All of these studies demonstrate that the choice of start-
ing material and the selection of chemical modifier play an
important role in reducing the applied field and achieving a
large strain. The present study provides a guideline for the
choice of the base composition as well as the chemical modi-
fier involving the field-induced phase transition.
In this respect, the solid solution of tetragonal Bi0.5
(Na0.78K0.22)0.5TiO3 (BNKT) was selected as the base
composition, and new bismuth-based (1  x)BNKT-xBi
(Mg0.5Ti0.5)O3 was investigated from the viewpoint of the
field-induced phase transition. To determine the suitability
of the material for actuator applications, the strain behavior
as a function of the electric field was evaluated. A large
Smax/Emax of 542 pm/V even at a very low electric field of
35 kV/cm was observed. This study provides an important
result of obtaining a large strain response at a low driving
field.
Bismuth-based (1  x)Bi0.5(Na0.78K0.22)0.5TiO3-xBi
(Mg0.5Ti0.5)O3 piezoelectric ceramics were prepared by the
conventional solid state reaction method using Bi2O3, TiO2
(99.9%, High Purity Chemicals), MgO (99.5%, Cerac
Specialty Inorganics), Na2CO3 (99.9%, Cerac Specialty
Inorganics), and K2CO3 (99%, Sigma-Aldrich) as raw
materials. The starting materials were added according to
the composition of the ceramics. After being ball-milled for
24 h in ethanol, the calcination of the dried slurries was car-
ried out at 800  C for 2 h followed by ball milling again for
24 h. After drying, the powders were pressed into disk sam-
ples with diameters of 13 mm using polyvinyl alcohol
(PVA) as a binder. The compressed disks were sintered at
1150–1170  C for 2 h. The crystalline structure of the sam-
ples was determined using X-ray diffraction (XRD, X’pert
PRO MRD, Philips). Silver paste was coated on both

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V

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022906-2 Ullah et al.
FIG. 1. X-ray diffraction patterns of (1  x)BNKT-xBMT ceramics
(x ¼ 0–0.100) in the 2h ranges from (a) 20 –60 and (b) 35 –50 .
surfaces of the specimens and then fired at 700  C to form
electrodes for the electrical property measurements.
Dielectric permittivity and loss of poled (4 kV/mm, 100  C
for 20 min, field-cooled) samples were measured using an
impedance analyzer (HP4192A). The hysteresis loops of
the samples were measured using a Sawyer-Tower circuit.
The electric field-induced strain was measured using a lin-
ear variable differential transducer (LVDT, Mitutoyo
MCH-331 & M401).
Figure 1(a) shows the XRD patterns of (1  x)BNKT-
xBi(Mg0.5Ti0.5)O3 (BMT) (x ¼ 0–0.100) in the 2h range of
20 -60 . All of the samples have a perovskite phase without
any other impurity phases, consistent with other reports of
BNT-BKT ceramics.9,10,12,17 To examine the effect of the
addition of BMT on BNKT, detailed XRD scans for the
ceramics in the 2h range from 35 to 50 are shown in Fig.
1(b). The samples with x  0.050 exhibited obvious splitting
of (002)/(200) peaks at 2h of around 46 , characteristic of tet-
ragonal symmetry. However, at high BMT concentration
(x  0.060), the (002)/(200) peaks of tetragonal phase merged
into a single (200) peak suggesting that the crystal structure of
the BNKT-BMT ceramics evolves from the tetragonal to a
pseudocubic symmetry.7,8,12,17
To investigate the suitability of BNKT-BMT ceramics
for actuator applications, the unipolar strains of samples
measured under a relatively low applied field of 55 kV/cm
are shown in Fig. 2(a). All of the BMT substituted samples
showed a high strain compared to the unmodified BNKT
ceramics. In particular, the sample with x ¼ 0.040 had a large
strain of 0.35%. A similar large strain has been reported in
other BNT-based ceramics. However, the applied field for
strain saturation was 70 kV/cm.3–10,13,15 The normalized
strains (Smax/Emax) derived from the unipolar strain data for
each composition are presented in Fig. 2(b). At a critical
composition, x ¼ 0.040, a large Smax/Emax of 636 pm/V was
obtained at 55 kV/cm. However, the Smax/Emax value drasti-
cally decreased to 181 pm/V as the BMT content was
increased to 0.100.
To examine the field-induced phase transition and to
understand the origin of this observed large strain, the
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Appl. Phys. Lett. 103, 022906 (2013)
FIG. 2. (a) Unipolar strain curves of BNKT-BMT with different BMT con-
tents and the (b) Smax/Emax of the BNKT-BMT ceramics as a function of the
BMT content.
bipolar strain loops and polarization hysteresis loops of
BNKT-BMT samples measured at an electric field of
55 kV/cm are provided in Figs. 3(a) and 3(b), respectively.
At the critical composition (4 mol. % BMT), similar to the
unipolar strain, a large strain of 0.35% was obtained.
Instead, a pronounced reduction of the negative strain from
0.14% for BNKT without BMT to 0.03% was observed.
Consistent with the bipolar strain loops, the polarization hys-
teresis loop also showed a dramatic change as a function of
the BMT concentration, as shown in Fig. 3(b). The polariza-
tion hysteresis loop of the base composition, BNKT with
x ¼ 0, strongly resembles the behavior of a typical ferroelec-
tric with a large remanent polarization and maximum polar-
ization of 22 lC/cm2 and 32 lC/cm2, respectively, along
with a coercive field of 30 kV/cm. Interestingly, like the
bipolar data, a drastic decrease of the remanent polarization
(9 lC/cm2) and coercive field (10 kV/cm) was noticed at the
critical composition without affecting the maximum polar-
ization (33 lC/cm2) resulted in a pinch hysteresis loop. It
implies that the dominant ferroelectric order in BNKT is dis-
turbed with the addition of BMT, leaving a “weak” ferro-
electric phase with a very small non-cubic distortion or a
“nonpolar” phase at zero electric field that transforms rever-
sibly into a ferroelectric phase by an applied field.12,14,15,17
The compositionally induced transformation from ferroelec-
tric to weakly polar is also confirmed from bipolar strain
loops, as presented in Fig. 3(a).
The degradation in polarization values, as well as in the
negative strain became more severe for all subsequent compo-
sitions and the bipolar strain loop as well as the polarization
022906-3 Ullah et al.
FIG. 3. (a) Bipolar strain curves and (b) polarization hysteresis loops of
BNKT-BMT with different BMT contents.
hysteresis loop revealed a clear deviation from that of typical
ferroelectric materials (x ¼ 0).
Based on the above findings, the massive reductions of
the negative strain and remanent polarization together with
the noticeable pinched polarization hysteresis loop and large
strain at a BMT content of 4 mol. % were suggested to origi-
nate from the coexistence of the ferroelectric and nonpolar
phases induced by the BMT substitution. The coexistence of
different polarization states at the critical composition may
indicate that the free energy of the ferroelectric phase seems
so comparable to that of the non-polar phase at zero fields
and the non-polar phase at a zero field can easily transform
into a long-range ferroelectric phase upon the application of
an electric field, resulting in a large strain response.5–9,12–15,17
However, when the BMT concentration was increased to
x ¼ 0.100, the pseudocubic non-polar phase dominates,
resulting in the delay transformation of non-polar to ferro-
electric phase, which is evident by the drastic reduction in the
maximum polarization.5,12,15,17
Temperature-dependent dielectric constant and loss of
(1  x)BNKT-xBMT ceramics (x ¼ 0, 0.040, and 0.100)
measured at different frequencies are displayed in Fig. 4.
Two inflection points, at 154  C and 278  C, were
observed for the sample with x ¼ 0 corresponding to depolari-
zation temperature (Td) and maximum dielectric constant
temperature (Tmax), respectively. Several features are noticed:
The first inflection point (Td) decreases from 154  C to 66  C
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Appl. Phys. Lett. 103, 022906 (2013)
FIG. 4. Dielectric constants and loss tangent of (1  x)BNKT-xBMT (x ¼ 0,
0.040, and 0.100) ceramics as a function of temperature and frequency.
as BMT increased from 0 to 0.040. However, at higher BMT
concentration (x ¼ 0.100), no distinctive Td is observed,
which implies that Td lies below room temperature.6,12,17 The
downward shift of Td with increasing BMT content is consid-
ered to be closely related to the less pronounced non-cubic
distortion (Fig. 1) and also in good agreement with the results
from strain as well as polarization hysteresis measurements
(Fig. 3).14,17 Moreover, with increasing BMT content, the
transitions at both inflection points became increasingly dif-
fuse, and the maximum dielectric constant decreased indicat-
ing compositionally induced ferroelectric to diffused phase
transition.
To optimize the material for actuator applications, it is
necessary to study the strain response of a material at different
electric fields. As discussed in Fig. 2(b), the highest Smax/Emax
of 636 pm/V was obtained with x ¼ 0.040 at an electric field
of 55 kV/cm. Therefore, the unipolar strain of the critical
composition, x ¼ 0.040, was measured under different applied
fields ranging from 35 kV/cm to 55 kV/cm, as depicted in Fig.
5. As shown in Fig. 5, when the applied field was reduced to a
level as low as 35 kV/cm, Smax/Emax decreased to 542 pm/V,
which is comparable to other lead-free BNT-based materials,
FIG. 5. Unipolar strain curves of BNKT-BMT with x ¼ 0.040 at different
applied fields.
022906-4 Ullah et al. Appl. Phys. Lett. 103, 022906 (2013)

1
in which Smax/Emax values greater than 500 pm/V were J. Rodel, W. Jo, K. T. P. Seifert, E.-M. Anton, T. Granzow, and D.
obtained at driving applied fields 70 kV/cm.6–11,13,15 Damjanovic, J. Am. Ceram. Soc. 92, 1153 (2009).
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strain at a driving field as low as 35 kV/cm. The achievable Phys. Lett. 91, 112906 (2007).
4
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(2008).
tuator applications. 5
K. T. P. Seifert, W. Jo, and J. Rodel, J. Am. Ceram. Soc. 93, 1392
In conclusion, the strain response of a lead-free BNKT- (2010).
6
BMT ceramic system induced by an applied electric field A. Singh and R. Chatterjee, J. Appl. Phys. 109, 024105 (2011).
7
ranging from 35 to 55 kV/cm was investigated. A large Smax/ D. N. Binh, A. Hussain, J. S. Lee, and W. P. Tai, J. Korean Phys. Soc. 57,
892 (2010).
Emax of 636 pm/V at 55 kV/cm was obtained with a BMT 8
K. N. Pham, H.-S. Han, J. K. Kang, and J. S. Lee, J. Korean Phys. Soc. 60,
content of 4 mol. %. The critical composition, x ¼ 0.040, 207 (2012).
9
maintained not only a large Smax/Emax of 542 pm/V even at a A. Hussain, C. W. Ahn, J. S. Lee, and I. W. Kim, Sens. Actuators, A 158,
very low driving field of 35 kV/cm, but also notably sup- 84 (2010).
10
A. Hussain, C. W. Ahn, J. S. Lee, and I. W. Kim, Jpn. J. Appl. Phys., Part
pressed the hysteresis, indicating that the developed material 1 49, 041504 (2010).
is highly promising for actuator applications. 11
D. S. Lee, M. S. Kim, K. H. Kim, and S. J. Jeong, Appl. Phys. Lett. 99,
062906 (2011).
This research was supported by Basic Science Research 12
A. Ullah, C. W. Ahn, and I. W. Kim, Curr. Appl. Phys. 10, 1367 (2010).
13
Program through the National Research Foundation of W. Bai, Y. Bian, J. Hao, B. Shen, and J. Zhai, J. Am. Ceram. Soc. 96, 246
Korea (NRF) funded by the Ministry of Education (2013).
14
K. Wang, A. Hussain, W. Jo, and J. Rodel, J. Am. Ceram. Soc. 95, 2241
(2012R1A1A2005922). This work was supported by Priority (2012).
Research Centers Program through the National Research 15
W. Jo, T. Granzow, E. Aulbach, J. Rodel, and D. Damjanovic, J. Appl.
Foundation of Korea (NRF) funded by the Ministry of Phys. 105, 094102 (2009).
16
Education (2009-0093818). This work (2011-0016790) was E. A. Patterson, D. P. Cann, J. Pokorny, and I. M. Reaney, J. Appl. Phys.
111, 094105 (2012).
supported by Mid-career Researcher Program through NRF 17
A. Ullah, C. W. Ahn, A. Hussain, and I. W. Kim, J. Am. Ceram. Soc. 94,
grant funded by the MEST. 3915 (2011).

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