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J. Am. Ceram. Soc.

, 1–7 (2014)
DOI: 10.1111/jace.13287
© 2014 The American Ceramic Society

Journal
Effects of CuO Addition on Electrical Properties of 0.6BiFeO3–0.4(Bi0.5K0.5)TiO3
Lead-Free Piezoelectric Ceramics
Manabu Hagiwara† and Shinobu Fujihara*
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku,
Yokohama 223-8522, Japan

0.6BiFeO3–0.4(Bi0.5K0.5)TiO3 (0.6BF–0.4BKT) ceramic sam- BF–BaTiO310 systems, have been extensively studied so as to
ples with 0.0–4.0 mol% CuO were prepared by the solid-state improve dielectric and piezoelectric properties by realizing a
reaction. The CuO addition aided the densification of the morphotropic phase boundary (MPB).
samples and slightly increased the lattice constant. The relax- Recently, some researchers have focused on the
or-like defuse dielectric peak of 0.6BF–0.4BKT became shar- BF–(Bi0.5K0.5)TiO3 (BF-BKT) solid solutions and investi-
per with increasing the CuO content. Polarization–electric field gated their ferroelectric and piezoelectric properties.11–15
curve of the undoped 0.6BF–0.4BKT was a pinched loop in the Matsuo et al. prepared the BF-BKT ceramics with various
as-sintered state, while that was a square hysteresis with a compositions by the flash creation method (FCM) and
large remanent polarization of 48 lC/cm2 after the thermal obtained a large Pr (52 lC/cm2), a superior piezoelectric d33
quenching, demonstrating a strong domain wall pinning due to coefficient (130 pC/N), and a high phase transition tempera-
defect dipoles. We found that the CuO addition up to 2.0 mol ture around 450°C at a composition of 0.6BF–0.4BKT.11
% facilitates the polarization switching in the as-sintered sam- The FCM is a technique to prepare metal-oxide nanopow-
ples to increase the remanent polarization and the piezoelectric ders, in which vaporized raw materials are introduced into a
d33 coefficient. The results of the structural and electrical inves- plasma-induced high-temperature region and then cooled
tigations suggested that the copper ion acts as a donor in rapidly to crystalize without the grain growth; this method
0.6BF–0.4BKT by compensating the potassium vacancy created realizes a lower concentration of defects in the resulting pow-
by the evaporation of K2O during the calcination and sintering der as well as a lower sintering temperature compared to the
processes. conventional solid-state method.16 In fact, according to the
other reports, the 0.6BF–0.4BKT ceramics prepared by the
conventional solid-state reaction did not show obvious ferro-
I. Introduction
electric switching and its Pr and d33 were very small (~10 lC/
cm2 and ~40 pC/N, respectively) even under high electric
S INCE its discovery in 1952, lead zirconate titanate [Pb
(ZrxTi1–x)O3; PZT] has been the mainstay for a wide
variety of piezoelectric ceramic applications including actua-
field amplitudes.13,15 This suggests that the ferroelectric and
piezoelectric properties of the 0.6BF–0.4BKT ceramics are
tors, resonators, and sensors for over half a century.1 How- highly process dependent, and the control of the defect con-
ever, the PZT-based ceramics necessarily contains a large centration is of great importance to obtain the superior prop-
amount of the toxic Pb element more than 60 wt%, and thus erties of this ceramics. One possible way to control defect
it has been required to develop alternative lead-reduced or concentration is the chemical modification using a small
lead-free piezoelectric ceramics. amount of an oxide additive. However, to the best of
One useful guideline for the development of new lead-free authors’ knowledge, there is no study investigating the dopant
piezoelectric ceramics is seeking the materials with a large effect in the BF-BKT system.
remanent polarization (Pr) and a high dielectric permittivity CuO is one of the most widely used additives for piezo-
(er) because the thermodynamic theory tells us that the piezo- electric ceramics, and many reports have shown that the
electric d coefficient is proportional to Pr and er: d = CuO addition can significantly lower the sintering tempera-
2e0erQPr, where Q is the electrostrictive coefficient, which is ture of both lead-based and lead-free piezoelectric ceram-
only weakly dependent on the composition in perovskite-type ics.17–20 On the other hand, the influence of the CuO additive
materials,2 and e0 is the dielectric permittivity of vacuum. on the ferroelectric and piezoelectric properties depends
From this point of view, BiFeO3 (BF), a ferroelectric with a sensitively on the composition of host ceramics because the
high ferroelectric–paraelectric phase transition temperature Cu2+ ion has the intermediate ionic radius between A- and
around 825°C, has attracted increasing attention due to its B-site ions in a common perovskite ABO3 lattice. For exam-
strong ferroelectricity. The large values of Pr of BF have ple, in PZT-based ceramics, the Cu2+ ion substitutes for the
been observed in its thin film (146 lC/cm2),3 single crystal B-site Ti4+ ion as an acceptor to make the ceramics
(60 lC/cm2),4 and ceramics (40 lC/cm2).5 However, the “harder”.18 Li et al. have suggested that the Cu2+ ion added
reported values of the piezoelectric d33 coefficient of BF are into (K0.5Na0.5)NbO3 (KNN)-based ceramics is firstly incor-
relatively low (15–60 pC/N),5–8 which can be attributed to its porated into the A site as a donor when the CuO amount is
low er less than 100.8 For this reason, solid-solution ceramics less than 0.1 wt%, while it replaces the B-site ion as an
including BF as an end-member, such as BF–PbTiO39 and acceptor when the CuO amount exceeds 0.1 wt%.21 In this
study, to clarify the role of the Cu2+ ion in the 0.6BF–
0.4BKT ceramics, we prepared 0.6BF–0.4BKT ceramic sam-
D. D. Viehland—contributing editor
ples with several different amounts of the CuO additive and
investigated their sintering behavior and electric properties.

Manuscript No. 35055. Received May 26, 2014; approved September 20, 2014.
II. Experimental Procedure
*Member, The American Ceramic Society.

Author to whom correspondence should be addressed. e-mail: hagiwara@applc. Undoped and CuO-doped 0.6BF–0.4BKT ceramic samples
keio.ac.jp were prepared by the conventional solid-state route using
1
2 Journal of the American Ceramic Society—Hagiwara and Fujihara

reagent-grade powders: TiO2 (99.9%, Toho Titanium Co., 100


Ltd., Kanagawa, Japan), KHCO3 (99.5%, Wako Pure Chemi-
cal Industries, Ltd., Osaka, Japan), Bi2O3 (99.9%, Kojundo 95
Chemical Laboratory Co., Ltd, Saitama, Japan), and Fe2O3
(99.9%, Toda Kogyo Corp., Hiroshima, Japan). KHCO3 was 90
used instead of K2CO3 to minimize the impact of the moisture

Relative density/%
absorption on the composition of the samples.22 The raw pow- 85
ders were weighted according to the stoichiometric formula
and ball-milled using ethanol and yttria-stabilized zirconia 80
balls for 24 h. The powder mixture was then dried and cal-
cined in an alumina crucible at 760°C for 2 h. A second calci- 4.0 mol%
75
nation step with an intermediate milling cycle was performed 2.0 mol%
to achieve better homogeneity of the final powder. After the
70 1.0 mol%
second calcination, the resulting powder was divided into five
batches and CuO powder (99.5%, Wako Pure Chemical Indus- 0.5 mol%
tries, Ltd.) was added to each batch in the amount of 0.0, 0.5, 65 0.0 mol%
1.0, 2.0, and 4.0 mol%. The powders doped with each amount
of CuO were ball-milled again with the same conditions used 60
for the initial milling step. The powders were then mixed with 800 840 880 920 960
3 wt% of an organic binder (polyvinyl acetate) and uniaxially Temperature/°C
pressed at 200 MPa into disks of 1 cm2 in area. The binder
was burnout by a heat treatment at 600°C for 1 h. Green pel- Fig. 1. Density as a function of the sintering temperature for the
0.6BF–0.4BKT ceramics with 0.0–4.0 mol% CuO.
lets were immerged in the calcined powder of the undoped
0.6BF–0.4BKT and sintered in air at various temperatures
from 800°C to 940°C for 4 h.
Microstructure of fracture surface of the sintered pellets liquid phases. Based on the above results, we denote a
was observed by a scanning electron microscope (SEM; 0.6BF–0.4BKT ceramic sample doped with x mol% CuO
JSM-7600F, JEOL, Tokyo, Japan). Phase determination for and sintered at T°C as xCuO-T in this study. And we discuss
the sintered pellets was performed using a X-ray diffractome- structural and electrical properties of the following five sam-
ter (XRD; D8-02 diffractometer, Bruker AXS, Yokohama, ples with different CuO contents: 0.0CuO-940, 0.5CuO-940,
Japan) with Cu Ka radiation. For electrical characterization, 1.0CuO-940, 2.0CuO-960, and 4.0CuO-880, which are the
the sintered pellets were ground to the thickness of samples sintered at the respective Ts.
0.4–0.5 mm, electroded with Ag-conductive paste, and fired Scanning electron micrographs of fracture surfaces of the
at 800°C for 10 min in air. Temperature dependence of above-mentioned five samples are presented in Fig. 2. All the
dielectric permittivity and dielectric loss of the samples were samples are well densified, without significant residual poros-
measured in a temperature range from room temperature to ity. From the low magnification SEM images, obvious sign
600°C using a LCR meter (ZM2371, NF Corp., Yokohama, of the formation of a liquid phase, as reported in Refs. [17,
Japan) in combination with a tube furnace. Frequency 18], cannot be seen in all the samples. Combined with the
dependence of the dielectric permittivity and dielectric loss at densification curve, it is considered that the externally added
room temperature were also measured using the LCR meter. CuO forms a transient liquid phase to aid the densification
Polarization (P) versus electric field (E) hysteresis measure- in the early stage of the sintering and then incorporates into
ments were performed at room temperature using a ferroelec- the grains. For the samples with 0.0–2.0 mol% CuO, the
tric test system (Precision LC, Radiant Technologies, grain size is ~ 0.5–1.0 lm, irrespective of the CuO content.
Albuquerque, NM). The samples were poled in silicon oil at On the other hand, 4.0CuO-880 has smaller grains. This is
room temperature under DC electric field of 80 kV/cm for considered to be due to the lower sintering temperature for
10 min. The low-field piezoelectric d33 coefficient of the poled 4.0CuO-880, rather than the suppression of the grain growth
samples was measured 24 h after poling using a d33 meter by the CuO. Thus, it can be stated that the CuO addition
(ZJ-4B, IACAS, Beijing, China). To investigate the influence into BF-BKT ceramics does not make a large impact on the
of ferroelectric domain wall pinning, thermal quenching grain growth, whereas it slightly aids the densification.
experiments were also carried out: the electroded samples Figure 3(a) shows XRD patterns of crushed powders from
were annealed at 800°C for 10 min and then immediately the undoped and CuO-doped 0.6BF–0.4BKT ceramics. All of
immersed into water (20°C), and P–E hysteresis and d33 of the the peaks can be indexed to the single phase of the pseudocu-
thermally quenched samples were measured. bic perovskite structure. As shown in Figs. 3(b) and (c), no
split of both 111 and 200 peaks is observed for all the sam-
ples regardless of the CuO content, demonstrating that all
III. Results and Discussion
the samples have the pseudocubic symmetry. The pseudocu-
Figure 1 shows density of the 0.6BF–0.4BKT ceramics with bic phase for the undoped 0.6BF–0.4BKT is consistent with
the CuO additive of 0.0–4.0 mol% as a function of the the result of XRD analysis in the previous report.11 More-
sintering temperature. It can be seen that the CuO addition over, the transmission electron microscopy observation per-
promotes the densification of the 0.6BF–0.4BKT ceramics. formed by Ozaki et al. has shown that the pseudocubic
This effect is obvious in the early stage of sintering at the phase of the 0.6BF–0.4BKT ceramics is composed of nonpo-
low temperatures below 860°C, but a change in the final tem- lar cubic regions and rhombohedrally distorted polar nanod-
perature necessary for achieving >95% of theoretical density omains with a size of 10 nm.23 Our XRD and SEM
(Ts) is not so large: Ts remains constant at 940°C for the investigations imply that the CuO additive up to 4.0 mol%
samples with CuO up to 1.0 mol%, and is lowered to 920°C forms no secondary phase and is mostly incorporated into
for 2.0 mol% and to 880°C for 4.0 mol%. Thus, it is sug- the perovskite lattice. Thus, we determined the pseudocubic
gested that the mechanism by which the CuO lowers the sin- lattice constant apc as a function of the CuO content using
tering temperature in 0.6BF–0.4BKT ceramics differs from the Si powder as an internal standard for the XRD patterns
that in other ceramics such as PZT based,17,18 (Bi0.5Na0.5) [Fig. 3(d)]. On the introduction of CuO, apc slightly increases
TiO3-based,19 and (K0.5Na0.5)NbO3-based20 one, in which the from 3.9619 A  for 0.0CuO-940 to 3.9638 A  for 4.0CuO-880.
CuO addition results in the significant decrease in the sinter- In what follows, we discuss possible mechanisms for the
ing temperature more than 100°C through the formation of increase in apc with increasing the amount of CuO.
CuO-Added 0.6BF-0.4BKT Ceramics 3

(a) (b) (c)

(d) (e)

Fig. 2. SEM images of fracture surface of the 0.6BF–0.4BKT ceramics with 0.0–4.0 mol% CuO: (a) 0.0CuO-940; (b) 0.5CuO-940; (c) 1.0CuO-
940; (d) 2.0CuO-920; (e) 4.0CuO-880.

ion replaces the B-site ions. However, the situation becomes


(a) *CuKβ (b) (c)
more complicated when the host ceramics contains a consid-
erable amount of vacancies because the existence of the
100

110

111

200

210

110

vacancies also may affect the lattice constant. In the present


Log Internsity (arb. unit)

4.0CuO BF-BKT system, the A-site ions, K+ and Bi3+, are both
Internsity (arb. unit)

* volatile and thus A-site and oxygen vacancies can be easily


generated as follows during the calcination and sintering
2.0CuO processes:
*

1.0CuO 2K 0 
K þ OO ! K2 O " þ2VK þ VO (1)
*
0.5CuO 2Bi  000 
Bi þ 3OO ! Bi2 O3 " þ2VBi þ 3VO (2)
*
0.0CuO Note that we use the Kr€ oger–Vink notation of defects in this
* study. In fact, the formation of A-site and oxygen vacancies
due to the volatility of the A-site ion has been reported for
both BF and BKT ceramics.8,25 On the other hand, B-site
20 30 40 50 60 39.0 39.6 45.4 46.0 vacancies are considered to be hardly formed in the BF-BKT
2θ/° 2θ/° ceramics. It is known that the formation of the A-site vacan-
cies and/or oxygen vacancies results in a decrease in the lat-
3.965 tice constant.26 Thus, it is reasonable to assume that a
(d) considerable amount of A-site vacancies is formed in the
solid-state-synthesized BF-BKT ceramics, resulting in the
Lattice constant, apc/Å

3.964 shrinkage of the crystal lattice. In this case, when the Cu2+
ion compensates the A-site vacancy, the lattice constant is
expected to increase. Considering the ionic radii and the
formation of A-site vacancies in the BF-BKT ceramics, the
3.963 following three scenarios are given as a possible reason of
the lattice expansion with the increasing amount of the CuO
additive: (1) substitution of the B-site ion (Fe3+ or Ti4+) by
3.962 the Cu2+ ion; (2) compensation of the Bi3+ vacancy by the
Cu2+ ion; (3) compensation of the K+ vacancy by the Cu2+
ion. Here, it should be noted that Cu2+ acts as an acceptor
in the scenario (1) and (2), while Cu2+ acts as a donor in the
3.961 scenario (3).
0.0 1.0 2.0 3.0 4.0 Figure 4 shows temperature dependence of the real part of
dielectric permittivity (er’) and dielectric loss tangent (tand)
CuO content/mol% measured at 100 kHz for the samples 0.0Cu-940, 0.5Cu-940,
Fig. 3. (a) XRD patterns of the 0.6BF–0.4BKT ceramics with 0.0– 1.0Cu-940, 2.0Cu-920, and 4.0Cu-880. All the samples show
4.0 mol% CuO, magnified images of (b) 111 and (c) 200 diffraction the relaxor-like diffuse peak of er’ with maximum values at
peaks, and (d) CuO content dependence of the lattice constant. around 430°C. We observed that the temperature of maxi-
mum permittivity (Tm) decreased with decreasing the measur-
ing frequency for all the samples, which is also a typical
 is smaller than
The ionic radius of the Cu2+ ion (0.73 A) feature of relaxors. Such relaxor-like phase transition behav-
 K+: 1.64 A)
the A-site ions (Bi3+: 1.03 A,  and larger than ior is consistent with the previous reports on the undoped
 Ti4+: 0.605 A).
the B-site ions (Fe3+: 0.55 A,  24 Thus, the 0.6BF–0.4BKT ceramics.11,15 With respect to tand, all the
lattice constant should decrease when the Cu2+ ion replaces samples exhibits common tendency: tand firstly decreases
the A-site ions, whereas it should increase when the Cu2+ with increasing temperature and represents a minimal
4 Journal of the American Ceramic Society—Hagiwara and Fujihara

10000 Table I. Phase Transition Parameters for the Undoped and


(a) 4.0CuO-880 CuO-Doped 0.6BF-0.4BKT Ceramics
2.0CuO-920 0
8000 1.0CuO-940 Sample em Tm/°C ξ D/○C
Permittivity, εr'

0.5CuO-940
0.0CuO-940 0.0Cu-940 4227 445 2.06 244
6000 0.5Cu-940 4729 442 2.02 239
1.0Cu-940 6221 435 2.04 186
4000 2.0Cu-920 7669 430 1.97 178
4.0Cu-880 (6893) (427) – –
2000

interfaces). The MW effect is commonly observed in the


0
0 100 200 300 400 500 600 materials with a poor electrical resistivity, and is also
reported for the BF-BKT system.28 In Table I, it is clear that
Temperature, T/°C the parameter ξ, which describes the character of the phase
1.0
transition, is very close to 2 for all the samples. This suggests
that there is no interaction between the polar nanodomains
(b) 4.0CuO-880
2.0CuO-920
in the 0.6BF–0.4BKT ceramics regardless of the additional
0.8 1.0CuO-940
content of CuO. On the other hand, values of em0 and D lar-
Dielectric loss, tanδ

0.5CuO-940 gely depend on the CuO content: em0 drastically increases


0.0CuO-940 and D decreases with an increase in the CuO content.
0.6
Therefore, it is found that the CuO addition into the 0.6BF–
0.4BKT ceramics sharpens the phase transition.
0.4 The origin of the DPT behavior of relaxor ferroelectrics
has been associated with a delay in the evolution of long-
range polar ordering during cooling.29 Moreover, it is known
0.2 for PZT-based ferroelectrics that A-site (Pb2+) ions rather
than B-site ions in the perovskite structure play important
0 roles in the establishment of the long-range polar ordering.
0 100 200 300 400 500 600 For example, the PZT-based ceramics with a higher content
Temperautre, T/°C of the A-site vacancy has been reported to exhibit a broader
phase transition and a smaller em0 .26,29 In the present case,
Fig. 4. Temperature dependence of (a) dielectric permittivity and the temperature dependence of er0 for the undoped 0.6BF–
(b) dielectric loss tangent for the 0.6BF–0.4BKT ceramics with 0.4BKT ceramics (0.0CuO-940) was broadest among all the
0.0–4.0 mol% CuO measured at 100 kHz. samples. It should also be noted that the undoped 0.6BF–
0.4BKT ceramics synthesized using the FCM shows much
value around 200°C, it then increases rapidly in the higher sharper phase transition and larger em0 .11 This implies that
temperature region. The increase in tand at the higher tem- the solid-state-synthesized 0.6BF–0.4BKT ceramics includes a
peratures is mainly because of electrical conduction of the large amount of the A-site vacancy, which is probably due to
samples, and it is most obvious for 4.0CuO-880. Thus, the the evaporation of K2O and/or Bi2O3 [Eqs. (1) and (2)].
4.0Cu-880 sample is expected to have a poorer electrical Moreover, the decrease in D by the CuO addition suggests
resistivity than the other samples. that the Cu2+ ions compensate the A-site vacancies (V000 Bi or
For ferroelectrics including relaxors, the temperature (T) V0K ) to make the polar ordering longer. This explanation
dependence of er’ above the ferroelectric–paraelectric phase corresponds to the scenarios (2) and (3) which have been
transition temperature is phenomenologically described by discussed from the XRD observation.
the following equation:27 Figure 5 shows the frequency dependence of er0 and tand
for 0.0CuO-940 and 2.0CuO-920 at room temperature. Both
e0m the samples show the relaxor-like strong dielectric dispersion,
e0r ¼ ; (3) which can be attributed to the dielectric response of the
1 þ fðT  Tm Þ=Dgn

where em0 is the maximum of the dielectric permittivity at a


given frequency, D is the diffuseness parameter related to the 1000 0.20
peak broadening of the phase transition, and ξ is the param- 0.0CuO-940
eter representing the character of the phase transition. ξ = 1 2.0CuO-920
corresponds to a normal ferroelectric transition, while ξ = 2 800
0.15
indicates a so-called complete diffuse phase transition (DPT).
Dielectric loss, tan δ

In DPT ferroelectrics, there is no interaction between the fer-


r
Permittivity, ε

600
roelectric polar regions. On the other hand, ξ between 1 and
2 corresponds to incomplete DPT, where the interaction 0.10
between the polar regions should be considered. The parame- 400
ters D and ξ can be estimated, respectively, from slope and
intercept of log(er0 /em0 –1) vs. log(T–Tm) plot. The parameters 0.05
ξ and D estimated from the plot as well as em0 and Tm are 200
summarized in Table I. For 4.0Cu-880, there was a large
mismatch between the experimental observation and the
0 2 0.0
phenomenological theory, so that ξ and D could not be 10
3
10 10
4
10
5

obtained. This mismatch is ascribed to the apparent permit-


Frequency, f/Hz
tivity arising from the Maxwell–Wagner (MW) effect, in
which the space charge concentrates at a boundary between Fig. 5. Frequency dependence of dielectric permittivity and
two phases with different relaxation times (i.e., electrode dielectric loss tangent for 0.0CuO-940 and 2.0CuO-920.
CuO-Added 0.6BF-0.4BKT Ceramics 5

nanodomains. Moreover, it is obvious that the CuO addition temperature, a freezing of the disordered state of the defects
decreases er0 ; 740 for 0.0CuO-940 and 680 for 2.0CuO-920 at can be achieved, which may release the domain walls. There-
1 kHz. This result also indicates that the CuO addition leads fore, the results of the P–E hysteresis measurement for the
to the longer polar ordering (i.e., larger nanodomains) in 0.0CuO-940 ceramics explicitly demonstrate the existence of
0.6BF–0.4BKT because smaller nanodomains can make the a considerable amount of the oxygen vacancy in the 0.0CuO-
net dielectric response larger. 940 sample. Here, it should be emphasized that the Pr value
To investigate the influence of the CuO addition on the of the quenched 0.0CuO-940 sample reaches to 48 lC/cm2,
ferroelectric property of the 0.6BF–0.4BKT ceramics, the which is in agreement with the result reported by Matsuo
P–E hysteresis measurement was conducted for the as- et al.11 The large Pr in the 0.6BF–0.4BKT ceramics could be
sintered and thermally quenched samples (Fig. 6). We could attributed to the strong ferroelectricity of BF and implies the
not obtain the P–E hysteresis data for 4.0CuO-880 because superior piezoelectric activity of this ceramics.
the electrical breakdown occurred when a high voltage was In Fig. 5, it is also found that P–E loops of the as-sintered
applied to the sample. With respect to the undoped 0.6BF– samples gradually become opened with the increasing
0.4BKT (0.0CuO-940), the as-sintered sample exhibits a amount of the CuO additive, whereas the CuO addition has
pinched loop and only a relatively small Pr of 9 lC/cm2 little influence on the shape of the loops of the quenched
is obtained in spite of the large applied-electric field of samples. The 2.0CuO-920 sample exhibited the highest Pr
90 kV/cm. On the other hand, when the sample is quenched value of 27 lC/cm2 among the as-sintered samples. This
from 800°C, a well-opened P–E loop is obtained. In the clearly indicates that the CuO addition decreases the concen-
perovskite structure, the oxygen vacancy is usually the most tration of the oxygen vacancy, that is, the Cu2+ ion acts as a
mobile defect because of the relatively short distance between donor in the 0.6BF–0.4BKT ceramics. Thus, we conclude
adjacent oxygen sites in the oxygen octahedron. The mobile that the scenario (3), in which the Cu2+ ions compensate the
and positively charged oxygen vacancy may bind to nega- potassium vacancies, is most reasonable as the mechanism
tively charged defect, such as an acceptor dopant or an for the incorporation of CuO into the 0.6BF–0.4BKT ceram-
A-site vacancy, to form defect dipole. When ferroelectric ics. It should be stated that the P–E hysteresis measurements
ceramics is slowly cooled from a high temperature above the were also conducted for the samples with Au-sputtered elec-
phase transition temperature to a lower temperature and trodes in this study, and they provided the same results with
accordingly ferroelectric domain structure is developed, the the samples with Ag electrodes. This indicates that the incor-
defect dipoles align with the polarization vector, resulting in poration of Ag+ ions into the samples does not occur in the
the stabilization of the domain structures and the pinning condition of this study.
of domain walls.30 On the other hand, if the ceramics From the above-discussed results of XRD, the er0 -T curve,
are rapidly cooled from temperatures above the transition and the P–E hysteresis, the effect of the CuO addition on the

100 100
(a) (b)
Polarization/μC·cm -2
Polarization/μC·cm -2

50 50

0 0

-50 -50
As-sintered As-sintered
Quenched Quenched
-100 -100
-100 -50 0 50 100 -100 -50 0 50 100
Electric field/kV·cm -1 Electric field/kV·cm -1

100 100
(c) (d)
Polarization/μC·cm -2

Polarization/μC·cm -2

50 50

0 0

-50 -50
As-sintered As-sintered
Quenched Quenched
-100 -100
-100 -50 0 50 100 -100 -50 0 50 100
Electric field/kV·cm -1 Electric field/kV·cm -1
Fig. 6. P–E hysteresis loops of the as-sintered and quenched 0.6BF–0.4BKT ceramics with 0.0–2.0 mol% CuO measured at 1 Hz: (a) 0.0CuO-
940; (b) 0.5CuO-940; (c) 1.0CuO-940; (d) 2.0CuO-920.
6 Journal of the American Ceramic Society—Hagiwara and Fujihara

150 necessary for achieving >95% of the theoretical density was


slightly decreased with increasing the CuO content. The
XRD measurement revealed that all the undoped and
Piezoelectric coefficient, d33/pC·N-1

CuO-doped ceramics were composed of a single phase of the


120 pseudocubic perovskite structure and the pseudocubic lattice
constant was increased by the CuO addition. It was found
that the CuO addition resulted in the sharper ferroelectric–
Quenched paraelectric phase transition. P–E hysteresis measurements
90 for the as-sintered and thermally quenched samples demon-
As-sintered strated that 0.6BF–0.4BKT has a strong ferroelectricity to
show a large Pr of 48 lC/cm but its polarization switching is
strongly prohibited due to the formation of defect dipoles in
60 the as-sintered state. The CuO addition was effective for the
depinning of the domains, and consequently the sample with
2.0 mol% CuO exhibited the largest Pr of 24 lC/cm2 and
the highest d33 of 82 pC/N among the as-sintered samples.
30 From these results, we concluded that the Cu2+ ion
0 0.5 1.0 1.5 2.0 compensates the potassium vacancy, which is caused by the
CuO content/mol% evaporation of K2O, and acts as a donor to decrease the
concentrations of potassium and oxygen vacancies.
Fig. 7. CuO content dependence of the piezoelectric d33 coefficient
in the 0.6BF–0.4BKT ceramics.
Acknowledgments
The authors would like to thank Dr. Takaaki Tsurumi, Dr. Hiroaki Takeda,
and Dr. Takuya Hoshina in Tokyo Institute of Technology for their assistance
electric properties of the 0.6BF–0.4BKT ceramics can be in carrying out the experiments. This work was supported by a Grant-in-Aid
explained as follows: for Research Activity Start-up (No. 25889049) from the Japan Society for the
Promotion of Science (JSPS).
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