J. Am. Ceram. Soc.
, 1–7 (2014)
Journal
Effects of CuO Addition on Electrical Properties of 0.6BiFeO3–0.4(Bi0.5K0.5)TiO3
Lead-Free Piezoelectric Ceramics
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku,
0.6BiFeO3–0.4(Bi0.5K0.5)TiO3 (0.6BF–0.4BKT) ceramic sam-
ples with 0.0–4.0 mol% CuO were prepared by the solid-state
reaction. The CuO addition aided the densification of the
samples and slightly increased the lattice constant. The relax-
or-like defuse dielectric peak of 0.6BF–0.4BKT became shar-
per with increasing the CuO content. Polarization–electric field
curve of the undoped 0.6BF–0.4BKT was a pinched loop in the
as-sintered state, while that was a square hysteresis with a
large remanent polarization of 48 lC/cm2 after the thermal
quenching, demonstrating a strong domain wall pinning due to
defect dipoles. We found that the CuO addition up to 2.0 mol
% facilitates the polarization switching in the as-sintered sam-
ples to increase the remanent polarization and the piezoelectric
d33 coefficient. The results of the structural and electrical inves-
tigations suggested that the copper ion acts as a donor in
0.6BF–0.4BKT by compensating the potassium vacancy created
by the evaporation of K2O during the calcination and sintering
processes.
I. Introduction
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-
tors, resonators, and sensors for over half a century.1 How-
ever, the PZT-based ceramics necessarily contains a large
amount of the toxic Pb element more than 60 wt%, and thus
it has been required to develop alternative lead-reduced or
lead-free piezoelectric ceramics.
One useful guideline for the development of new lead-free
piezoelectric ceramics is seeking the materials with a large
remanent polarization (Pr) and a high dielectric permittivity
(er) because the thermodynamic theory tells us that the piezo-
electric d coefficient is proportional to Pr and er: d =
2e0erQPr, where Q is the electrostrictive coefficient, which is
only weakly dependent on the composition in perovskite-type
materials,2 and e0 is the dielectric permittivity of vacuum.
From this point of view, BiFeO3 (BF), a ferroelectric with a
high ferroelectric–paraelectric phase transition temperature
around 825°C, has attracted increasing attention due to its
strong ferroelectricity. The large values of Pr of BF have
been observed in its thin film (146 lC/cm2),3 single crystal
(60 lC/cm2),4 and ceramics (40 lC/cm2).5 However, the
reported values of the piezoelectric d33 coefficient of BF are
relatively low (15–60 pC/N),5–8 which can be attributed to its
low er less than 100.8 For this reason, solid-solution ceramics
including BF as an end-member, such as BF–PbTiO39 and
D. D. Viehland—contributing editor
Manuscript No. 35055. Received May 26, 2014; approved September 20, 2014.
*Member, The American Ceramic Society.
†
Author to whom correspondence should be addressed. e-mail: hagiwara@applc.
keio.ac.jp
1
DOI: 10.1111/jace.13287
© 2014 The American Ceramic Society
Manabu Hagiwara† and Shinobu Fujihara*
Yokohama 223-8522, Japan
BF–BaTiO310 systems, have been extensively studied so as to
improve dielectric and piezoelectric properties by realizing a
morphotropic phase boundary (MPB).
Recently, some researchers have focused on the
BF–(Bi0.5K0.5)TiO3 (BF-BKT) solid solutions and investi-
gated their ferroelectric and piezoelectric properties.11–15
Matsuo et al. prepared the BF-BKT ceramics with various
compositions by the flash creation method (FCM) and
obtained a large Pr (52 lC/cm2), a superior piezoelectric d33
coefficient (130 pC/N), and a high phase transition tempera-
ture around 450°C at a composition of 0.6BF–0.4BKT.11
The FCM is a technique to prepare metal-oxide nanopow-
ders, in which vaporized raw materials are introduced into a
plasma-induced high-temperature region and then cooled
rapidly to crystalize without the grain growth; this method
realizes a lower concentration of defects in the resulting pow-
der as well as a lower sintering temperature compared to the
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-
electric switching and its Pr and d33 were very small (~10 lC/
cm2 and ~40 pC/N, respectively) even under high electric
field amplitudes.13,15 This suggests that the ferroelectric and
piezoelectric properties of the 0.6BF–0.4BKT ceramics are
highly process dependent, and the control of the defect con-
centration is of great importance to obtain the superior prop-
erties of this ceramics. One possible way to control defect
concentration is the chemical modification using a small
amount of an oxide additive. However, to the best of
authors’ knowledge, there is no study investigating the dopant
effect in the BF-BKT system.
CuO is one of the most widely used additives for piezo-
electric ceramics, and many reports have shown that the
CuO addition can significantly lower the sintering tempera-
ture of both lead-based and lead-free piezoelectric ceram-
ics.17–20 On the other hand, the influence of the CuO additive
on the ferroelectric and piezoelectric properties depends
sensitively on the composition of host ceramics because the
Cu2+ ion has the intermediate ionic radius between A- and
B-site ions in a common perovskite ABO3 lattice. For exam-
ple, in PZT-based ceramics, the Cu2+ ion substitutes for the
B-site Ti4+ ion as an acceptor to make the ceramics
“harder”.18 Li et al. have suggested that the Cu2+ ion added
into (K0.5Na0.5)NbO3 (KNN)-based ceramics is firstly incor-
porated into the A site as a donor when the CuO amount is
less than 0.1 wt%, while it replaces the B-site ion as an
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-
ples with several different amounts of the CuO additive and
investigated their sintering behavior and electric properties.
II. Experimental Procedure
Undoped and CuO-doped 0.6BF–0.4BKT ceramic samples
were prepared by the conventional solid-state route using
2 Journal of the American Ceramic Society—Hagiwara and Fujihara
reagent-grade powders: TiO2 (99.9%, Toho Titanium Co.,
Ltd., Kanagawa, Japan), KHCO3 (99.5%, Wako Pure Chemi-
cal Industries, Ltd., Osaka, Japan), Bi2O3 (99.9%, Kojundo
Chemical Laboratory Co., Ltd, Saitama, Japan), and Fe2O3
(99.9%, Toda Kogyo Corp., Hiroshima, Japan). KHCO3 was
used instead of K2CO3 to minimize the impact of the moisture
absorption on the composition of the samples.22 The raw pow-
ders were weighted according to the stoichiometric formula
and ball-milled using ethanol and yttria-stabilized zirconia
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-
nation step with an intermediate milling cycle was performed
to achieve better homogeneity of the final powder. After the
second calcination, the resulting powder was divided into five
batches and CuO powder (99.5%, Wako Pure Chemical Indus-
tries, Ltd.) was added to each batch in the amount of 0.0, 0.5,
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
for the initial milling step. The powders were then mixed with
3 wt% of an organic binder (polyvinyl acetate) and uniaxially
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-
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
was observed by a scanning electron microscope (SEM;
JSM-7600F, JEOL, Tokyo, Japan). Phase determination for
the sintered pellets was performed using a X-ray diffractome-
ter (XRD; D8-02 diffractometer, Bruker AXS, Yokohama,
Japan) with Cu Ka radiation. For electrical characterization,
the sintered pellets were ground to the thickness of
0.4–0.5 mm, electroded with Ag-conductive paste, and fired
at 800°C for 10 min in air. Temperature dependence of
dielectric permittivity and dielectric loss of the samples were
measured in a temperature range from room temperature to
600°C using a LCR meter (ZM2371, NF Corp., Yokohama,
Japan) in combination with a tube furnace. Frequency
dependence of the dielectric permittivity and dielectric loss at
room temperature were also measured using the LCR meter.
Polarization (P) versus electric field (E) hysteresis measure-
ments were performed at room temperature using a ferroelec-
tric test system (Precision LC, Radiant Technologies,
Albuquerque, NM). The samples were poled in silicon oil at
room temperature under DC electric field of 80 kV/cm for
10 min. The low-field piezoelectric d33 coefficient of the poled
samples was measured 24 h after poling using a d33 meter
(ZJ-4B, IACAS, Beijing, China). To investigate the influence
of ferroelectric domain wall pinning, thermal quenching
experiments were also carried out: the electroded samples
were annealed at 800°C for 10 min and then immediately
immersed into water (20°C), and P–E hysteresis and d33 of the
thermally quenched samples were measured.
III. Results and Discussion
Figure 1 shows density of the 0.6BF–0.4BKT ceramics with
the CuO additive of 0.0–4.0 mol% as a function of the
sintering temperature. It can be seen that the CuO addition
promotes the densification of the 0.6BF–0.4BKT ceramics.
This effect is obvious in the early stage of sintering at the
low temperatures below 860°C, but a change in the final tem-
perature necessary for achieving >95% of theoretical density
(Ts) is not so large: Ts remains constant at 940°C for the
samples with CuO up to 1.0 mol%, and is lowered to 920°C
for 2.0 mol% and to 880°C for 4.0 mol%. Thus, it is sug-
gested that the mechanism by which the CuO lowers the sin-
tering temperature in 0.6BF–0.4BKT ceramics differs from
that in other ceramics such as PZT based,17,18 (Bi0.5Na0.5)
TiO3-based,19 and (K0.5Na0.5)NbO3-based20 one, in which the
CuO addition results in the significant decrease in the sinter-
ing temperature more than 100°C through the formation of
100
95
90
Relative density/%
85
80
4.0 mol%
75
2.0 mol%
70 1.0 mol%
0.5 mol%
65 0.0 mol%
60
800 840 880 920 960
Temperature/°C
Fig. 1. Density as a function of the sintering temperature for the
0.6BF–0.4BKT ceramics with 0.0–4.0 mol% CuO.
liquid phases. Based on the above results, we denote a
0.6BF–0.4BKT ceramic sample doped with x mol% CuO
and sintered at T°C as xCuO-T in this study. And we discuss
structural and electrical properties of the following five sam-
ples with different CuO contents: 0.0CuO-940, 0.5CuO-940,
1.0CuO-940, 2.0CuO-960, and 4.0CuO-880, which are the
samples sintered at the respective Ts.
Scanning electron micrographs of fracture surfaces of the
above-mentioned five samples are presented in Fig. 2. All the
samples are well densified, without significant residual poros-
ity. From the low magnification SEM images, obvious sign
of the formation of a liquid phase, as reported in Refs. [17,
18], cannot be seen in all the samples. Combined with the
densification curve, it is considered that the externally added
CuO forms a transient liquid phase to aid the densification
in the early stage of the sintering and then incorporates into
the grains. For the samples with 0.0–2.0 mol% CuO, the
grain size is ~ 0.5–1.0 lm, irrespective of the CuO content.
On the other hand, 4.0CuO-880 has smaller grains. This is
considered to be due to the lower sintering temperature for
4.0CuO-880, rather than the suppression of the grain growth
by the CuO. Thus, it can be stated that the CuO addition
into BF-BKT ceramics does not make a large impact on the
grain growth, whereas it slightly aids the densification.
Figure 3(a) shows XRD patterns of crushed powders from
the undoped and CuO-doped 0.6BF–0.4BKT ceramics. All of
the peaks can be indexed to the single phase of the pseudocu-
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
the samples have the pseudocubic symmetry. The pseudocu-
bic phase for the undoped 0.6BF–0.4BKT is consistent with
the result of XRD analysis in the previous report.11 More-
over, the transmission electron microscopy observation per-
formed by Ozaki et al. has shown that the pseudocubic
phase of the 0.6BF–0.4BKT ceramics is composed of nonpo-
lar cubic regions and rhombohedrally distorted polar nanod-
omains with a size of 10 nm.23 Our XRD and SEM
investigations imply that the CuO additive up to 4.0 mol%
forms no secondary phase and is mostly incorporated into
the perovskite lattice. Thus, we determined the pseudocubic
lattice constant apc as a function of the CuO content using
the Si powder as an internal standard for the XRD patterns
[Fig. 3(d)]. On the introduction of CuO, apc slightly increases
from 3.9619 A
for 0.0CuO-940 to 3.9638 A
for 4.0CuO-880.
In what follows, we discuss possible mechanisms for the
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
0.6
0.4
0.2
0 roles in the establishment of the long-range polar ordering.
0 100 200 300
Temperautre, T/°C
Fig. 4. Temperature dependence of (a) dielectric permittivity and
(b) dielectric loss tangent for the 0.6BF–0.4BKT ceramics with
0.0–4.0 mol% CuO measured at 100 kHz.
value around 200°C, it then increases rapidly in the higher
temperature region. The increase in tand at the higher tem-
peratures is mainly because of electrical conduction of the
samples, and it is most obvious for 4.0CuO-880. Thus, the
4.0Cu-880 sample is expected to have a poorer electrical
resistivity than the other samples.
For ferroelectrics including relaxors, the temperature (T)
dependence of er’ above the ferroelectric–paraelectric phase
transition temperature is phenomenologically described by
the following equation:27
e0m
e0r ¼ ; (3)
1 þ fðT  Tm Þ=Dgn
and D decreases with an increase in the CuO content.
Therefore, it is found that the CuO addition into the 0.6BF–
0.4BKT ceramics sharpens the phase transition.
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
for PZT-based ferroelectrics that A-site (Pb2+) ions rather
than B-site ions in the perovskite structure play important
400 500 600 For example, the PZT-based ceramics with a higher content
of the A-site vacancy has been reported to exhibit a broader
phase transition and a smaller em0 .26,29 In the present case,
the temperature dependence of er0 for the undoped 0.6BF–
0.4BKT ceramics (0.0CuO-940) was broadest among all the
samples. It should also be noted that the undoped 0.6BF–
0.4BKT ceramics synthesized using the FCM shows much
sharper phase transition and larger em0 .11 This implies that
the solid-state-synthesized 0.6BF–0.4BKT ceramics includes a
large amount of the A-site vacancy, which is probably due to
the evaporation of K2O and/or Bi2O3 [Eqs. (1) and (2)].
Moreover, the decrease in D by the CuO addition suggests
that the Cu2+ ions compensate the A-site vacancies (V000 Bi or
V0K ) to make the polar ordering longer. This explanation
corresponds to the scenarios (2) and (3) which have been
discussed from the XRD observation.
Figure 5 shows the frequency dependence of er0 and tand
for 0.0CuO-940 and 2.0CuO-920 at room temperature. Both
the samples show the relaxor-like strong dielectric dispersion,
which can be attributed to the dielectric response of the

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
decreases er0 ; 740 for 0.0CuO-940 and 680 for 2.0CuO-920 at
1 kHz. This result also indicates that the CuO addition leads
to the longer polar ordering (i.e., larger nanodomains) in
0.6BF–0.4BKT because smaller nanodomains can make the
net dielectric response larger.
To investigate the influence of the CuO addition on the
ferroelectric property of the 0.6BF–0.4BKT ceramics, the
P–E hysteresis measurement was conducted for the as-
sintered and thermally quenched samples (Fig. 6). We could
not obtain the P–E hysteresis data for 4.0CuO-880 because
the electrical breakdown occurred when a high voltage was
applied to the sample. With respect to the undoped 0.6BF–
0.4BKT (0.0CuO-940), the as-sintered sample exhibits a
pinched loop and only a relatively small Pr of 9 lC/cm2
is obtained in spite of the large applied-electric field of
90 kV/cm. On the other hand, when the sample is quenched
from 800°C, a well-opened P–E loop is obtained. In the
perovskite structure, the oxygen vacancy is usually the most
mobile defect because of the relatively short distance between
adjacent oxygen sites in the oxygen octahedron. The mobile
and positively charged oxygen vacancy may bind to nega-
tively charged defect, such as an acceptor dopant or an
A-site vacancy, to form defect dipole. When ferroelectric
ceramics is slowly cooled from a high temperature above the
phase transition temperature to a lower temperature and
accordingly ferroelectric domain structure is developed, the
defect dipoles align with the polarization vector, resulting in
the stabilization of the domain structures and the pinning
of domain walls.30 On the other hand, if the ceramics
are rapidly cooled from temperatures above the transition
temperature, a freezing of the disordered state of the defects
can be achieved, which may release the domain walls. There-
fore, the results of the P–E hysteresis measurement for the
0.0CuO-940 ceramics explicitly demonstrate the existence of
a considerable amount of the oxygen vacancy in the 0.0CuO-
940 sample. Here, it should be emphasized that the Pr value
of the quenched 0.0CuO-940 sample reaches to 48 lC/cm2,
which is in agreement with the result reported by Matsuo
et al.11 The large Pr in the 0.6BF–0.4BKT ceramics could be
attributed to the strong ferroelectricity of BF and implies the
superior piezoelectric activity of this ceramics.
In Fig. 5, it is also found that P–E loops of the as-sintered
samples gradually become opened with the increasing
amount of the CuO additive, whereas the CuO addition has
little influence on the shape of the loops of the quenched
samples. The 2.0CuO-920 sample exhibited the highest Pr
value of 27 lC/cm2 among the as-sintered samples. This
clearly indicates that the CuO addition decreases the concen-
tration of the oxygen vacancy, that is, the Cu2+ ion acts as a
donor in the 0.6BF–0.4BKT ceramics. Thus, we conclude
that the scenario (3), in which the Cu2+ ions compensate the
potassium vacancies, is most reasonable as the mechanism
for the incorporation of CuO into the 0.6BF–0.4BKT ceram-
ics. It should be stated that the P–E hysteresis measurements
were also conducted for the samples with Au-sputtered elec-
trodes in this study, and they provided the same results with
the samples with Ag electrodes. This indicates that the incor-
poration of Ag+ ions into the samples does not occur in the
condition of this study.
From the above-discussed results of XRD, the er0 -T curve,
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
Piezoelectric coefficient, d33/pC·N-1
120
Quenched
90
As-sintered
60
30
0 0.5 1.0 1.5
CuO content/mol%
Fig. 7. CuO content dependence of the piezoelectric d33 coefficient
in the 0.6BF–0.4BKT ceramics.
electric properties of the 0.6BF–0.4BKT ceramics can be
explained as follows:
1. In the undoped 0.6BF–0.4BKT ceramics, potassium
vacancies (V0K ) and oxygen vacancies (VO ) are formed
by the evaporation of K2O [Eq. (1)], resulting in the
shrinking of the crystal lattice, the broad phase transi-
tion, and the pinning of domain walls.
2. When CuO is added externally, the Cu2+ ion compen-
sates V0K to reduce the concentration of both V0K and
V
O as follows:


CuO þ V0K þ V
O ! CuK þ OO
3. The reduced concentration of V0K aids the evolution of
long-range ferroelectric polar ordering, resulting in the
sharper phase transition in the CuO-doped samples,
while the reduction of the VO concentration leads to
the depinning of the nanodomains.
The piezoelectric d33 coefficient of the as-sintered and ther-
mally quenched samples measured with the d33 meter is plot-
ted as a function of CuO content in Fig. 7. The quenched
samples exhibit higher d33 values around 130 pC/N. This
value is well consistent with the value previously reported in
Ref. [11], where the effective d*33 of the 06BF–0.4BKT
ceramics was estimated from the initial slope (<10 kV/cm) of
the electric-filed-induced strain curve. With respect to the as-
sintered samples, the d33 value monotonically increases as the
CuO content increases and reaches 82 pC/N at 2.0 mol%,
which can be attributed to the increase in Pr by the CuO
addition.
As shown for the quenched samples, the 0.6BF–0.4BKT
ceramics possesses the large Pr and the superior piezoelec-
tric property as well as the high transition temperature
exceeding 400°C, which make it a good candidate for a
new trend of lead-free piezoelectric ceramics. Although
complete ferroelectric switching in the as-sintered ceramics
has not been achieved by the CuO doping, we believe that
this work opens up the possibility of improving the
electrical properties of the BF-BKT system by the chemical
modification.
IV. Conclusions
The 0.6BF–0.4BKT ceramics with varying amounts of the
CuO additive up to 4.0 mol% were prepared by the conven-
tional solid-state method. The sintering temperature
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
CuO-doped ceramics were composed of a single phase of the
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–
paraelectric phase transition. P–E hysteresis measurements
for the as-sintered and thermally quenched samples demon-
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
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.
From these results, we concluded that the Cu2+ ion
2.0 compensates the potassium vacancy, which is caused by the
evaporation of K2O, and acts as a donor to decrease the
concentrations of potassium and oxygen vacancies.
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
in carrying out the experiments. This work was supported by a Grant-in-Aid
for Research Activity Start-up (No. 25889049) from the Japan Society for the
Promotion of Science (JSPS).
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