Professional Documents
Culture Documents
, 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
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
(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.
110
111
200
210
110
4.0CuO BF-BKT system, the A-site ions, K+ and Bi3+, are both
Internsity (arb. unit)
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
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
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
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