Front. Mater. Sci.

2012, 6(4): 311–318

DOI 10.1007/s11706-012-0186-0

RESEARCH ARTICLE

BiCoO3-doped (K0.475Na0.475Li0.05)(Nb0.8Ta0.2)O3
lead-free piezoelectric ceramics

Ke-Pi CHEN (✉) and Zhe ZHANG

School of Energy, Power and Mechanical Engineering, North China Electric Power University, Beijing 102206, China

© Higher Education Press and Springer-Verlag Berlin Heidelberg 2012

ABSTRACT: (1–x)(K0.475Na0.475Li0.05)(Nb0.8Ta0.2)O3–xBiCoO3 (KNLNT–BC) lead-free

piezoelectric ceramics were prepared by the conventional solid-state sintering method.
Effects of the BC content on the phase structure, microstructure and electrical properties
of KNLNT–BC ceramics were investigated. XRD patterns reveal that all the ceramic
samples are in the pure perovskite-type structure, and the phase structure changes from
the tetragonal to pseudo-cubic phase with the increase of the BC content. After the
substitution of BC, the grain size is significantly reduced and relaxer behaviors are
induced. By adding a small amount of BC to KNLNT ceramics, piezoelectric properties are
improved, while further addition of BC makes the piezoelectric properties deteriorate
markedly. The optimized electrical properties at x = 0.005 are as follows: d33 = 194 pC/N, kp
= 0.44.

KEYWORDS: lead-free ceramic, potassium sodium niobate, BiCoO3, piezoelectric

property

1 Introduction past decade. Among the various possible choices, most

Piezoelectric ceramics play a technologically important
role in the field of sensors, transducers and actuators, which
have been widely used in ultrasonic medical imaging,
micromotors, energy harvesting devices, magnetoelectric
sensors, and high power transformers [1–3]. Owing to their
outstanding piezoelectric properties, lead-based piezo-
electric ceramics such as Pb(Zr, Ti)O3 (PZT), Pb(Mg1/3-
Nb2/3)O3–PbTiO3 (PMN–PT) and Pb(Zn1/3Nb2/3)O3–
PbTiO3 (PZN–PT) have been dominating the defense and
civilian applications in the past few decades [4–5].
However, because of the toxicity of lead oxide and the
requirement of environmental protection, lead-free piezo-
electric ceramics have received much attention over the
Received September 28, 2012; accepted October 25, 2012
E-mail: ckp@ncepu.edu.cn
widely investigated lead-free systems are (K0.5Na0.5)NbO3
(KNN), (Na0.5Bi0.5)TiO3 (NBT) and BaTiO3 (BT) based
materials [6–9].
In recent years, KNN is considered as a leading lead-free
candidate because of its high Curie temperature and good
piezoelectric properties. However, it is very difficult to
obtain dense KNN ceramics due to the high volatility of
alkaline elements and difficult in controlling the quantity of
the liquid phase at high temperatures. To improve
densification and piezoelectric properties of KNN cera-
mics, various additions are added into KNN to form new
KNN-based ceramics, such as KNN–LiNbO3 [10–12],
KNN–LiTaO3 [13–15], KNN–BaTiO3 [16–17], KNN–
SrTiO3 [18–19], KNN–CaTiO3 [20–21], KNN–LiSbO3
[22–24], KNN–(Bi0.5Na0.5)TiO3 [25] and KNN–LiTaO3–
LiSbO3 [26–30].
BiCoO3 (BC) is a new lead-free multiferric compound,
312 Front. Mater. Sci. 2012, 6(4): 311–318
which possess the PbTiO3-type structure and magnetic ions
[31]. The tetragonality of BC (c/a = 1.27) is much larger
than that of PbTiO3 (c/a = 1.06), which suggests very large
spontaneous polarization. First principle Berry-phase
calculations predicted that its electric polarization reach
179 μC/cm2, the largest calculated point-charge polariza-
tion of any Pb- or Bi-based perovskite reported previously
[32]. Recently, it was shown that the addition of BC is of
great value to improve the piezoelectric properties of KNN
ceramics. The improvement in electrical properties of
KNN–BC ceramics is induced by shifting the rhombohe-
dral to orthorhombic phase transition around room
temperature [33]. However, there are no systematic
investigations on the solid solution between tetragonal
structure (K, Na, Li)(Nb, Ta)O3 and BC ceramics till now.
In the present work, a small amount of BC was used to
partially substitute (K0.475Na0.475Li0.05)(Nb0.8Ta0.2)O3
(KNLNT) with tetragonal structure. The influence of BC
addition on phase transitions and electrical properties of
KNLNT ceramics was investigated.
2 Experimental
(1 – x)KNLNT–xBC (x = 0, 0.005, 0.010, 0.015, 0.020,
0.025, 0.030, 0.035) ceramics were prepared by the
conventional mixed oxide method. Analytical-grade
metal oxide or carbonate powders of Nb2O5 (99.5%),
K2CO3 (99%), Na2CO3 (99.8%), Li2CO3 (99%), Bi2O3
(99%) and Co2O3 (99.5%) were used as starting materials.
After being dried at 180°C for 12 h, the starting powders
were weighed according to the stoichiometric formula and
ball-milled with zirconia grinding ball and ethanol for 24 h.
The dried powders were calcined at 850°C for 4 h, and then
they were ball-milled, dried and pressed into disks under
~20 MPa using polyvinyl alcohol (PVA) as a binder, with
the diameter of ~15 mm and the thickness of ~1.0 mm.
After burning off PVA, the ceramic disks were sintered at
1060°C in air, and the soaking time is 2 and 24 h,
respectively. Silver paste was fired on both sides of the
specimens at ~550°C for 30 min to form electrodes for
dielectric and piezoelectric measurements. The specimens
were poled in a silicon oil bath at 120°C for 30 min under
the 4.5 kV/mm dc electrical field. All the electrical
measurements were conducted on specimens aged for
more than 24 h.
The crystal structure was examined by X-ray diffraction
(XRD; Shimadzu, Max B) and scanning electron micro-
scopy (SEM; Ritachi S4800, Ibaraki, Japan). Dielectric
properties were obtained using an impedance analyzer (TH
2816A) by measuring the capacitance from 30°C to 500°C.
The piezoelectric constant d33 was measured using a
quasistatic piezoelectric constant testing meter (ZJ-4AN,
Institute of Acoustics, Chinese Academy of Sciences,
Beijing, China). The electromechanical coupling factor kp
and the mechanical quality factor Qm were determined by
the resonance method according to the IEEE Standard 176
using an impedance analyzer (HP 4294A).
3 Results and discussion
Figure 1(a) shows the XRD patterns of KNLNT ceramics
with various BC contents. It can be seen that the phase
structure of all samples was pure perovskite phase and no
secondary impurity was observed. Figure 1(b) shows the
{200} diffraction lines in the 2θ range between 44° and
47°. It is well known that a tetragonal symmetry with a =
b < c is characterized by the splitting of (002) and (200)
peaks. At the same time, the (002) line has a smaller Bragg
angle than that of the (200) line and the intensity ratio of
such two peaks I(002)/I(200) is about 0.5 [15]. So for the
ceramics with x = 0.00 has a tetragonal structure at room
temperature as shown in Fig. 1(b). The KNLNT–BC
ceramics with x = 0.005 still maintain the tetragonal
structure. With further increase of the BC content to x =
0.035, the ceramics are of a pseudo-cubic structure, where
the split {200} peaks emerge into a single peak. These
results indicate that a coexistence of tetragonal and pseudo-
cubic structures is formed at room temperature in the
composition range of 0.01£x£0.03, where the (200)
peaks is broader than that of the tetragonal structure. These
above results also indicate that BC has completely diffused
into the KNLNT lattice to form a homogeneous solid
solution.
The dielectric constant of (1 – x)KNLNT–xBC ceramics
as a function of temperature is measured at 1 kHz and the
Curie points of ceramics is plotted in Fig. 2. The obvious
liner decrease of the compositional tendency of the Curie
temperature further confirms that BC has completely
diffused into the KNLNT lattice to form a homogeneous
solid solution.
Figure 3 shows, as example, the temperature dependence
of the dielectric constant ε for ceramics with x = 0, x =
0.005 and x = 0.025, respectively. It can be seen that the
transition peak broadened considerably at x = 0.025. This
implies that the transition has become a diffuse phase
transition (DPT), which also was observed in KNN-based
 Ke-Pi CHEN et al. BC-doped KNLNT lead-free piezoelectric ceramics 313

Fig. 1 XRD patterns of (1 – x)KNLNT–xBC ceramics with the 2θ degree (a) ranging from 20° to 80° and (b) ranging from 44.3° to 46.8°.

Fig. 2 Compositional dependence of Curie points for the (1 – x) Fig. 3 Temperature dependence of dielectric constant for the
KNLNT–xBC ceramics. (1 – x)KNLNT–xBC ceramics.

ceramics doped by CaTiO3 [21], SrTiO3 [18], (Bi0.5Na0.5)-
TiO3 [25], Bi(Mg2/3Nb1/3)O3 [34], etc. Although the origin
of DPT is not fully understood yet at present, it is widely
accepted that the presence of polar microregions in
nanoscale and local compositional fluctuation are respon-
sible for the relaxor behaviors [35].
Figure 4 shows the surface morphology of the (1 – x)
KNLNT–xBCO (x = 0–0.035) ceramic samples sintered at
1060°C for 2 h. The sample with x = 0 has a bimodal
microstructure, consisting of small matrix grains ~0.5 μm
in radius and large abnormal grains up to 10 μm in radius,
as shown in Fig. 4(a). When the BC content is increased to
x = 0.005, the grain size in the ceramics becomes smaller
and is more uniform. The average size of the grains is about
2 μm (Fig. 4(b)). With the increase of the BC content, as
shown in Figs. 4(c)–4(h), the grain size drastically
decreases to smaller than 0.4 μm. The decrease of grain
size should be attributed to the addition of Bi3+, which
inhibits the grain growth. Similar phenomena have also
been observed in KNN-based ceramics doped with Bi2O3
[36], Bi(Mg2/3Nb1/3)O3 [34], Bi(Zn1/2Ti1/2)O3 [37] and
BiScO3 [38]. From Fig. 4, it can also be seen that
314 Front. Mater. Sci. 2012, 6(4): 311–318

Fig. 4 Surface morphologies of (1 – x)KNLNT–xBC ceramic samples sintered at 1060°C for 2 h: (a) x = 0; (b) x = 0.005; (c) x = 0.01; (d)
x = 0.015; (e) x = 0.02; (f) x = 0.025; (g) x = 0.03; (h) x = 0.035.
 Ke-Pi CHEN et al. BC-doped KNLNT lead-free piezoelectric ceramics 315

crystallization imperfection was induced when x > 0.005. method to promote grain growth. Figure 5 shows SEM
It is well known that prolonging sintering time is a useful results of the samples sintered at 1060°C for 24 h. It is

Fig. 5 Surface morphologies of (1 – x)KNLNT–xBC ceramics sintered at 1060°C for 24 h: (a) x = 0; (b) x = 0.005; (c) x = 0.01; (d) x =
0.015; (e) x = 0.02; (f) x = 0.025; (g) x = 0.03; (h) x = 0.035.
316 Front. Mater. Sci. 2012, 6(4): 311–318
obvious that soaking time has an important influence on
grain size and crystallization imperfection. After sintering
for 24 h, the grain size of KNLNT-based ceramics with x =
0 and x = 0.005 were increased, as shown in Figs. 5(a) and
5(b). As the BC content increases to x > 0.005, the grain
size of the KNLNT-based ceramic samples is about 500
nm, which is not significantly increased. However,
crystallization imperfection considerably decreased when
the soaking time was 24 h for these ceramics.
Figure 6 shows the compositional dependence of
electrical properties of (1 – x)KNLNT–xBC ceramics
sintered at 1060°C for 2 and 24 h, respectively. The
electrical properties of ceramics with x > 0.025 are not
present here owing to its large leakage current result in
poling difficult. From Fig. 6, it can be seen that the d33 and
kp values of ceramics sintered for 2 h increase with the
addition of BC, and then rapidly decrease with further
increasing the addition of BC. The best piezoelectric
properties with d33 ~ 194 pC/N and kp ~ 0.48 appear in the
composition with x = 0.005. These results indicate that the
0.995KNLNT–0.005BC ceramics possess optimum piezo-
electric properties at room temperature owing to its desired
microstructure.
Fig. 6 Compositional dependence of piezoelectric coefficient
d33, electromechanical coupling factor kp, and mechanical quality
factor Qm for (1 – x)KNLNT–xBC ceramics.
As can be seen from Fig. 6, the soaking time has obvious
effect on the d33 value of KNLNT-based ceramics. The
improvement of the d33 value could be attributed to the
increased grain size and the improved crystallization
imperfection, because the domain rotation was eased for
the specimens with large and perfect grains.
Especially, the Qm value of the ceramics sintered for 24 h
increases with the addition of BC, which may be attributed
to the pinning effect of the domain walls for the ceramics
due to the increase in the number of oxygen vacancies
generated by the addition of Co [33].
4 Conclusions
The effects of the BC content on the phase structure,
microstructure, electrical properties of the (1 – x)KNLNT–
xBC ceramics were investigated. The phase structure
changed from the tetragonal to pseudo cubic phase with
the increasing amount of the BC content. After the
substitute on of BC, grain size significantly reduced and
relaxer behavior was induced. By adding a small amount of
BC to KNLNT ceramics, the piezoelectric properties
increased. However, further addition of BC makes the
piezoelectric properties deteriorate markedly. The opti-
mized electrical properties at x = 0.005 were as follows: d33
= 194 pC/N, kp = 0.44.
Acknowledgements This work was supported by the National Natural
Science Foundation of China (Grant No. 50802029), Program for New
Century Excellent Talents in University (Grant No. NCET-11-0630), and
Fundamental Research Funds for the Central Universities (Grant No.
12ZX11).
References
[1] Shung K K, Cannata J M, Zhou Q F. Piezoelectric materials for
high frequency medical imaging applications: A review. Journal of
Electroceramics, 2007, 19(1): 141–147
[2] Damjanovic D. Contributions to the piezoelectric effect in
ferroelectric single crystals and ceramics. Journal of the American
Ceramic Society, 2005, 88(10): 2663–2676
[3] Aksel E, Jones J L. Advances in lead-free piezoelectric materials
for sensors and actuators. Sensors, 2010, 10(3): 1935–1954
[4] Jaffe B, Cook W R, Jaffe H. Piezoelectric Ceramics. London:
Academic, 1971
[5] Ye Z G, ed. Handbook of Advanced Dielectric, Piezoelectric and
Ferroelectric Materials: Synthesis, Properties and Applications.
Cambridge, UK: Woodhead Publishing Ltd., 2008
[6] Panda P K. Review: environmental friendly lead-free piezoelectric
materials. Journal of Materials Science, 2009, 44(19): 5049–5062
[7] Rodel J, Jo W, Seifert K T P, et al. Perspective on the development
of lead-free piezoceramics. Journal of the American Ceramic
Society, 2009, 92(6): 1153–1177
[8] Takenaka T, Nagata H. Current status and prospects of lead-free
 Ke-Pi CHEN et al. BC-doped KNLNT lead-free piezoelectric ceramics
piezoelectric ceramics. Journal of the European Ceramic Society,
2005, 25(12): 2693–2700
[9] Shrout T R, Zhang S J. Lead-free piezoelectric ceramics:
Alternatives for PZT? Journal of Electroceramics, 2007, 19(1):
113–126
[10] Guo Y P, Kakimoto K, Ohsato H. Phase transitional behavior and
piezoelectric properties of (Na0.5K0.5)NbO3–LiNbO3 ceramics.
Applied Physics Letters, 2004, 85(18): 4121–4123
[11] Du H L, Tang F S, Liu D, et al. The microstructure and
ferroelectric properties of (K0.5Na0.5)NbO3–LiNbO3 lead-free
piezoelectric ceramics. Materials Science and Engineering B:
Solid State Materials for Advanced Technology, 2007, 136(2–3):
165–169
[12] Kumar P, Palei P. Effect of sintering temperature on ferroelectric
properties of 0.94(K0.5Na0.5)NbO3–0.06LiNbO3 system. Cera-
mics International, 2010, 36(5): 1725–1729
[13] Guo Y P, Kakimoto K, Ohsato H. (Na0.5K0.5)NbO3–LiTaO3 lead-
free piezoelectric ceramics. Materials Letters, 2005, 59(2–3): 241–
244
[14] Hollenstein E, Davis M, Damjanovic D, et al. Piezoelectric
properties of Li- and Ta-modified (K0.5Na0.5)NbO3 ceramics.
Applied Physics Letters, 2005, 87(18): 182905 (3 pages)
[15] Dai Y J, Zhang X W, Zhou G. Phase transitional behavior in
K0.5Na0.5NbO3–LiTaO3 ceramics. Applied Physics Letters, 2007,
90(26): 262903 (3 pages)
[16] Guo Y P, Kakimoto K-I, Ohsato H. Structure and electrical
properties of lead-free (Na0.5K0.5)NbO3–BaTiO3 ceramics. Japa-
nese Journal of Applied Physics Part 1, 2004, 43(9B): 6662–6666
[17] Ahn C-W, Park C-S, Viehland D, et al. Correlation between phase
transitions and piezoelectric properties in lead-free (K,Na,Li)-
NbO3–BaTiO3 ceramics. Japanese Journal of Applied Physics,
2008, 47(12): 8880–8883
[18] Guo Y P, Kakimoto K, Ohsato H. Dielectric and piezoelectric
properties of lead-free (Na0.5K0.5)NbO3–SrTiO3 ceramics. Solid
State Communications, 2004, 129(5): 279–284
[19] Kano J, Sasanuma K, Tsukada S, et al. Piezoelectric (Na0.5K0.5)-
NbO3–SrTiO3 ceramics in the tetragonal-orthorhombic phase
boundary studied by Raman spectroscopy. Ferroelectrics, 2007,
347(1): 55–59
[20] Chang R C, Chu S Y, Lin Y F, et al. An investigation of
(Na0.5K0.5)NbO3–CaTiO3 based lead-free ceramics and surface
acoustic wave devices. Journal of the European Ceramic Society,
2007, 27(16): 4453–4460
[21] Park H-Y, Cho K-H, Paik D-S, et al. Microstructure and
piezoelectric properties of lead-free (1 – x)(Na0.5K0.5)NbO3–
xCaTiO3 ceramics. Journal of Applied Physics, 2007, 102(12):
124101 (5 page)
[22] Yang Z P, Chang Y F, Liu B, et al. Effects of composition on phase
317
structure, microstructure and electrical properties of (K0.5Na0.5)-
NbO3–LiSbO3 ceramics. Materials Science and Engineering A:
Structural Materials Properties Microstructure and Processing,
2006, 432(1–2): 292–298
[23] Zhang S J, Xia R, Shrout T R, et al. Characterization of lead free
(K0.5Na0.5)NbO3–LiSbO3 piezoceramic. Solid State Communica-
tions, 2007, 141(12): 675–679
[24] Wu J G, Xiao D Q, Wang Y Y, et al. Compositional dependence of
phase structure and electrical properties in (K0.42Na0.58)NbO3–
LiSbO3 lead-free ceramics. Journal of Applied Physics, 2007, 102
(11): 114113 (5 pages)
[25] Du H L, Zhou W C, Luo F, et al. Structure and electrical
properties’ investigation of (K0.5Na0.5)NbO3–(Bi0.5Na0.5)TiO3
lead-free piezoelectric ceramics. Journal of Physics D: Applied
Physics, 2008, 41(8): 085416
[26] Saito Y, Takao H, Tani T, et al. Lead-free piezoceramics. Nature,
2004, 432(7013): 84–87
[27] Chang Y F, Yang Z P, Wei L L. Microstructure, density, and
dielectric properties of lead-free (K0.44Na0.52Li0.04)(Nb0.96 – x-
TaxSb0.04)O3 piezoelectric ceramics. Journal of the American
Ceramic Society, 2007, 90(5): 1656–1658
[28] Li E, Kakemoto H, Wada S, et al. Effect of small amount CuO
doping on microstructure and properties of the alkaline
niobate-based lead-free ceramics. Ferroelectrics, 2007, 358(1):
153–160
[29] Lin D, Kwok K W, Chan H L W. Phase structures and electrical
properties of K0.5Na0.5(Nb0.925Ta0.075)O3–LiSbO3 lead-free piezo-
electric ceramics. Journal of Physics D: Applied Physics, 2007, 40
(19): 6060–6065
[30] Lin D, Kwok K W, Lam K H, et al. Structure, piezoelectric and
ferroelectric properties of Li- and Sb-modified K0.5Na0.5NbO3
lead-free ceramics. Journal of Physics D: Applied Physics, 2007,
40(11): 3500–3505
[31] Belik A A, Azuma M, Saito T, et al. Crystallographic features and
tetragonal phase stability of PbVO3, a new member of PbTiO3
family. Chemistry of Materials, 2005, 17(2): 269–273
[32] Uratani Y, Shishidou T, Ishii F, et al. First-principles predictions
of giant electric polarization. Japanese Journal of Applied Physics
Part 1, 2005, 44(9B): 7130–7133
[33] Wu W J, Xiao D Q, Wu J G, et al. Polymorphic phase transition-
induced electrical behavior of BiCoO3-modified (K0.48Na0.52)-
NbO3 lead-free piezoelectric ceramics. Journal of Alloys and
Compounds, 2011, 509(29): L284–L288
[34] Zhao J, Du H, Qu S, et al. The effects of Bi(Mg2/3Nb1/3)O3 on
piezoelectric and ferroelectric properties of K0.5Na0.5NbO3 lead-
free piezoelectric ceramics. Journal of Alloys and Compounds,
2011, 509(8): 3537–3540
[35] Liu Z-R, Gu B-L, Zhang X-W. Effects of ac field amplitude on the
318 Front. Mater. Sci. 2012, 6(4): 311–318

dielectric susceptibility of relaxors. Physical Review B: Con-
densed Matter and Materials Physics, 2000, 62(1): 1–4
[36] Du H L, Liu D J, Tang F S, et al. Microstructure, piezoelectric, and
ferroelectric properties of Bi2O3-added (K0.5Na0.5Nb)O3 lead-free
ceramics. Journal of the American Ceramic Society, 2007, 90(9):
2824–2829
[37] Sutapun M, Huang C C, Cann D P, et al. Phase transitional
behavior and dielectric properties of lead free (1 – x)(K0.5Na0.5)-
NbO3–xBi(Zn0.5Ti0.5)O3 ceramics. Journal of Alloys and Com-
pounds, 2009, 479(1–2): 462–466
[38] Skidmore T A, Comyn T P, Milne S J. Dielectric and
piezoelectric properties in the system: (1 – x)[(Na0.5K0.5Nb-
O3)0.93–(LiTaO3)0.07]–x[BiScO3]. Journal of the American Cera-
mic Society, 2010, 93(3): 624–626