J. Am. Ceram. Soc.

, 99 [6] 2170–2174 (2016)

DOI: 10.1111/jace.14184
© 2016 The American Ceramic Society

Journal
Phase Transition and Large Electrostrain in Lead-Free Li-Doped (Ba, Ca)(Ti, Zr)
O3 Ceramics
Xiaoming Chen,‡,§,¶,† Yongsheng Li,‡ Jiangtao Zeng,§ Liaoying Zheng,§ Chul Hong Park,k and
Guorong Li§
‡
School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
§
Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences,
Shanghai 200050, China
¶
University of Chinese Academy of Sciences, Beijing 100039, China
k
Department of Physics Education, Pusan National University, Pusan 609735, South Korea

Large piezoelectric effect is achieved in Li-doped Ba0.85 phase transition around room temperature. The Li+-con-
Ca0.15Ti0.90Zr0.10O3(BCTZ) ceramics by use of tuning the taining additives have the similar effect.14–17 For example,
phase boundaries. Rhombohedral–orthorhombic (R–O) and Ma et al.15 observed that Li2O-doped BT ceramics become
orthorhombic–tetragonal (O–T) multiphase coexistence is con- densification at low sintering temperature (1050°C vs
structed in the ceramics by changing Li contents. The high 1250°C, BT) and keep good piezoelectric properties
piezoelectric constant d33 (493 pC/N) and large electrostrain (d33 = 200 pC/CN) by shifting the orthorhombic (O)–te-
(dSmax/dEmax = 931 pm/V) have been observed in the Li- tragonal (T) phase transition to room temperature. Yang
doped (Ba, Ca)(Ti, Zr)O3 ceramics at low sintering tempera- et al.16 also reported that LiF-doped BT ceramics sintered
ture (1350°C/2 h). The significant enhancement in materials at 1100°C have a high d33 (270 pC/N), caused by O–T
properties is ascribed to the multiphase region around room phase coexistence at room temperature. For BCTZ-based
temperature induced by Li-doped effect. ceramics, we have reported that as the O–T polymorphic
transition temperature is adjusted to room temperature
through the combination of Li-doped effect and sintering
I. Introduction
effect, the Li2CO3-doped BCZT ceramics (BCTZL) achieve
large piezoelectricity (d33 = 512 pC/N) and great improve-
R ECENTLY, lead-free piezoelectric ceramic materials have
attracted much attention due to the environmental
problems resulting from the toxicity of lead oxide and its
ment of Qm (190) simultaneously.17 As mentioned above,
the excellent property of BT-based ceramics occurs when
evaporation during the sintering process of lead-based ceram- two ferroelectric phases are shifted around room tempera-
ics.1,2 A number of lead-free piezoelectric ceramics have been ture by tuning dopant. It will be interesting to find
intensively studied. BaTiO3 (abbreviated as BT) has been whether it is possible to improve useful properties by tun-
considered as one of the good candidates for lead-free piezo- ing dopant concentration to make three ferroelectric phases
electric ceramics because of its promising properties and high (rhombohedral, O and T) of BCZT composition in close
degree of solid solution with other perovskites, for example, proximity to each other around room temperature.
(Ba, Ca)(Ti, Sn)O3,3 (Ba, Ca)(Ti, Sn)O3–(Ba, Ca)(Ti, Zr)O3,4 In this work, we report our achievement on the above-
BaTiO3-KNbO3,5 Ba(Ti, Hf)O3-(Ba, Ca)TiO3,6 and Ba(Ti, mentioned issues in BCZT-based ceramics. A multiphase
Sn)O3–(Ba, Ca)TiO3.7 transition region has been obtained where R, O, and T
Among them, the (Ba, Ca)(Ti, Zr)O3 (BCTZ) lead-free phases are close to the room temperature by adjusting Li-
ceramics has an excellent piezoelectricity due to the role of dopant level. The appearance of a phase transition region
the polymorphic phase transition (PPT).8,9 Wang et al.9 contributes to generation of large electrostrain response and
reported that large piezoelectric coefficient d33 (about 650 strong ferroelectricity. Moreover, related mechanisms for
pC/N) of BCTZ ceramics is attained by sintering at the these phenomena are also given in detail.
optimum temperature (1540°C). The hard sintering condi-
tion of BCTZ ceramics is detrimental to mass production
II. Experimental Procedure
because of high-energy consumption. Consequently,
researchers manage to keep high piezoelectric properties Piezoceramics Ba0.85Ca0.15Ti0.9 Zr0.1O3 + x wt%Li2CO3
and reduce the sintering temperature of BCTZ ceramics by (x = 0.1, 0.3, 0.5, 0.7, 1.0, BCTZL-x) were prepared by the
the introduction of metal oxides, such as ZnO,10 CuO,11 conventional ceramic process. Analytical-grade metal oxides
Y2O3,12 and CeO2.13 Furthermore, dopants with lower or carbonate powders of BaCO3 (99%), TiO2 (99.48%),
valence (Zn2+,10 Cu2+11) can tune the phase boundaries of CaCO3 (99%), and ZrO2 (99.84%) were used as starting raw
BCTZ-based ceramics and contribute to the occurrence of materials. All the oxides and carbonates were mixed by ball-
milling for 6–7 h in anhydrous ethanol. The mixture was cal-
cined at 1200°C for 2 h. After calcination, Li2CO3 (99.31%)
were added, ball-milled again for 6–7 h. Then, the dried
D. Damjanovic—contributing editor powders were mixed with polyvinyl alcohol (PVA: 5 wt%)
binder solution and pressed into disks with a diameter of
12 mm. After excluding PVA binder at 700°C for 2 h, the
Manuscript No. 37716. Received November 1, 2015; revised January 28, 2016;
pellets were sintered at 1350°C for 2 h in air. The samples
approved January 30, 2016. were painted with silver paste on both sides and were
†
Author to whom correspondence should be addressed. e-mail: chenxiaoming@student. annealed at 700°C for 20 min, and then poled by applying a
sic.ac.cn

2170
June 2016 Correlation Between Phase Transition and Large Electrostrain 2171

DC field of 2–4 kV/mm for 15–30 min at 30°C in a stirred (a)

silicone oil bath.
The crystal structure of the sintered samples was analyzed
by X-ray diffraction (XRD) using CuKa radiation (Bruker
D8 Advance, Karlsruhe, Germany) at room temperature
(26°C). In order to determine the phase structure of the
ceramics, fine scanning was performed with a step interval of
0.02° in the ranges of 44°–46°.
The lattice parameters of the BCTZL-x ceramics were
refined by the Rietveld refinement method18 and MAUD
software (version 2.33).19–21 A scanning electron microscope
(SEM, KYKY-EM3200, KYKY Technology Development
Ltd., Beijing, China) was used to observe the surface
microstructure of the sintered samples. Density of samples
was determined by the Archimedes method. The temperature
dependence of dielectric properties was measured by using a
broadband dielectric spectrometer (Novocontrol Alpha-A (b)
BroadBand Dielectric Spectrometer, Hundsangen, Germany)
with the testing temperature ranged from 100°C to 250°C
at a heating rate of 3 K/min. Piezoelectric constant d33 was
tested by a Burlincourt-type d33 meter (ZJ-4AN, Institute of
Acoustic Academia Sinica, Chinese Academy of Sciences,
Beijing, China). The planar electromechanical coupling factor
kp and the mechanical quality factor Qm were measured by
using an impedance analyzer (Agilent, Palo Alto, CA,
4294A). Ferroelectric hysteresis loops (P–E) and strain curves
were measured by a modified Sawyer-Tower circuit at 10 Hz
(TF Analyzer 2000, aixACCT Systems GmbH, Aachen,
Germany).

III. Results and Discussion

The X-ray diffraction patterns in Fig. 1(a) indicate that all the
ceramics possess pure single phase of perovskite structure.
Furthermore, a fine scanning of ceramics in the 2h ranges 44°– Fig. 1. (a) X-ray diffraction patterns of the BCTZL-x ceramics. (b)
46° is shown in Fig. 1(b). When the content of Li+ increases, The fine scanning in the 2h ranges of 44°–46° of BCTZL-x ceramics.
the peaks near 45° clearly shift toward lower diffraction
angles, which should be attributed to the enlargement of lattice
parameters of the BCTZL-x ceramics according to Bragg’s
equation (2d sinh = k). The change of lattice parameters can Table I. Lattice Parameters and Absolute Value of Density
be explained by the influence of Li+ occupation on crystal of BCTZL-x Ceramics
structure. If Li+ enter into the A sites for BCTZ ceramics, it Space Cell volume Density [g/
may result in the lattice parameters decreasing, which can be X group

a, b, c [A] V [A
3] Sigma cm3]
ascribed to the fact that the ionic radius of Li+
(rLi+ = 1.18 A
22) for 12-fold coordination is smaller than that 0.1 Amm2 a = 4.0238(9) 129.8067 1.9023 4.0489
of A-site cations (rBa2+ = 1.61 A,
rCa2+ = 1.34 A).

Accord- b = 5.6829(8)
ingly, the Li+ occupation in B sites should be taken into con- c = 5.6764(2)
sideration. Since Li+ enter the sixfold coordinated B sites, the 0.3 Amm2 a = 4.0225(3) 129.4119 1.8382 4.9888
occupation of Li+ with large radius (r = 0.76 A,
CN = 6) b = 5.6721
for Ti4+ or Zr4+ with small radius (rTi4+ = 0.61 A,
rZr4+ + c = 5.6719(4)

23 can result in the enlargement for the lattice, as
= 0.74 A) P4mm a = 4.0022(7) 64.3895 1.5279
shown in Table I. However, the introduction of Li+ in B sites c = 4.0197(8)
of BCTZ ceramics can produce oxygen vacancies owing to its 0.5 Amm2 a = 4.0209(8) 129.1612 1.8339 5.4504
lower valence compared to Ti4+ or Zr4+. The oxygen vacan- b = 5.6677(9)
cies can lead to shrinkage of the lattice.24 Therefore, the + c = 5.6674(3)
enlargement of lattice parameters of the BCTZL-x ceramics P4mm a = 4.0074887 64.5613 1.7785
can be explained by the fact that the radius effects caused by c = 4.0200157
the occupation of Li+ in B sites, which has become more dom- 0.7 Amm2 a = 4.013 129.2870 1.9502 5.4212
inant than that of oxygen vacancies. On the other hand, it was b = 5.67535
obvious that the crystal phase of BCTZL-x ceramics is altered + c = 5.67665
by the addition of Li+, as indicated by the change of peaks at P4mm a = 4.0184510 64.9376 1.9564
around 2h of 45°. The peaks at 45° gradually change with the c = 4.0214143
increase of Li+ dopant. The peak’ s variation indicates the 1.0 P4mm a = 4.0077450 64.6002 1.6502 5.3379
BCTZL-x ceramics experience the phase transition from O c = 4.0219220
phase (PDF#81-2200) to coexistence of O and T phase
(PDF#05-0626).
To investigate the phase transition, the temperature depen-
dence of dielectric properties (1 kHz) for BCTZL-x ceramics which is shown in the inset of Fig. 2(a). The peaks of the dif-
is shown in Fig. 2(a). The BCTZL-x ceramics show dielectric ferential curve are used to determine rhombohedral (R)–O,
anomalies, which are analogous to the previous report of O–T, and T-cubic (C) phase transition. With increasing Li+
pure BCTZ ceramics.25 The permittivity curve (1 kHz) is dif- concentration, R–O phase transition gradually shift to
ferentiated in order to investigate dielectric anomalies,25 high temperature, and the T-cubic (C) phase transition obvi-
2172 Journal of the American Ceramic Society—Chen et al. Vol. 99, No. 6

ously moves to low temperature (62°C) at x = 1.0. The The R–O phase boundary is stabilized near room tempera-
phenomenon may be attributed to existence of pinching effect ture at x > 0.1. Additionally, it can be seen that the tempera-
in these compositions that the temperature of lower tempera- ture span between the TR–O and TO–T is less than 15°C when
ture phase transition increases, while the Curie temperature x > 0.1, indicating existence of a narrow temperature range
(Tc) decreases. It is coincided with the reported result of between R and T phases. It also suggests that BCTZL-x
occupation of Zr4+ in B sites of the Ba(Ti1–xZrx)O3 ceramics are in the proximity of multiphase transition region
system.26,27 (R, O, and T phases). As a consequence, it can make ferro-
The phase diagram of BCTZL-x ceramics is shown in electric domains easily switched under phase transition
Fig. 2(b), which originates from the results of the XRD and region, and produce large piezoelectric response around
temperature-dependent dielectric response. With further room temperature.
increase in Li+ content, O–T phase transition temperature The P–E hysteresis loops measured at room temperature
(TO–T) moves from 41°C at x = 0.1 to 25°C at x = 1, indicat- are displayed in Fig. 3(a). It has been found that the ceram-
ing the final coexistence of O and T phases at room tempera- ics exhibit well-saturated hysteresis shape when x > 0.1. The
ture, while R–O phase transition temperature (TR–O) exhibits values of remnant polarization (Pr) first increases to 8.47 lC/cm2
an increasing trend from –7°C at x = 0.1 to 15°C at x = 1. for BCTZL-0.5 ceramics and then decreases, while the coer-

(a) (b)

(c) (d)

(e)

Fig. 2. (a) Temperature dependence of er for BCTZL-x ceramics at 1 kHz (x = 0.1, 0.3, 0.5, 1.0); (b) Phase diagram of BCZTL-x ceramics.
June 2016 Correlation Between Phase Transition and Large Electrostrain 2173

cive field (Ec) obviously decreases to 2.04 kV/cm at x = 1.0, piezoceramics. (Qm of soft Pb(Ti, Zr)O3 piezoceramics is
as shown in the inset of Fig. 3(a). The low Ec and large Pr commonly about 50).17 Enhanced Qm can be attributed to
show the easy reversals of polarization under dc bias, which the fact that the Li+ occupation in B sites of perovskite
are favorable to the electrical properties of ceramics.28,29 structure generates oxygen vacancies, which pin the move-
The electrostrain (S) versus electric field (E) loops for ment of domain walls and make BCTZL-x ceramics hard-
BCZTL-x ceramics are observed in Fig. 3(b). Similar to the ened.34–36
Pr variation dependent on the increase of Li+, electrostrain In our case, the BCZTL-x ceramics sintered at low tem-
reach the maximum (0.1024%) for BCZTL-0.5 ceramics perature (1350°C/2 h) achieve the improvement of electrical
under a DC field of 11 kv/cm, which is consistent well with properties and produce large piezoelectric response. It may
ferroelectric properties. The maximum dS/dE value of be associated with dense microstructure,14,17,37 radius effects,
931 pm/V can be obtained at x = 0.5, as shown in the inset oxygen vacancies,38–40 but are mainly dependent on existence
of Fig. 3(b). The result may be attributed to the following of multiphase transition region (R, O, and T phases) around
mechanism. The improvement of electrostrain for ferro- room temperature caused by Li-doped effect. As x = 0.1, the
electrics originates mainly from the contribution of non-180° ceramics show poor performance (low permittivity and low
domain switching.30 The appearance of multiphase transition electrostrain) due to the low density of the sample. When
region at room temperature leads to the easy rotation of x > 0.1, the BCTZL-x ceramics become dense, which are in
non-180° domain, and produce large electrostrain.31–33 the proximity of multiphase transition region at room tem-
Figure 4(a) and (b) exhibit the piezoelectric, relative densi- perature, as shown in Fig. 2(b). Ferroelectric domains can be
ties and dielectric properties of BCZTL-x ceramics as a func- easily switched under phase transition region, which leads to
tion of the Li2CO3 content. The piezoelectric constant and generation of large piezoelectric response (dSmax/
planar electromechanical coupling factor of BCTZL-x ceram- dEmax = 931 pm/V) around room temperature.
ics reaches the maximum value (d33 = 493 pC/N, kp = 0.47)
at x = 0.5, and then decreases, while the relative permittivity
IV. Conclusions
shows a similar trend as d33, giving the maximum value at
x = 0.7. Moreover, the loss tangent tand has a decreasing In this work, the phase transition, piezoelectric response, and
trend with the amount of Li+ increasing. The improvement electrical properties of BCTZL-x lead-free piezoceramics are
of electrical properties is in agreement with dense microstruc- investigated. Both the R–O and O–T phase transitions can
ture that the relative densities of BCTZL-x ceramics increase be stabilized around room temperature by changing Li+
by Li+ dopant and are higher than 90% of the theoretical dopant. The existence of phase transition region at room
ones when x ≥ 0.3,9 as shown in Table I and Fig. 4(a). It is temperature produces large piezoelectric response and con-
to be noted that the maximum value (158) of Qm occurs at tributes to the great improvement in electrical properties of
x = 0.3, which have the characteristics of relatively hard PZT ceramics. The BCTZL-0.5 ceramics sintered at 1350°C/2 h
exhibit good electrical properties and large electromechanical
strains, which are as follow: d33 = 493 pC/N, kp = 0.47,
er = 5289, tan d = 1.5%, Qm = 145, Ec = 2.51 kv/cm,
(a)

(a)

(b) (b)

Fig. 4. (a) Piezoelectric properties and relative densities of the

Fig. 3. (a) Ferroelectric properties of BCZTL-x ceramics; (b) BCZTL-x ceramics. (b) dielectric properties of the BCZTL-x
electromechanical strain data for compositions sintered at 1350°C/2 h. ceramics.
2174 Journal of the American Ceramic Society—Chen et al. Vol. 99, No. 6

Pr = 8.47 lC/cm2, and dSmax/dEmax = 931 pm/V. The results 18

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