Review

Journal of Advanced Dielectrics Vol. 1, No. 3 (2011) 269288 World Scientic Publishing Company DOI: 10.1142/S2010135X11000409

A REVIEW ON LEAD-FREE PIEZOELECTRIC CERAMICS STUDIES IN CHINA

YI-QING LU and YONG-XIANG LI* The Key Lab of Inorganic Functional Materials and Devices Shanghai Institute of Ceramics, Chinese Academy of Sciences 1295 Dingxi Road, Shanghai 200050, P. R. China yxli@mail.sic.ac.cn Received 3 May 2011 Revised 27 May 2011
There are a large number of research publications on the hot topic of environmental friendly leadfree piezoelectric materials worldwide in the last decade. The number of researchers and institutions involved from China is much larger than other countries or regions. The publications by Chinese researchers cover a broad spectrum on the preparations, structures, properties and applications of lead-free piezoelectric ceramics. This has motivated us to come out with a review on recent advances in development of lead-free piezoelectric ceramics in China. The emphases are especially on the preparation and electric properties of barium titanate-based materials, bismuth sodium titanate and related materials, alkaline niobate and related materials, bismuth layerstructured materials, as well as texture engineering of ceramics and some of their single crystals. Hopefully, this could give further impetus to the researchers to continue their eorts in this promising area and also draw the attentions from legislature, research oce, industrial and publics. Keywords: Lead-free; piezoelectric ceramic; barium titanate; bismuth sodium titanate; potassium sodium niobate; bismuth layer-structured ferroelectrics; texture; single crystal.

1. Introduction
From the early 1960s, Prof. Zhi-Wen Yin, who was the founder of the functional ceramics center of Shanghai Institute of Ceramics, Chinese Academy of Sciences, China, headed a group with more than 50 researchers studied BaTiO3 and PbZrTiO3 piezoelectric ceramics and the applications. Various devices were developed such as sensors, transducers and actuators. The technology was transferred, and hundreds of piezoelectric components and ultrasonic equipment companies were established across China. In 1973, Yan-Yi Guo et al. studied tungsten bronze structure barium sodium niobate (Ba2x Srx NaNb5 O15 ,
*Corresponding

BNN) ceramics, and three dierent frequencies of 465 kHz, 915 kHz and 1.5 MHz narrow band lters were developed and commercialized. In 1977, Da-ren Cheng et al. studied bismuth layer-structured ferroelectric (BLSF) Bi4 MTi4 O15 (M Ca, Sr, Ba, Pb) ceramics, and high temperature vibration transducers used at 350  C were developed, which were used in the aeronautics and astronautics industry of China. The above nonperovskite structure piezoelectric materials studies and applications were mainly because BNN ceramics have excellent properties with high frequency constant (Np 3650 Hzm),

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high mechanical quality factor (Qm 2000), low temperature coecient of resonant frequency (35 10 6 , 55  C to 85  C) and BLSF ceramics have high d33 (>25 pC/N) and high Curie temperatures (TC > 650  C). Unfortunately, these early studies were only archived as internal technical reports or published in Chinese journals. From 1978, Tian-bao Wang et al. initiated the investigations on the perovskite structure lead-free piezoelectric ceramics, 1xBi0:5 Na0:5 TiO3 xBaTiO3 (BNTBT), 1xBi0:5 Na0:5 TiO3 xBi0:5 K0:5 TiO3 (BNTBKT), which were the rst attempt to nd substitutions of PZT ceramics in China.13 They found that good piezoelectric properties for BNTBT system on the MPB region of x 6%, for BNTBKT system of x 19%. The optimized compositions of two systems named E6 C7 and BNNEA were used for ultrasonic transducers for medical imaging, which showed great potentials. At the 9th International Meeting on Ferroelectricity (August 2429, 1997, Seoul, Korea), Prof. Ding-Quan Xiao was aware of the demands of ecomaterials or environmental friendly materials, and pointed out that \ferroelectric materials should comprise non-hazardous substances with a small environmental load, and the manufacturing processes for these materials should also be with a small environmental load," and \the research on lead-free piezoelectric ceramics is a typical example."4 Since then, his group has paid great attention to the research of lead-free piezoelectric ceramics, especially concentrated on perovskite structure lead-free piezoelectric ceramics. For details, a review paper can be found elsewhere.5 Starting from new millennium, global warming, energy shortage and environment protection have been serious concerns. The European Union (EU) in 2003 included lead (Pb) in its legislature to be substituted as a hazardous substance. There are similar activities and regulations in the countries all over the world. In China, the EU legislations were adopted since July 1, 2006. The WEEE (Waste Electrical and Electronic Equipment) and RoHS (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment) directives spurred the research for lead-free piezoceramics, which had started from 2000. It can be clearly seen from Fig. 1 that the research on lead-free piezoceramics worldwide reected by the number of publications is increasing steadily in last decade. Publications from

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Fig. 1. Publications on lead-free piezoelectric ceramic over the last decade (20002010) in refereed journals. Total number of papers is 1755. The search and statistics are conducted from the database of \ISI Web of Science," SCI-EXPANDED, CPCI-S, CCR-EXPANDED and IC, in a period of time 20002010, using query of TS (piezoelectric SAME ceramics) NOT TS (Pb or lead or nite element or PbTiO3* or PbZrO3* or PZT* or PMN* or PT or PbO* or PMS* or PZN* or PLSZT* or PIN* or xPb*) OR TS (piezoelectric SAME ceramics) AND TS (lead SAME free or Pb SAME free) NOT TS (nite element).
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Fig. 2. The percentage of publications on lead-free piezoelectric ceramics divided from countries and regions.

East Asia are predominant. Especially, more than 45% papers are from China (Fig. 2). There are also 148 patents related to \lead-free piezoelectric ceramic" (20002010) registered by State Intellectual Property Oce of P. R. China, which are not included in this review. This is because there are large groups from research institutions, and a large numbers research programs/projects funded from The National Nature Science Foundation of China (NSFC), The Ministry of Sciences and Technology of China (MOST) through 973-projects and 863-projects, many of provincial governments. More importantly, there are hundreds small- and medium-sized enterprises in Yangtze River

A Review on Lead-Free Piezoelectric Ceramics Studies in China

Univ Elect Sci & TechnolChina Yangzhou Univ Hefei Univ Technol Nanjing Univ

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Fig. 3. The publications from top 10 research institutions in China on lead-free piezoelectric ceramics.

and Pearl River Delta economic zones which show their enthusiasm and demands for lead-free piezoelectric ceramics and devices. The import and export of electronic products from these regions occupy a decisive position and inuence in the international markets, which must meet the regulations of dierent nationals. There are many universities and laboratories in China studying in the area of lead-free piezoelectric materials; the top 10 institutions are listed in Fig. 3 which are ranked with their publications in the year 20002010. The current review is based on these publications, and organized into compositional families including: barium titanate-based materials, bismuth sodium titanate and related materials, alkaline niobate and related materials, and bismuth layer-structured materials. In addition, researches on the texture engineering and single crystals of lead-free piezoelectric materials are reviewed with special emphasis.

2. Barium Titanate-Based Materials

Barium titanate BaTiO3 (BT) is the rst practically used piezoelectric ceramics and the prototype polymorphic phase transition (PPT)-based highperformance piezoelectric material. However, the poor piezoelectric properties (d33 190 pC/N) and low Curie temperature (TC 120  C) of BT ceramics have been the main obstacle for their wider commercial application in actuators and sensors. In order to improve the piezoelectric properties and temperature stability of BT ceramics, extensive

eorts centered on compositional investigations have been carried out. It has been discovered that the substitution of Ti 4 with quadrivalence ions (such as Zr 4 and Hf 4 can improve the properties of BT ceramics. Zheng et al. found that the piezoelectric temperature stability could be greatly enhanced by a proper combination of partially substituting Ti 4 with Zr 4 and adding a small amount of CuO additive.6 CuO-modied BaTi0:9625 Zr0:0375 O3 ceramics possess excellent piezoelectric properties of d33 300 pC/N, and its kp remains larger than 0.40 in a broad temperature range from 43  C to 73  C and is almost constant between 25  C and 55  C. Tian et al. reported that the three phase transitions in BT are pinched by substituting Ti with Hf, and the Curie temperatures decrease as the Hf content increases in the compounds.7 A high piezoelectric parameter (d33 305 pC/N) is obtained for BaHf0:05 Ti0:95 O3 composition between the orthorhombic and rhombohedral phases. In 2009, Liu et al. reported a high performance lead-free piezoelectric system Ba(Zr0:2 Ti0:8 O3 x (Ba0:7 Ca0:3 TiO3 (BZTxBCT) which shows a surprisingly high piezoelectric coecient d33 of 620 pC/N at the morphotropic phase boundary (MPB) composition x 50.8 The phase diagram of this BZTxBCT system and a few typical dielectric permittivity (") versus temperature (T ) curves are shown in Fig. 4. BZTx BCT shows a phase diagram similar to the lead-based systems like PZT and PMNPT, that is, with a MPB starting from a triple point of a paraelectric cubic phase (C), ferroelectric rhombohedral (R) and tetragonal (T) phase. Subsequent investigation conrmed that the high piezoelectric properties could be ascribed to the low polarization anisotropy as well as the elastic softening at MPB.9 Their work gives a new insight into how to design lead-free piezoelectric ceramics with high piezoelectricity. However, the Curie temperature of BZT50BCT is relatively low (93  C). By increasing the TC of both tetragonal and rhombohedral terminals of the leadfree system BZTxBCT, the modied system Ba (Zr0:15 Ti0:85 O3x(Ba0:8 Ca0:2 TiO3 (BZ0:15 TxBC0:2 T) with a higher TC of 114  C at x 53 was obtained.14 The phase diagram and temperature dependence of dielectric permittivity of BZ0:15 TxBC0:2 T system are shown in Fig. 5. It was found that both d33 and " along MPB decreased with a deviation from the cubictetragonalrhombohedral triple point.

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Fig. 4. (Color online) (a) Phase diagram of pseudo-binary ferroelectric system BZTxBCT. (b)(d) Dielectric permittivity curves for 20BCT, 50BCT and 90BCT, respectively.8 Source: Reprinted with permission. Copyright 2009 by the American Physical Society.

Fig. 5. (Color online) (a) Phase diagram of BZ0:15 TxBC0:2 T system. (b)(f) Temperature dependence of dielectric permittivity for BZ0:15 TxBC0:2 T (x 15, 20, 40, 53, 90).14 Source: Reprinted with permission from IOP.

Other reports also indicated that optimizing Ca and Zr content is an eective way to enhance the piezoelectric properties of (Ba, Ca)(Ti, Zr)O3 ceramics.1013,15,16 The properties of some compositionally modied BT ceramics are summarized in Table 1. Recently, structural engineering techniques by several groups have led to enhanced piezoelectric properties in BT ceramics. The structural engineering techniques, which including optimization of grain size and orientation as well as domain engineering, focuses on controlling the micro and/or nanoscale structure of a piezoelectric material.17 For BT ceramics, it is believed that there is also a critical grain size, below which the lattice changes
Table 1. Compositions BaTi0:9625 Zr0:0375 O3 CuO BaTi0:95 Hf 0:05 O3 BaZr0:2 Ti0:8 O3 50Ba0:7 Ca0:3 TiO3 (Ba0:92 Ca0:08 Ti0:95 Zr0:05 O3 Ba0:84 Ca0:16 Ti0:9 Zr0:1 O3 Ba0:99 Ca0:01 Ti0:98 Zr0:02 O3 Ba0:96 Ca0:04 Ti0:95 Zr0:05 O3

from tetragonal to cubic and ferroelectricity is lost. Wang et al. investigated the grain size eect on the nanometer scale of nanocrystalline BT ceramics obtained by spark plasma sintering (SPS) and twostep sintering.18,19 Their results revealed that ferroelectricity could remain in BT ceramics with a grain size as small as 8 nm in diameter.19 Shao et al. synthesized BT ceramics through the conventional solid-state reaction route starting from ordinary BaCO3 and TiO2 powders.20 They found that the d33 decreased from 419 pC/N to 185 pC/N when its average grain size increased from 3.5 to 9.5 m, while its average domain width remained approximately constant at around 240 nm. They suggested that the largeness of the domain wall is an

Properties of some compositionally modied BT ceramics. TC (  C) 109.2 93 110 115 2070 "r 1546 4050 4800 d33 (pC/N) 300 305 620 365 328 375 338 kp (%) 49.3 53 48.5 37.6 44.1 36 kt (%) 48.9 42 k33 (%) 65.1 57 65 k31 (%) 30.4 31 References 6 7 8 10 11 12 13

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Fig. 6. TEM image for poled BT ceramics prepared by SPS using hydrothermally synthesized 100 nm BaTiO3 powders.21 Source: Reprinted with permission from the Ceramic Society of Japan.

important factor, which signicantly inuences the piezoelectric properties. In other works, ne-grain BT ceramics with enhanced piezoelectric properties were prepared by SPS and microwave sintering using hydrothermally synthesized nanoscale particles. Shen et al. found that d33 of BT ceramics prepared by SPS showed great dependence on the size of ferroelectric domains.21 Their results showed that nanodomain smaller than 50 nm could be achieved in the case of large grain size (> 10 m) by SPS (Fig. 6), suggesting that nano-domain structure is a dominant factor to inuence the piezoelectric properties of BT ceramics. The physical properties of some structurally engineered BT ceramics are summarized in Table 2.

3. Bismuth Sodium Titanate and Related Materials

Bismuth sodium titanate (Bi0:5 Na0:5 )TiO3 (BNT) with a rhombohedral perovskite structure have been studied for a long time as a promising alternative to lead-based piezoelectrics. BNT shows strong ferroelectric properties of a relatively large remnant polarization, Pr 38 C/cm 2 , and has a relatively
Table 2. BaTiO3 Normal sintering (for comparison) Spark plasma sintering Normal sintering (ne grain) Microwave sintering

high Curie temperature, TC 320  C. However, BNT-based ceramics undergo another phase transition below TC that is known as depolarization temperature (Td ), which often occurs below 200  C. When the depolarization takes place at this phase transition, the piezoelectric properties of these ceramics are reduced signicantly. Consequently, Td is a more important parameter than TC in the view of practical uses. Another major challenge in the performance of pure BNT piezoelectric ceramics exists because of their very large coercive eld and high conductivity, which leads to the poor poling treatments and thus underdeveloped piezoelectric performance. BT and (Bi0:5 K0:5 )TiO3 (BKT) are well-known lead-free piezoelectric materials with the tetragonal symmetry. Among the BNT-based lead-free piezoelectric systems, the binary systems of BNTBKT and BNTBT have obtained the most extensive investigation because they have good piezoelectric performance near the rhombohedraltetragonal MPB. In addition, BNT-based compositions modied with (Bi0:5 Li0:5 )TiO3 , Ba(Cu0:5 W0:5 )O3 , NaNbO3 and Er2 O3 have been reported.2327 Some of the BNT-based solid solutions and their electrical properties are presented in Table 3. The study of BNT-based lead-free piezoelectric ceramics in China began in 1978. Wang et al. studied the piezoelectric and ferroelectric properties of xBNT(1x)BKT (0:73 x 1:0) and yBNT (1yBT (0:81 y 0:99) ceramic systems.13 It was found that the MPB between tetragonal and rhombohedral phases of the systems were located at the compositions of x 0:81 and y 0:94, respectively. The Na-rich compositions near the boundaries of BNT-based systems with higher thickness coupling factor kt , lower planar coupling factor kp , higher frequency constants Np and lower dielectric constants " T were obtained, as shown in Fig. 7. Ultrasonic 33 transducers based on these materials were developed. The development of BNT-based ceramics in the last 10 years are summarized in the following three sections.

Physical properties of structurally engineered BT ceramics derived from dierent preparation methods.  (g/cm 3 ) 5.85 5.94 5.79 "r 3088 4301 3181 1570 tan (%) 3.3 2.9 1.4 1.12 d33 (pC/N) 193 416 419 374 kp (%) 27.3 41.5 45.3 References 21 21 20 22

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Y.-Q. Lu & Y.-X. Li Table 3. Properties of some BNT-based solid solution systems. "r 328 624 893 1261 1437 tan  (%) 1.5 5.9 3.7 5.1 4.0 d33 (pC/N) 110 80 88 144 207 132 215 170 168 231 171 160 155 152 153 137 139 133 205 149 171 208 168 159 147 135 110 148 150 149 $ 143 205 194 kp (%) 18 18.1 17.9 29 29.8 27.8 35 36.6 36.8 30.0 30 36.7 34 36.4 23 27 29 50.5 334 38 288 105 136 kt (%) TC (  C) 308 Td (  C) References 23 24 25 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57

Compositions 0.85BNT0.15(Bi0:5 Li0:5 TiO3 0.995BNT0.005Ba(Cu0:5 W0:5 O3 0.98BNT0.02NaNO3 0.82BNT0.18BKT 0.77BNT0.23BKT 1 mol% Bi2 O3 0.88BNT0.12BKT 0.2 wt% CeO2 0.82BNT0.16BKT0.02KN 0.79BNT0.18BKT0.03BiFeO3 0.805BNT0.18BKT0.015BiCrO3 0.7BNT0.2BKT0.1(Bi0:5 Li0:5 TiO3 0.7BNT0.2BKT0.1(Bi0:5 Li0:5 TiO3 Na 0.9(0.79BNT0.21BKT)0.1(Bi0:5 Ag0:5 TiO3 0.94BNT0.06BT 0.94BNT0.06BT 0.4 wt% CeO2 0.92BNT0.08BT 0.3 wt% MnO 0.93BNT0.07BT 0.8 wt% CoO 0.94BNT0.06BT 0.5 mol% Co2 O3 0.985(0.94BNT0.06BT)0.0075La2 O5 0.93BNT0.07BT 0.16 wt% In2 O3 0.92BNT0.08BT Nb2 O5 0.995(0.94BNT0.06BT)0.005Ta2 O5 0.865BNT0.06BT0.075(Bi0:5 Li0:5 TiO3 0.94[0.94BNT0.06(Bi0:5 Ag0:5 TiO3 ]0.06BT 0.92BNT0.06BT0.02(Y0:5 Na0:5 TiO3 0.91BNT0.09Ba(Ti0:942 Zr0:058 O3 0.92BNT0.08Ba(Ti0:95 Hf0:05 O3 0.95BNT0.02BT0.03NaNO3 0.90BNT0.05BKT0.05BT 0.895BNT0.07BKT0.035BT 0.85BNT0.12BKT0.03BT 0.85BNT0.12BKT0.03BT Co2 O3 (Bi0:98 Na0:755 K0:15 Li0:075 0:5 Ba0:02 TiO3 (Bi0:95 Na0:75 K0:15 Li0:05 0:5 Ba0:05 TiO3

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3.1. BNTBKT system

Recent work by Yang et al. demonstrated the formation of an MPB in the BNTBKT solid solution, in the range of 0.16 to 0.2 BKT. The d33 of 144 pC/ N, kp of 0.29, and dielectric permittivity of 893 were achieved for MPB composition.28 Zhang et al. investigated the inuence of sintering temperature on the piezoelectric, dielectric and ferroelectric properties of 0.5 mol% Bi2 O3 -compensated BNTBKT near the composition of MPB.58 It was demonstrated that both sintered density and electrical properties were sensitive to sintering temperature; particularly, the piezoelectric properties deteriorated when the ceramics were sintered above the optimum temperature. The highest d33 of 192 pC/N was obtained in the ceramics of

0.78BNT0.22BKT sintered at 1150  C. On the other hand, the MPB of 1.0 mol% Bi-compensated BNTBKT system exists in the range of 2024 mol% BKT.29 This MPB range slightly shifts to the BKT side as compared to previous results, probably due to the comprehensive eects of Bi compensation. The 1.0 mol% Bi-compensated 0.77BNT0.23BKT ceramics showed the highest piezoelectric constant d33 of 207 pC/N. In order to further enhance the properties, BNT BKT compositions have been modied with CeO2 , NaNbO3 , KNbO3 (KN), BiFeO3 and BiCrO3 .3033,59 Fan et al. investigated the MPB phase diagram of BNTBKTKN ternary system (Fig. 8).31 The addition of KN may improve the crystal symmetry of the ternary system and make the rhombohedral and

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Fig. 7. Piezoelectic properties and dielectric constants of BNTBKT ceramics as a function of the amount of BNT.1

tetragonal MPB move toward lower BKT content. Near the MPB, the optimum properties are d33 of 215 pC/N and kp of 35% for BNTBKTKN 82/16/2 ceramics, and d33 of 138 pC/N and kp of 38% for BNTBKTKN 87/10/3 ceramics. Zhou et al. investigated the eect of BiFeO3 addition on

microstructure and electrical properties of (0.82x) BNT0.18BKTxBiFeO3 ceramics.32 The specimens with x 0:05 maintained a rhombohedral tetragonal phase co-existence and changed into a rhombohedral phase when x > 0:05. The piezoelectric constant d33 and the electromechanical coupling factor kp showed an obvious improvement by the addition of small amount of BiFeO3 , which showed optimum values of d33 170 pC/N and kp 0:366 at x 0:03. The mechanisms of intrinsic and extrinsic contributions to the dielectric and piezoelectric responses have been proposed. In the (1xy)BNTxBKTyBiCrO3 system, it was found that the MPB with rhombohedral and tetragonal co-existence lies in the range of x 0:180.21 and y 00:02.33 The optimum values of d33 , kp were 168 pC/N, 0.32 at x 0:18, y 0:015 and x 0:18, y 0:01, respectively. Recently, some studies have been conducted to modify the BNTBKT system by incorporating other A-site dopants, such as Li and Ag , to further enhance their ferroelectric and piezoelectric properties. Bi0:5 (Na1xy Kx Liy 0:5 TiO3 lead-free piezoelectric ceramics have been investigated by Lin et al.34,60 The partial substitution of Na by K and Li eectively decreases the coercive eld Ec but simultaneously maintain the very strong ferroelectricity, which results in an obvious improvement on the piezoelectric properties. The optimized piezoelectric properties d33 of 231 pC/N, kp of 41.0%, and kt of 50.5% were obtained. The Td of the composition with x 0:15 and y 0:075 was reported to be approximately 195  C. Another study by Zhang et al. focused on Bi0:5 (Na0:7 K0:2 Li0:1 0:5 TiO3 composition ceramics by adding Na2 CO3 as sintering aid.35 The excess of Na2 CO3 could eectively reduce sintering temperature to 1020  C without deterioration of the piezoelectric properties. The Bi0:5 (Na0:7 K0:2 Li0:1 0:5 TiO3 ceramics with an excess of 5 mol% Na2 CO3 exhibited the optimum properties (d33 171 pC/N, kp 30:0%, Pr 31:9 C/cm 2 .

3.2. BNTBT system

It has been reported that the BNTBT system has a rhombohedraltetragonal MPB at x 0:06.44 Compared with pure BNT, the BNTBT compositions near the MPB provide substantially improved poling and piezoelectric properties. Inuences of nonstoichiometry and doping on the structures and piezoelectric properties of BNTBT

Fig. 8. MPB phase diagram of BNTBKTKN ternary system.31 Source: Reprinted with permission. Copyright 2007, American Institute of Physics.

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compositions near the MPB have been studied extensively.44,61 Various oxides, such as CeO2 , SnO2 , MnO, CuO, CoO, Co2 O3 , In2 O3 , La2 O3 , Nb2 O5 and Ta2 O5 have been employed as additives for the BNTBT ceramics.3845,6264 Researchers have investigated the eects of small amount of dopants on the properties of BNTBT ceramics, and found that introducing these dopants can improve the piezoelectric and dielectric properties to some extent. Wang et al. reported that the addition of CeO2 at a certain amount improved the piezoelectric and dielectric properties of 0.94BNT0.06BT ceramics signicantly, showing the double eects in increasing the coupling factor and decreasing the dissipation factor.38 During sintering CeO2 diused into the lattice to form a solid solution, but did not change co-existence of tetragonal and rhombohedral phases. Zhu et al. observed that the sintering properties of 0.92BNT0.08BT ceramics could be improved by adding a small amount of MnO.39 The optimal electrical properties were acquired at the solution limit of MnO at 0.30 wt%. The suitable substitution of Mn ion into the B-site induces the lattice distortion of BNTBT perovskite. Zhou et al. synthesized In2 O3 -doped 0.93BNT0.07BT ceramics by direct reaction sintering.43 It was found that the direct reaction sintering promotes growing of ceramic grains while doping of In2 O3 contributes to inhibit and homogenize the grain growth. Optimum properties with kt 0:503, d33 205 pC/N, " T ="0 1046, and tan  0:036 were achieved in 33 samples with 0.16 wt % In2 O3 . Zuo et al. investigated tantalum-doped 0.94BNT0.06BT lead-free piezoelectric ceramics.45 Due to the occupation of tantalum on B-site as a donor, the material properties thus get softer electrically. The piezoelectric constants are slightly improved; however, the desirable working temperature for a piezoelectric ceramic is reduced. With increasing tantalum content, the antiferroelectric phase zone gets broader. The partial substitutions of analogous ions for A-site or B-site ions of BNTBT, such as Na substituted by Li or Ag , Bi 3 substituted by Y 3 , Ba 2 substituted by Sr 2 , Ti 4 substituted by Zr 4 or Hf 4 , have been investigated in order to obtain a solid solution with enhanced piezoelectric properties.4650,65,66 In the 1xyBNTxBTyBLT system (BLT stands for Bi0:5 Li0:5 TiO3 , the ceramics close to the MPB (x 0:06, y 0:075) exhibit the optimum piezoelectricity but the lowest Td .46 In the

(1xBNTxBa(Ti0:942 Zr0:058 O3 system, phase transition from rhombohedral to tetragonal was observed with increasing x in the range from 3 to 12 mol%, indicating the existence of MPB in this system.49 The maximum value of piezoelectric constant d33 of 147 pC/N was obtained for the ceramics with the composition x 0:09 near the MPB region.

3.3. BNTBKTBT system

The ternary BNTBKTBT system has also been widely investigated due to relatively high Curie temperatures and large piezoelectric properties near the rhombohedraltetragonal MPB. Wang et al. investigated the eects of amount of BKT on the electrical properties and crystal structure of (0:95x)BNTxBKT0.05BT ceramics.52 During sintering, the incorporated BKT diuses into the BNTBT lattice to form a solid solution, but changes the crystal structure from rhombohedral to tetragonal symmetry at higher BKT amounts. The incorporation of 5 mol% BKT enhanced the piezoelectric properties signicantly. The properties of 0.90BNT0.05BKT0.05BT composition are good enough to replace PZT in certain applications such as ultrasonic wire-bonding, transducers and accelerometers.67,68 Li et al. investigated BNTBKTBT system by keeping the BKT and BT ratio constant.53,54,69 The MPB between rhombohedral and tetragonal exists in the range of 0:024 x 0:030 for 15xNBT 4xKBTxBT system and 0:025 y 0:035 for 1 3y NBT2yKBTyBT system at room temperature. The compositions near the MPB have relatively high piezoelectric due to the coexistence of rhombohedral and tetragonal phases. Figure 9 depicts the MPB phase diagram of the ternary BNT BKTBT system based on their XRD results and other references.69 Another report described the Co2 O3 -added BNTBKTBT system.55 The dependence of the valence state of Co cations on the Co2 O3 addition impacts on the microstructure, depolarization temperature and electrical properties of the ceramics signicantly. The Td is elevated to 157  C for 0.5 mol% Co2 O3 addition; and the Qm reaches a maximum of 626 at 1.5 mol% Co2 O3 addition. Further enhanced performance was found in Li-modied BNTBKTBT system. Lin et al. reported that the multicomponent lead-free piezoelectric ceramics [Bi1z (Na1xyz Kx Liy ]0:5 Baz TiO3

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Fig. 9. MPB phase diagram of BNTBKTBT ternary system.69 Source: Reprinted with kind permission from Springer ScienceBusiness Media.

exhibited good piezoelectric performances and strong ferroelectricity.56 The maximum d33 of 205 pC/N was obtained for x=y=z 0:15/0.075/0.02, the high depolarization temperature of this composition was found to be 210  C.

KNN is a solid solution of ferroelectric KNbO3 and antiferroelectric NaNbO3 .70 Both end members of the solid solution are orthorhombic at room temperature. Pure KNN ceramics sintered by the conventional solid-state reaction in air exhibit a high Curie temperature (TC = 420  C), a good ferroelectricity (Pr 33 C/cm 2 , while poor piezoelectricity (d33 80 pC/N) and bulk density.71 The obstacles of the processing for KNN-based ceramics is largely due to the instability of the KNN phase and volatility of the alkali oxides sintering at high temperatures, which make it dicult to obtain high density. Numerous studies have been carried out in order to improve the piezoelectric properties of KNNbased ceramics, especially following Saito et al. 2004 Nature paper.72 The Chinese researchers account for a large proportion of this area. Some typical physical properties for KNN-based ceramics published by Chinese researchers are summarized in Table 4.

4.1. The optimizations of the processing for KNN-based ceramics

To suppress the high volatilization of alkali metal oxides at a high temperature during sintering, Zhen et al. designed a double crucible method, as shown in Fig. 10, to calcinate and sinter the ceramic samples in atmospheric powder in sealed crucibles.73 It was found that the density increased greatly within a narrow temperature range. On the other hand, alkali

4. Alkaline Niobate and Related Materials

The alkaline niobates (K1x Nax NbO3 (KNN)based ceramics are considered as one of the most promising candidates for lead-free piezoceramics.
Table 4. Compositions K0:48 Na0:52 NbO3 K0:5 Na0:5 NbO3 (SPS) K0:5 Na0:5 NbO3 1 mol% CuO K0:5 Na0:5 NbO3 0.75 mol% K5:4 Cu1:3 Ta10 O29 K0:5 Na0:5 NbO3 1 wt% K4 CuNb8 O23 0.92Na0:535 K0:48 NbO3 0.08LiNbO3 0.92Na0:535 K0:48 NbO3 0.08LiNbO3 (domain engineering) (K0:55 Na0:45 0:965 Li0:035 Nb0:80 Ta0:20 O3 0.948K0:5 Na0:5 NbO3 0.052LiSbO3 K0:38 Na0:58 Li0:04 Nb0:91 Ta0:05 Sb0:04 O3 0.91K0:5 Na0:5 NbO3 0.09AgSbO3 0.75 mol% MnO2 K0:42 Na0:52 Li0:04 Ag0:02 Nb0:91 Ta0:05 Sb0:04 O3 (K0:47 Na0:47 Li0:06 0:985 Bi0:005 NbO3 0.98Na0:475 K0:475 Li0:05 NbO3 0.02Bi0:48 Na0:48 Ba0:04 TiO3 0.97Na0:5 K0:5 NbO3 0.03Bi0:5 Na0:5 TiO3 0.9825K0:5 Na0:5 NbO3 0.0175BiScO3 0.94K0:5 Na0:5 NbO3 0.06Ba(Zr0:05 Ti0:95 O3 0.94K0:5 Na0:5 NbO3 0.06BaTiO3 1 mol% CuO

Dielectric and piezoelectric properties of KNN-based ceramics. "r $ 600 606 360 d33 (pC/N) kp (%) kt (%) TC (  C) TOT (  C) References 160 148 82 90 100 280 324 262 286 306 216 263 185 328 195 253 234 193 47 38.9 39 41 40 48.3 53 51 48 44 45.3 43 48 43 48 49 43 47 46 $ 410 395 421 383 475 325 385 337 215 353 455 415 375 351 318 314 $ 204 201 206 $ 50 40 35 $ 40 114 10 141 100 $ 30 $ 30 97 75 98 99 80 89 86 100 101 102 103 104 93 105 106 107 108 109

1290 1372 1327 1400 1478 1020 702 $ 1000 1191 230

49 43 45

49 48 40

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Fig. 10. Schematic illustration showing how to use double crucibles for the normal sintering of KNN-based ceramics.73 Source: Reprinted with permission from John Wiley and Sons.

elements were added in excessively to compensate their losses at high temperature. Enhanced piezoelectric properties are obtained for the 0.058LiNbO3 0.942Na0:535 K0:480 NbO3 ceramics by excessively adding alkali metal oxide (TC 490  C, d33 314 pC/N, kp 41:2%).74 The SPS method is suitable for the improvement of the density of KNN-based ceramics because of its advantages of a rapid sintering process and a short soaking time.7578 Post-annealing in air is always required to reduce conductivity due to oxygen deciency. Li et al. used SPS method to prepare Na0:5 K0:5 NbO3 ceramics, achieved > 99% relative density and nearly twice the d33 value of conventionally sintered KNN ceramics (d33 148 pC/N).75 The incorporation of liquid phase sintering aids, like K4 CuNb8 O23 , K5:4 Cu1:3 Ta10 O29 and CuO, are also used to reduce sintering temperature and promote the densication for KNN-based ceramics, giving a larger relative density > 96%.7981 It should be noted that copper-compound sintering aids make KNN-based ceramics become \hard," and the mechanical quality factor Qm increased largely. Besides, after the addition of copper-compound sintering aids, both TC and TOT decrease with the PE loop becoming constricted. Moreover, ZnO, CdO, Sc2 O3 and SnO2 can improve the sintering behaviors, while the addition of oxides, like CeO2 , Y2 O3 and WO3 , severely inhibit sintering.82 MnO2 lowers "r and tan , and improves Qm and kp .83,84 The addition of Bi2 O3 increases the melting point of the system and raises the sintering temperature of K0:5 Na0:5 NbO3 ceramics as well.85 Recently, Wang et al. proposed a general approach, domain engineering, toward piezoelectric response enhancement in KNN-based piezoelectric ceramics.86 A high d33 of 324 pC/N was obtained for the 0.92(Na0:535 K0:48 NbO3 0.08LiNbO3 ceramics,

(a)

(b) Fig. 11. (a) The piezoelectric coecient d33 as well as the TOT of (1x)(Na0:535 K0:48 NbO3 xLiNbO3 ceramics as a function of LiNbO3 content, after both the rst and second poling; (b) Comparison of the PE hysteresis loop for the sample with x 0:080 after the rst and second poling.86 Source: Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.

with a second poling treatment after the rst poling and room temperature aging for two months (Fig. 11). A mechanism corresponding to details of spontaneous polarization change in the domain level was proposed, concerning the combined eect of the migration of oxygen vacancies, and interaction between defect dipoles and spontaneous polarization inside the domains. This work is a successful example of domain engineering applied to lead-free piezoceramics. In addition, Du et al. reported a new approach to further improve piezoelectric properties of KNNbased ceramics.87 They pointed out that the optimum poling temperatures of KNN-based ceramics should be chosen near the PPT temperatures.

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Piezoelectric constant d33 of 0.93K0:5 Na0:5 NbO3 0.07LiNbO3 ceramics increases from 210 to 274 pC/ N by selecting optimum poling temperature.

4.2.2. Eects of B-site ions substitution on KNN-based ceramics

Tantalum and antimony have been widely used as dopants in the B-site ions substitution on the KNN-based ceramics.110114 Generally speaking, both tantalum and antimony doping hinder abnormal grain growth and decrease both TC and TOT transition temperature, while increasing the rhombohedral to orthorhombic PPT temperature TRO . It should be noted that for the (Na0:52 K0:48 )(Nb1y Sby ) O3 (NKNSy ) ceramics, TRO can be tuned to near room temperature at y ! 0:09 by the substitution of Sb 5 , leading to optimum piezoelectric properties of d33 230 pC/N, as shown in Fig. 12.114 The existence of successive PPT above room temperature makes the samples exhibit dierent thermal stability characteristics from previously reported KNN-based ceramics.

4.2. Eects of doping on KNN-based ceramics

A lot of research works have been explored to enhance the piezoelectric properties of KNN-based ceramics by composition design. All of these studies obtained enhanced properties mainly by shifting the orthorhombic to tetragonal PPT temperature TOT to slightly above or below room temperature. It is believed that the enhancement of the piezoelectric properties in PPT-based ceramics results from a combination of a \softening" the crystal lattice and increased alignment of ferroelectric domains following poling due to the coexistence of two phases.17 However, the piezoelectric properties exhibit poor temperature stability in most modied KNN-based ceramics.

4.2.1. Eects of A-site ions substitution on KNN-based ceramics

The researches by A-site doping of KNN-based ceramics are mainly focused on the addition of Li , Ag , Bi 3 , and alkaline-earth AE 2 (AE Mg, Ca, Sr, Ba) ions, in which Li modied KNN ceramics are widely studied.74,8894 Generally speaking, Li doping decreases the TOT to room temperature at about 6 mol% A-site substitution and increases TC while also improving densication and achieving relative high piezoelectric properties (d33 > 200 pC/N). There are some reports about Ag substitution for A-site of the (K0:5 Na0:5 1x AgxNbO3 ceramics.90,91 The results from Xu et al. show that after the addition of AgNbO3 , both TC and TOT decrease slightly, and the electrical properties of the ceramics with x 0:10 are found to be optimum: d33 135 pC/N, kp 0:43, kt 0:46, TC 394  C.90 However, for the Ag and Li co-modied K0:5 Na0:5 NbO3 ceramics, Ag substitution largely increases the Curie temperature (TC > 476  C) while decreasing TOT , and exhibits good piezoelectric properties (d33 176220 pC/N).95,96 Du et al. found that Li and Bi 3 co-modied KNN ceramics can possess not only high Curie temperature (TC 455  C) and piezoelectric properties (d33 185 pC/N), but also as low as possible TOT (10  C), giving good temperature stability of piezoelectric properties.93

4.2.3. Eects of both A-site and B-site ions substitution on KNN-based ceramics
Currently, A-site and B-site ions co-modication is the most investigated approach to improve the piezoelectric properties of KNN-based Ceramics. The B-site ions Nb 5 can be substituted by Ta 5 or/and Sb 5 ions, while the A-site is doped by Li or/and Ag .101,104,115121 On the other hand, there are lots of researches chosen alkaline earth ions AE 2 for A-site while Ti 4 for B-site substitutions.122125 Recently, there are some reports that used both trivalent ions for A-site and B-site dopants, such as Bi 3 for A-site, while Fe 3 , Sc 3 , Al 3 for B-site.107,126128

Fig. 12. (Color online) Phase transition temperatures changing as a function of the Sb content y for NKNSy ceramics.114 Source: Reprinted with permission from John Wiley and Sons.

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LiTaO3 -doped KNN ceramics exhibits a coexistence of orthorhombic and tetragonal phases at 45 mol% of LiTaO3 accompanied by enhancement of piezoelectric properties; the piezoelectric coecient d33 have been reported in the range of 200265 pC/N.129 The introduction of LiSbO3 into the KNN solid solution decreases slightly TC , but greatly shifts TOT to room temperature, reaching a maximum (d33 > 260 pC/N) at approximately 5 mol % of LiSbO3 content. 101;121 Wu et al. studied the Li , Ag and Ta 5 co-modied KNN ceramics, achieved enhanced electrical properties d33 263 pC/N and good aging characteristics.104 Lin et al. prepared \softened" KNN ceramics by the addition of AgSbO3 , and obtained excellent piezoelectric properties (d33 130216 pC/N).103 AETiO3 doping of KNN produces relaxor behavior. Moreover, the orthorhombic to tetragonal phase transition temperature in KNN can be eectively lowered by addition of CaTiO3 .125,130 Wu et al. found that CaTiO3 -modied [(K0:5 Na0:5 0:94 Li0:06 ] (Nb0:94 Sb0:06 O3 ceramics possessed good electrical properties (d33 252 pC/N and kp 49%) and improved temperature stability for the PPT below room temperature.125 Chang et al. observed that adding MgTiO3 and BaTiO3 to KNN reduced density and deteriorated electrical properties, while adding CaTiO3 and SrTiO3 can promote densication and optimize electrical properties.131 Bismuth containing compounds, such as K0:5 Na0:5 NbO3 BiMeO3 (Me 3 Fe 3 , Sc 3 , Al 3 , K0:5 Na0:5 NbO3 BNT solid solutions are other types of KNN-based lead-free piezoceramics.105107,127,132134 The 1 xK0:5 Na0:5 NbO3 xBiScO3 ceramics at x 0:0175 exhibit excellent electrical properties d33 253 pC/N.107

Li -doped KNN ceramics, but not for pure KNN ceramics. Zeng et al. and Wang et al. studied the eects of KLN on the phase structure, dielectric and piezoelectric properties of KNN ceramics.136,137 The results showed that the piezoelectric properties of KNN ceramics modied by small amount of KLN were improved. The addition of KLN markedly increased TC , but greatly shifted TOT down to near room temperature. Small amount of KLN decreased the amount of defects, thus the remnant polarization increased and the coercive eld decreased markedly. A coexistence of the orthorhombic and tetragonal phases was identied at approximately 0:12 x 0:18 for the 1 x(K0:48 Na0:52 NbO3 (x/5.15) K2:9 Li1:95 Nb5:15 O15:3 ceramics (KNNKLN100x).137 The ceramics with x 0:16 exhibited excellent piezoelectric properties: d33 235 pC/N, kp 41:6%, TC 473  C, TOT 53  C, "r 728, tan  0:02. Moreover, the KNNKLN100x ceramics also have an excellent thermal stability in the severe aging test up close to their Curie temperatures, as shown in Fig. 13.

5. Bismuth Layer-Structured Materials

The bismuth layer-structured ferroelectrics (BLSFs) with general formula Bi2 An1 Bn O3n3 consist of nperovskite layers (An1 Bn O3n1 2 sandwiched between bismuth oxygen sheets (Bi2 O2 2 . A is a mono-, di- or tri-valent ions or a mixture of them, B is a combination of cations well suited to form an octahedron, and n can be 1, 2, 3, 4 or the mixture

4.2.4. Eect of tungsten bronze compounds doping on KNN-based ceramics

Though many solid solutions of KNN with other ferroelectrics or nonferroelectrics have been studied, there is little work on establishing phase diagrams of KNN with tungsten bronze compounds (TBC), like potassium lithium niobate (KLN) with stued tungsten bronze structure. It was reported that KLN phase began to appear at x 0:08 in 1 xK0:5 Na0:5 NbO3 xLiNbO3 solid solution, and the piezoelectric properties decreased markedly.135 However, the conclusion may be suitable for

Fig. 13. (Color online) (a) Thermal annealing temperature dependence of d33 and tan  determined at 10 kHz of the KNNKLN100x ceramics with x 0:16; (b) the variation of TC and TOT as a function of x.137

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of the adjacent them. So far, there are total ve types, which are Bi3 TiNO9 -based, Bi4 Ti3 O12 based, MBi2 N2 O9 -based, MBi4 Ti4 O15 -based, and the intergrowth bismuth layer-structured ferroelectrics (iBLSF), where M is Sr 2 , Ca 2 , Ba 2 , (Bi0:5 Na0:5 2 , (Bi0:5 K0:5 2 , respectively, N is Nb 5 , Ta 5 , respectively. BLSFs are characterized by their low dielectric constant, low dielectric dissipation factor, high Curie temperature and large anisotropy in the electromechanical coupling factor. Therefore, the BLSF ceramics are considered as superior candidates for high temperature piezoelectric applications. Especially for some demanding applications with work temperature above 600  C, while BLSF ceramics show good stability of d33 at elevated temperature.138141 However, owing to its two-dimensional orientation restriction on the permissible rotations of the spontaneous polarization and low resistivity, the piezoelectric activities in BLSF ceramics are rather low. Therefore, a lot of works have been done on the doping eects in order to improve of physical properties and high temperature stability of BLSF ceramics. Doping in A-site, B-site and A/B-site normally takes place in the perovskite layers (An1 Bn O3n1 2 . It is seldom that doping takes place in the (Bi2 O2 2 layer structure. Rare elements like La 3 , Nd 3 , Sm 3 for A-site doping,
Table 5. Compositions CaBi2 NbTiO9 Ca0:9 (K, Ce)0:05 Bi2 NbTiO9 Bi4 Ti3 O12 Bi4 Ti3 O12 4%mol Nb2 O5 Bi4 Ti2:98 V0:02 O12:01 Bi4 Ti2:975 W0:025 O12:025 0.2 wt% Cr2 O3 Bi3:84 Nd0:16 Ti2:98 V0:02 O12:01 Bi3:25 La0:75 Ti2:92 Mn0:08 O12 Bi3:5 Nd0:5 Ti3 O12 Na0:5 Bi4:5 Ti4 O15 Na0:5 Bi4:5 Ti4 O15 0.5 wt% CeO2 Na0:5 Bi4:5 Ti4 O15 0.3 wt% CoO CaBi4 Ti4 O15 CaBi4 Ti3:975 W0:025 O15 Ca1x Srx Bi4 Ti4 O15 1.5 mol% MnO2 CaBi4 Ti3:95 V0:05 O15 CaBi3:75 Nd0:25 Ti4 O15 Bi7 Ti4 NbO21 Bi6:25 La0:75 Ti4 NbO21

Nb 5 , V 5 , W 6 for B-site doping and their combination for co-doping are mainly investigated. Some of these doping eects on physic properties of BLSF ceramics are listed in Table 5. From Table 5, it can be seen that A-site doping is more eective for the d33 or Pr enhancement than that of B-site doping. Li et al. reported that the solid solubility of A-site has crucial inuence than that of B-site.154 B-site doping can signicantly increase resistivity, leading to enhanced d33 by enabling poling at high temperature and high electric eld, particularly for Bi4 Ti3 O12 ceramics. Zeng et al. reported that both V 5 and W 6 doping increase the conductivity of CaBi4 Ti4 O15 , which indicate that CaBi4 Ti4 O15 ceramics show an n-type conductivity.149 It is dierent from the conductivity mechanism of Bi4 Ti3 O12 . Wang et al. reported that B-site cobalt modication signicantly enhanced the piezoelectric activity of Na0:5 Bi4:5 Ti4 O15 piezoelectric ceramics.139 Thermal annealing studies demonstrated that high temperature piezoelectric applications are possible up to 500  C in this cobaltmodied BLSF ceramics. Yu et al. investigated the three-dimensional domain structure and the variation of local elasticity on Nb-doped Bi4 Ti3 O12 ceramics by Scanning Probe Microscopy in a piezoresponse mode and low frequency acoustic mode, respectively.155 In acoustic mode, the 90  domain structures contribute strongly

Doping eects on BLSF piezoelectric ceramics. TC (  C) 936 868 672 630 674 658 648 "r 97 118 176 224 170 178 tan  (%) 1.5 0.18 0.95 0.23 2 1.8 d33 (pC/N) 5 16 4 18 20 22 Pr (C/cm 2 ) References 139 139 141 141 142 143 144 145 146 147 147 148 5.3 3.2 11.6 5.96 9.6 10 12 149 149 150 151 152 153 153

6 13.5 16.6 19

668 655 663 789 789 677 791 756 841 700

153 146 152 143 158 122 159 150 180

0.35 0.14 0.1 0.19 0.125 0.34 0.082

18 28 30 7 10 21 14 12 13 17

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(a)

(b)

(c)

Fig. 14. In-situ obtained images of Nb-doped Bi4 Ti3 O12 ceramics in piezoresponse mode; (a) Topography; (b) vertical piezoresponse image and (c) interal piezoresponse image.155 Source: Reprinted from Ref. 155. Copyright 2005, with permission from Elsevier.

to the image contrast because of the ferroelastic behavior (Fig. 14). However, the 180  domain patterns have little eect on it and the features observed do not correlate with the local elasticity. Yi et al. investigated the ferroelectric and piezoelectric properties of the La-doped intergrowth Aurivillius phase ceramics Bi5x Lax TiNbWO15 and Bi7x Lax Ti4 NbO21 (x 0:001.75).153,156159 It was found that the La doping is in favor of the domain switching. Enhanced ferro-/piezoelectric properties, such as 2Pr of 24.4 mC/cm 2 and d33 of 16.6 pC/N, were obtained in the Bi7x Lax Ti4 NbO21 ceramics. The high temperature electrical behavior indicates that the Bi5x Lax TiNbWO15 ceramics are semiconducting whereas the La-doped Bi7 Ti4 NbO21 ceramics are worthy to be further studied toward high temperature piezoelectric applications. Besides the doping eects, processing for ne powders, such as co-precipitate, solgel, led to enhanced densication or lowered dielectric loss of BLSF ceramics are also reported.160,161

6. Application of Texture Techniques in Lead-Free Piezoelectric Ceramics

Texture control of polycrystalline ceramics is a convenient and eective approach to improve the piezoelectric properties by tailoring the microstructure of ceramics without drastically changing the composition of the materials. Many methods have been used to prepare lead-free textured anisotropic ceramics, for example, hot processing, templated grain growth (TGG), screen-printing and other techniques. Hot processing is a traditional grain orientation textured technique, mainly including hot-forging, hot-pressing and hot-extrusion. Using hot processing, dislocation movements take place in the crystal

interior and grain boundary slides under external force at a high temperature, thus ceramic grain orientation arrangement is achieved. The hot processing technique has some disadvantages (e.g., complexity of the process), so that it has not been widely studied. Hao et al. prepared SrBi4 Ti4 O15 ceramics with a grain orientation degree of 85.7% via hot-forging technique.162 Zhang et al. prepared grain-orientated ferroelectric Bi3 NbTiO9 ceramics with remarkable anisotropy and doubled the value of d33 by hot-pressing technique.163 Reactive templated grain growth (RTGG) is a processing method in which reactive template particles are mixed with complementary reactants and aligned, and the product is formed in-situ during heat-treatment, preserving the orientation of the templates. RTGG technique includes two key steps, preparation of the anisotropic template grain (generally plate-like or needle-like) and the template alignment process such as tape casting or extrusion. As a versatile and eective processing technique for the fabrication of textured ceramics, TGG/RTGG method has been widely applied to texture perovskite-structure, tungstenbronze-structure and BLSF ceramics with enhanced piezoelectric properties. Some of the textured lead-free piezoceramics and their templates by TGG/RTGG are listed in Table 6. Screen printing, which has numerous advantages over tape casting including the realization of polymorphism and streamline production, is a high volume technique employed for fabricating thicklm electronic materials. But screen-printing technique has remained relatively neglected for processing textured ceramics. The use of screenprinting multilayer grain growth of texturing ceramics was proposed by Zeng et al. for textured CaBi4 Ti4 O15 BLSF with a grain orientation of 96%

A Review on Lead-Free Piezoelectric Ceramics Studies in China Table 6. Templates plate-like SrBi2 Nb2 O9 plate-like Bi4 Ti3 O12 Some of the textured lead-free piezoceramics and the templates used by TGG/RTGG. Textured composition SrBi2 Nb2 O9 0.8BNT0.2BKT 0.84BNT0.16BKT 0.94BNT0.06BT Bi4 Ti3 O12 0.94BNT0.06BT 0.7BNT0.2BKT0.1(Bi0:5 Li0:5 TiO3 0.92BNT0.08BT BNTBT K0:476 Na0:524 NbO3 CuO (K0:5 Na0:5 Nb0:97 Sb0:03 O3 Ba2 NaNb5 O15 Sr0:4 Ba0:6 Nb2 O6 Orientation degree (%) 68 90 70 95 92 87 60 69 58 99 97 80 86 d33 (pC/N) 195 134 241 299 300 98 146 218

283

References 168 169 170 171 172, 173 174 175 176 177 178 179 180 181

plate-like BNT plate-like Bi2:5 Na3:5 Nb5 O18 plate-like NaNbO3 acicular Ba2 NaNb5 O15 acicular Sr0:39 Ba0:48 K0:32 Nb2 O6

in 2005.164,165 Later, a screen-printing RTGG (sp-RTGG) has been used successfully for the perovskite-structure 0.94BNT0.06BT ceramics with a grain orientation of 92%.166,167 In recent years, strong magnetic eld has been used on the study of textured piezoelectric ceramics. Zhao et al. prepared 0.94BNT0.06BT textured ceramics using the pulsed strong magnetic eld and template grain growth.182 The gel-casting technique has been introduced to prepare green bodies. A pulsed strong magnetic eld was applied to induce internal grain orientation in the materials during the solidication of the green bodies. The orientation degree of the obtained textured ceramics reaches 76%, and the d33 is 123 pC/N.

7. Lead-Free Piezoelectric Single Crystals

Lead-free single crystals with optimal crystallographic orientation and domain engineering may have better piezoelectric properties when compared with its polycrystalline counterpart. While compared
Table 7. Single crystals Mn: BNT 0.7BNT0.3BKT BNTBT Mn: BNTBT K0:5 Na0:5 NbO3 Mn: K0:5 Na0:5 NbO3 0.95(K0:5 Na0:5 NbO3 0.05LiNbO3

with lead-free piezoelectric ceramics, the researches on lead-free single crystals are carried out insuciently until now. Recently, high piezoelectric and ferroelectric properties have been found in Mn-doped BNTBT single crystals, which were grown by a top-seeded solution method.183 The electrical resistivity, dielectric constant, ferroelectric and piezoelectric properties were all found to be notably enhanced by Mn-doping. Tetragonal and rhombohedral phases were found to coexist in the as-grown condition. An induced phase stability change from rhombohedral to tetragonal phases occurred under an electric-eld applied along the h001i direction.184 In the KNN-based system, 0.95(K0:5 Na0:5 NbO3 0.05LiNbO3 crystal was grown by the Bridgman method and the piezoelectric coecient d33 was found to be on the order of 204405 pC/N.185 Lin et al. prepared MnO2 -doped (K0:5 Na0:5 NbO3 single crystals by high-temperature solution method using K2 CO3 Na2 CO3 eutectic composition as ux.186 The MnKNN crystals were found to exhibit higher d33 and "r when compared with pure KNN crystal.

Properties of some of lead-free single crystals. "r d33 (pC/N) 120 160 283 486 160 270 405 kt (%) 49 50 55.6 45 61 TC (  C) 365 References 187 188 189 183 190 186 185

1230 240 730

393 416 426

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The smaller domain size (high domain density) in MnKNN crystals gave rise to the enhanced dielectric and piezoelectric properties. Some of the lead-free single crystals and their electrical properties are summarized in Table 7.

8. Summary
The current status of the research activities and progresses from China in the last decade were reviewed in this paper, including the compositions, dopants, sintering aids, processing, texturing and single crystal growths of the BT-based, BNT-based, KNN-based and BLSF-based lead-free materials. (1) BZTBCT system has excellent piezoelectric response, but the low Curie temperature and coercive eld Ec make it suitable for sensors and detectors; (2) BNTBKTBT system shows large piezoelectric constants, high curie temperature, high electromechanical coupling factors, which is suitable for high-power applications such as actuators and transducers. (3) The KNN family has the advantages of low density, high coupling coecient kt , lower acoustical impedance, and higher mechanical strength that make it suitable for high frequency transducers. But, the processing and sintering of KNN-based materials are still problematic, such as volatilization of K2 O and Na2 O, moisture sensitivity and density of the ceramics, more importantly the cost of Nb2 O5 and Ta2 O5 raw materials. (4) Some of the BLSF-based materials, especially the iBLSF, show a good stability and enhanced properties at elevated temperatures (> 600  C). It can be used as ceramics accelerometers, sensors, resonators and lters with high mechanical quality factor and low temperature coecient of resonances frequency. Till date, there is no one composition system of lead-free material that can replace PZT-based system, it is inevitable that specic features of individual lead-free material can be used to the required piezoelectric properties for each device. Future work on the research and development of lead-free piezoelectric materials seem to be focused on (1) compositional design, modeling and computation of new materials, the nature of piezoelectric activity with MPB and PPT, domain and domain wall engineering, control of grain size and grain boundary are the fundamentals; (2) high quality single crystals and their microstructure characterization (synchrotron and neutron diraction, spherical aberration corrected TEM/STEM), phase transition, domain

structure and the structure-property relations are the key for a better understanding and a path for searching new advanced lead-free materials; (3) textured grain orientation ceramics prepared by use of TGG and RTGG (sp-RTGG) methods that can be mass produced with high eciency; (4) thin lms, think lms and multilayered structure devices of lead-free ceramics is an important trend; (5) the methods and standard of piezoelectric measurement, the classications of lead-free materials should be taken into account from now on; (6) more importantly, international cooperation and team-work with multidiscipline are needed for the deep understanding of the piezoelectrics of lead-free materials, industrial applications, as well as the legislatures.

Acknowledgments
The authors are thankful to many of our colleagues and students, Prof. Qing-rui Yin, Prof. Tian-bao Wang, Mr. You-liang Wang, Mr. Pan Wang, Ms. Ya-li Li, Ms. Chang-wei Shao, Mr. Fa-qiang Zhang, Prof. Dong Wang, Dr. Qun-bao Yang, Dr. Xue-zheng Jing, Dr. Jiang-tao Zeng, Dr. Zhi-guo Yi, Dr. Ying Wang, Dr. Hong-zhang Song, Dr. Meng-jia Wu, Dr. Zheng-fa Li, Mr. Yu Zhao, Ms. Yi-lin Wang and Mr. Wen-jun Wu, for their invaluable contributions in various aspects of the related research programs. The nancial supports from The National Nature Science Foundation of China (NSFC, Nos. 50072039, 20151003, 50572113, 50932007), The Ministry of Sciences and Technology of China (MOST) through 973-projects (Nos. 2002CB613307, 2009CB623305) and 863Projects (Nos. 2001AA325070, 2006AA03Z430), The Science and Technology Commission of Shanghai Municipality (Nos. 05JC14079, 08JC1420500, 10XD1404700), and Shanghai Institute of Ceramics (No. SCX200409), are gratefully acknowledged.

References
1. T. B. Wang, L. E. Wang, Y. K. Lu and D. P. Zhou, J. Chin. Ceram. Soc. 14, 14 (1986). 2. T. B. Wang, M. Gao, L. E. Wang, Y. K. Lu and D. P. Zhou, J. Inorg. Mater. 2, 223 (1987). 3. T. B. Wang, L. E. Wang, Y. K. Lu and D. P. Zhou, J. Chin. Ceram. Soc. 15, 248 (1987). 4. D. Q. Xiao, J. Korean Phys. Soc. 32, S1798 (1998). 5. D. Q. Xiao, J. Adv. Dielectr. 1, 33 (2011). 6. P. Zheng, J. L. Zhang, S. F. Shao, Y. Q. Tan and C. L. Wang, Appl. Phys. Lett. 94, 032902 (2009).

A Review on Lead-Free Piezoelectric Ceramics Studies in China

285

7. H. Y. Tian, Y. Wang, J. Miao, H. L. W. Chan and C. L. Choy, J. Alloys Compd. 431, 197 (2007). 8. W. F. Liu and X. B. Ren, Phys. Rev. Lett. 103, 257602 (2009). 9. D. Z. Xue, Y. M. Zhou, H. X. Bao, C. Zhou, J. H. Gao and X. B. Ren, J. Appl. Phys. 109, 054110 (2011). 10. W. Li, Z. J. Xu, R. Q. Chu, P. Fu and G. Z. Zang, J. Am. Ceram. Soc. 93, 2942 (2010). 11. W. Li, Z. J. Xu, R. Q. Chu, P. Fu and G. Z. Zang, Phys. B-Condens. Matter 405, 4513 (2010). 12. W. Li, Z. J. Xu, R. Q. Chu, P. Fu and G. Z. Zang, Mater. Lett. 64, 2325 (2010). 13. S. W. Zhang, H. L. Zhang, B. P. Zhang and S. Yang, J. Alloys Compd. 506, 131 (2010). 14. H. X. Bao, C. Zhou, D. Z. Xue, J. H. Gao and X. B. Ren, J. Phys. D: Appl. Phys. 43, 465401 (2010). 15. W. Li, Z. J. Xu, R. Q. Chu, P. Fu and G. Z. Zang, Mater. Sci. Eng. B 176, 65 (2011). 16. S. W. Zhang, H. L. Zhang, B. P. Zhang and G. L. Zhao, J. Eur. Ceram. Soc. 29, 3235 (2009). 17. S. O. Leontsev and R. E. Eitel, Sci. Technol. Adv. Mater. 11, 044302 (2010). 18. X. Y. Deng, X. H. Wang, H. Wen, A. G. Kang, Z. L. Gui and L. T. Li, J. Am. Ceram. Soc. 89, 1059 (2006). 19. X. H. Wang, X. Y. Deng, H. Wen and L. T. Li, Appl. Phys. Lett. 89, 162902 (2006). 20. S. F. Shao, J. L. Zhang, Z. Zhang, P. Zheng, M. L. Zhao, J. C. Li and C. L. Wang, J. Phys. D: Appl. Phys. 41, 125408 (2008). 21. Z. Y. Shen and J. F. Li, J. Ceram. Soc. Jpn. 118, 940 (2010). 22. K. J. Zhu, J. H. Qiu, H. L. Ji and Y. S. Chen, J. Ceram. Process. Res. 11, 293 (2010). 23. W. Z. Lu, G. F. Fan, X. H. Wang and F. Liang, Jpn. J. Appl. Phys. 45, 8763 (2006). 24. X. X. Wang, H. L. W. Chan and C. L. Choy, J. Am. Ceram. Soc. 86, 1809 (2003). 25. Y. M. Li, W. Chen, J. Zhou, Q. Xu, H. Sun and R. X. Xu, Mater. Sci. Eng. B 112, 5 (2004). 26. M. J. Wu, Y. Q. Lu and Y. X. Li, J. Am. Ceram. Soc. 90, 3642 (2007). 27. Y. M. Li, W. Chen, J. Zhou, Q. Xu, X. Y. Gu and R. H. Liao, Phys. B-Condens. Matter 365, 76 (2005). 28. Z. P. Yang, B. Liu, L. L. Wei and Y. T. Hou, Mater. Res. Bull. 43, 81 (2008). 29. Y. R. Zhang, J. F. Li, B. P. Zhang and C. E. Peng, J. Appl. Phys. 103, 074109 (2008). 30. Y. M. Li, W. Chen, Q. Xu, J. Zhou, Y. Wang and H. J. Sun, Ceram. Int. 33, 95 (2007). 31. G. F. Fan, W. Z. Lu, X. H. Wang and F. Liang, Appl. Phys. Lett. 91, 202908 (2007).

32. C. R. Zhou, X. Y. Liu and W. Z. Li, Mater. Sci. Eng. B 153, 31 (2008). 33. C. R. Zhou, X. Y. Liu, W. Z. Li and C. L. Yuan, J. Alloys Compd. 478, 381 (2009). 34. D. M. Lin, D. Q. Xiao, J. G. Zhu and P. Yu, Appl. Phys. Lett. 88, 062901 (2006). 35. Y. J. Zhang, R. Q. Chu, Z. J. Xu, J. G. Hao, G. R. Li and Q. R. Yin, Phys. B-Condens. Matter 405, 1228 (2010). 36. Y. Q. Lu, Y. X. Li, D. Wang and Q. R. Yin, Ferroelectrics 358, 991 (2007). 37. C. G. Xu, D. M. Lin and K. W. Kwok, Solid State Sci. 10, 934 (2008). 38. X. X. Wang, H. L. W. Chan and C. L. Choy, Solid State Commun. 125, 395 (2003). 39. M. K. Zhu, L. Y. Liu, Y. D. Hou, H. Wang and H. Yan, J. Am. Ceram. Soc. 90, 120 (2007). 40. Q. Xu, M. Chen, W. Chen, H. X. Liu, B. H. Kim and B. K. Ahn, Acta Mater. 56, 642 (2008). 41. H. D. Li, C. D. Feng and W. L. Yao, Mater. Lett. 58, 1194 (2004). 42. H. D. Li, C. D. Feng and P. H. Xiang, Jpn. J. Appl. Phys. 42, 7387 (2003). 43. T. S. Zhou, R. X. Huang, X. Z. Shang, F. Peng, J. Y. Guo, L. Y. Chai and H. S. Gu, Appl. Phys. Lett. 90, 182903 (2007). 44. B. J. Chu, D. R. Chen, G. R. Li and Q. R. Yin, J. Eur. Ceram. Soc. 22, 2115 (2002). 45. R. Z. Zuo, C. Ye, X. S. Fang and J. W. Li, J. Eur. Ceram. Soc. 28, 871 (2008). 46. D. Lin, K. W. Kwok and H. L. W. Chan, Solid State Ionics 178, 1930 (2008). 47. L. Wu, D. Q. Xiao, D. M. Lin, J. G. Zhu and P. Yu, Jpn. J. Appl. Phys. 44, 8515 (2005). 48. D. M. Lin and K. W. Kwok, J. Mater. Sci.: Mater. Electron 21, 291 (2010). 49. C. Peng, J. F. Li and W. Gong, Mater. Lett. 59, 1576 (2005). 50. H. Y. Tian, D. Y. Wang, D. M. Lin, J. T. Zeng, K. W. Kwok and H. L. W. Chan, Solid State Commun. 142, 10 (2007). 51. Y. G. Wu, H. L. Zhang, Y. Zhang, J. Y. Ma and D. H. Xie, J. Mater. Sci. 38, 987 (2003). 52. X. X. Wang, X. G. Tang and H. L. W. Chan, Appl. Phys. Lett. 85, 91 (2004). 53. Y. M. Li, W. Chen, Q. Xu, J. Zhou, X. Y. Gu and S. Q. Fang, Mater. Chem. Phys. 94, 328 (2005). 54. Y. M. Li, W. Chen, Q. Xu, J. Zhou and X. Y. Gu, Mater. Lett. 59, 1361 (2005). 55. H. C. Hu, M. K. Zhu, F. Y. Xie, N. Lei, J. Chen, Y. D. Hou and H. Yan, J. Am. Ceram. Soc. 92, 2039 (2009). 56. D. M. Lin, D. Q. Xiao, J. G. Zhu and P. Yu, Phys. Status Solidi A 202, R89 (2005).

286

Y.-Q. Lu & Y.-X. Li

57. X. Y. Wang, C. L. Wang, M. L. Zhao, J. F. Wang, K. Yang and J. C. Li, Mater. Lett. 61, 3847 (2007). 58. Y. R. Zhang, J. F. Li and B. P. Zhang, J. Am. Ceram. Soc. 91, 2716 (2008). 59. Y. M. Li, W. Chen, Q. Xu, J. Zhou, H. J. Sun and M. S. Liao, J. Electroceram. 14, 53 (2005). 60. D. M. Lin, D. Q. Xiao, J. G. Zhu, P. Yu, H. J. Yan and L. Z. Li, Mater. Lett. 58, 615 (2004). 61. X. X. Wang, S. W. Or, X. G. Tang, H. L. W. Chan, P. K. Choy and P. C. K. Liu, Solid State Commun. 134, 659 (2005). 62. L. J. Liu and H. Q. Fan, J. Electroceram. 16, 293 (2006). 63. J. H. Shi and W. M. Yang, J. Alloys Compd. 472, 267 (2009). 64. X. Y. Zhou, H. S. Gu, Y. Wang, W. Li and T. S. Zhou, Mater. Lett. 59, 1649 (2005). 65. H. J. Yan, D. Q. Xiao, J. G. Zhu, P. Yu, L. Z. Li, D. M. Lin, G. Y. Li and W. Zhang, J. Wuhan Univ. Technol. Mater. Sci. Ed. 20, 97 (2005). 66. D. M. Lin, D. Q. Xiao, J. G. Zhu and P. Yu, J. Eur. Ceram. Soc. 26, 3247 (2006). 67. S. H. Choy, X. X. Wang, C. P. Chong, H. L. W. Chan, P. C. K. Liu and C. L. Choy, Appl. Phys. A 84, 313 (2006). 68. S. H. Choy, X. X. Wang, H. L. W. Chan and C. L. Choy, Appl. Phys. A 82, 715 (2006). 69. W. Chen, Y. M. Li, Q. Xu and J. Zhou, J. Electroceram. 15, 229 (2005). 70. W. R. Cook B. Jae and H. Jae, Piezoelectric Ceramics (Academic Press, London, 1971). 71. L. Egerton and D. M. Dillon, J. Am. Ceram. Soc. 42, 438 (1959). 72. Y. Saito, H. Takao, T. Tani, T. Nonoyama, K. Takatori, T. Homma, T. Nagaya and M. Nakamura, Nature 432, 84 (2004). 73. Y. H. Zhen and J. F. Li, J. Am. Ceram. Soc. 89, 3669 (2006). 74. P. Zhao, B. P. Zhang and J. F. Li, Appl. Phys. Lett. 90, 242909 (2007). 75. J. F. Li, K. Wang, B. P. Zhang and L. M. Zhang, J. Am. Ceram. Soc. 89, 706 (2006). 76. N. Liu, K. Wang, J. F. Li and Z. H. Liu, J. Am. Ceram. Soc. 92, 1884 (2009). 77. Z. Y. Shen, J. F. Li, K. Wang, S. Y. Xu, W. Jiang and Q. H. Deng, J. Am. Ceram. Soc. 93, 1378 (2010). 78. B. P. Zhang, J. F. Li, K. Wang and H. L. Zhang, J. Am. Ceram. Soc. 89, 1605 (2006). 79. D. M. Lin, K. W. Kwok and H. L. W. Chan, J. Appl. Phys. 103, 064105 (2008). 80. Q. Chen, L. Chen, Q. S. Li, X. Yue, D. Q. Xiao, J. G. Zhu, X. L. Shi and Z. Q. Liu, J. Appl. Phys. 102, 104109 (2007). 81. D. M. Lin, K. W. Kwok and H. L. W. Chan, J. Phys. D: Appl. Phys. 41, 045401 (2008).

82. R. Z. Zuo, J. Rodel, R. Z. Chen and L. T. Li, J. Am. Ceram. Soc. 89, 2010 (2006). 83. D. M. Lin, K. W. Kwok and H. L. W. Chan, J. Alloys Comp. 461, 273 (2008). 84. D. M. Lin, K. W. Kwok, H. Y. Tian and Hwlw Chan, J. Am. Ceram. Soc. 90, 1458 (2007). 85. H. L. Du, D. J. Liu, F. S. Tang, D. M. Zhu and W. C. Zhou, J. Am. Ceram. Soc. 90, 2824 (2007). 86. K. Wang and J. F. Li, Adv. Funct. Mater. 20, 1924 (2010). 87. H. L. Du, W. C. Zhou, F. Luo, D. M. Zhu, S. B. Qu and Z. B. Pei, Appl. Phys. Lett. 91, 202907 (2007). 88. H. L. Du, F. S. Tang, F. Luo, D. M. Zhu, S. B. Qu, Z. B. Pei and W. C. Zhou, Mater. Res. Bull. 42, 1594 (2007). 89. K. Wang, J. F. Li and N. Liu, Appl. Phys. Lett. 93, 092904 (2008). 90. C. Xu, D. Lin and K. W. Kwok, J. Mater. Sci.: Mater. Electron 19, 1054 (2008). 91. L. M. Zhang, B. P. Zhang, J. F. Li, X. N. Ding and H. L. Zhang, Rare Metal Mater. Eng. 36, 509 (2007). 92. H. L. Du, F. Luo, S. B. Qu, Z. B. Pei, D. M. Zhu and W. C. Zhou, J. Appl. Phys. 102, 054102 (2007). 93. H. L. Du, W. C. Zhou, F. Luo, D. M. Zhu, S. B. Qu and Z. B. Pei, Appl. Phys. Lett. 91, 182909 (2007). 94. Y. Wang, Y. X. Li, K. Kalantar-Zadeh, T. B. Wang, D. Wang and Q. R. Yin, J. Electroceram. 21, 629 (2008). 95. Y. Y. Wang, J. G. Wu, D. Q. Xiao, J. G. Zhu, P. Yu, L. Wu and X. A. Li, J. Alloys Compd. 459, 414 (2008). 96. Y. Y. Wang, J. H. Wu, D. Q. Xiao, W. J. Wu, B. Zhang, J. G. Zhu, P. Yu and L. Wu, J. Alloys Compd. 472, L6 (2009). 97. Y. J. Dai, X. W. Zhang and K. P. Chen, Appl. Phys. Lett. 94, 042905 (2009). 98. D. M. Lin, K. W. Kwok and H. L. W. Chan, Appl. Phys. Lett. 90, 232903 (2007). 99. D. M. Lin, K. W. Kwok and H. L. W. Chan, J. Appl. Phys. 103, 064105 (2008). 100. J. L. Zhang, X. J. Zong, L. Wu, Y. Gao, P. Zheng and S. F. Shao, Appl. Phys. Lett. 95, 022909 (2009). 101. G. Z. Zang, J. F. Wang, H. C. Chen, W. B. Su, C. M. Wang, P. Qi, B. Q. Ming, J. Du and L. M. Zheng, Appl. Phys. Lett. 88, 212908 (2006). 102. J. G. Wu, D. Q. Xiao, Y. Y. Wang, J. G. Zhu, L. Wu and Y. H. Jiang, Appl. Phys. Lett. 91, 252907 (2007). 103. D. M. Lin, K. W. Kwok and H. L. W. Chan, J. Appl. Phys. 106, 034102 (2009). 104. J. G. Wu, Y. Y. Wang, D. Q. Xiao, J. G. Zhu and Z. H. Pu, Appl. Phys. Lett. 91, 132914 (2007). 105. R. Z. Zuo and C. Ye, Appl. Phys. Lett. 91, 062916 (2007).

A Review on Lead-Free Piezoelectric Ceramics Studies in China

287

106. R. Z. Zuo, X. S. Fang and C. Ye, Appl. Phys. Lett. 90, 092904 (2007). 107. H. L. Du, W. C. Zhou, F. Luo, D. M. Zhu, S. B. Qu, Y. Li and Z. B. Pei, J. Appl. Phys. 104, 034104 (2008). 108. D. Lin, K. W. Kwok and H. W. L. Chan, Appl. Phys. Lett. 91, 143513 (2007). 109. D. Lin, K. W. Kwok and H. L. W. Chan, J. Appl. Phys. 102, 074113 (2007). 110. Q. A. Chen, Z. H. Peng, X. Yue, J. L. Zhu, D. Q. Xiao and J. G. Zhu, Ferroelectrics 404, 76 (2010). 111. Y. G. Lv, C. L. Wang, J. L. Zhang, L. Wu, M. L. Zhao and J. P. Xu, Mater. Res. Bull. 44, 284 (2009). 112. Y. G. Lv, C. L. Wang, J. L. Zhang, M. L. Zhao, M. K. Li and H. C. Wang, Mater. Lett. 62, 3425 (2008). 113. Y. Zhou, M. Guo, C. Zhang and M. Zhang, Ceram. Int. 35, 3253 (2009). 114. R. Z. Zuo, J. A. Fu, D. Y. Lv and Y. Liu, J. Am. Ceram. Soc. 93, 2783 (2010). 115. Y. F. Chang, Z. P. Yang, Y. T. Hou, Z. H. Liu and Z. L. Wang, Appl. Phys. Lett. 90, 232905 (2007). 116. Y. J. Dai, X. W. Zhang and G. Y. Zhou, Appl. Phys. Lett. 90, 262903 (2007). 117. D. Lin, K. W. Kwok and H. L. W. Chan, J. Appl. Phys. 102, 034102 (2007). 118. D. M. Lin, K. W. Kwok, K. H. Lam and H. L. W. Chan, J. Appl. Phys. 101, 074111 (2007). 119. B. Q. Ming, J. F. Wang, P. Qi and G. Z. Zang, J. Appl. Phys. 101, 054103 (2007). 120. Z. P. Yang, Y. F. Chang and L. L. Wei, Appl. Phys. Lett. 90, 042911 (2007). 121. S. J. Zhang, R. Xia, T. R. Shrout, G. Z. Zang and J. F. Wang, J. Appl. Phys. 100, 104108 (2006). 122. R. C. Chang, S. Y. Chu, Y. F. Lin, C. S. Hong and Y. P. Wong, J. Eur. Ceram. Soc. 27, 4453 (2007). 123. M. Jiang, X. H. Li, J. Liu, J. L. Zhu, X. H. Zhu, L. H. Li, Q. Chen, J. G. Zhu and D. Q. Xiao, J. Alloys Compd. 479, L18 (2009). 124. Y. T. Lu, X. M. Chen, D. Z. Jin and X. Hu, Mater. Res. Bull. 40, 1847 (2005). 125. J. G. Wu, D. Q. Xiao, Y. Y. Wang, W. J. Wu, B. Zhang, J. Li and J. G. Zhu, Scr. Mater. 59, 750 (2008). 126. M. H. Jiang, X. Y. Liu and G. H. Chen, Scripta Mater. 60, 909 (2009). 127. R. Z. Zuo, D. Y. Lv, J. Fu, Y. Liu and L. T. Li, J. Alloys Compd. 476, 836 (2009). 128. R. Z. Zuo, C. Ye and X. S. Fang, Jpn. J. Appl. Phys. 46, 6733 (2007). 129. P. Zhao, B. P. Zhang and J. F. Li, Appl. Phys. Lett. 91, 172901 (2007). 130. J. G. Wu, D. Q. Xiao, Y. Y. Wang, W. J. Wu, B. Zhang and J. G. Zhu, J. Appl. Phys. 104, 024102 (2008).

131. Y. F. Chang, Z. P. Yang, X. L. Chao, R. Zhang and X. R. Li, Mater. Lett. 61, 785 (2007). 132. H. L. Du, W. C. Zhou, D. M. Zhu and L. Fa, J. Am. Ceram. Soc. 91, 2903 (2008). 133. D. Lin, K. W. Kwok and H. W. L. Chan, Appl. Phys. A 91, 143513 (2007). 134. R. Z. Zuo, X. S. Fang, C. Ye and L. T. Li, J. Am. Ceram. Soc. 90, 2424 (2007). 135. Y. P. Guo, K. Kakimoto and H. Ohsato, Appl. Phys. Lett. 85, 4121 (2004). 136. J. T. Zeng, Y. H. Zhang, L. Y. Zheng, G. R. Li and Q. R. Yin, J. Am. Ceram. Soc. 92, 752 (2009). 137. Y. L. Wang, Y. Q. Lu, M. J. Wu, D. Wang and Y. X. Li, Int. J. Appl. Ceram. Technol. (2011), doi:10.1111/j.1744-7402.2011.02650.x. 138. C. M. Wang, S. J. Zhang, J. F. Wang, M. L. Zhao and C. L. Wang, Mater. Chem. Phys. 118, 21 (2009). 139. C. M. Wang, J. F. Wang, S. J. Zhang and T. R. Shrout, Phys. Status Solidi 3, 49 (2009). 140. H. X. Yan, C. G. Li, J. G. Zhou, W. M. Zhu, L. X. He and Y. X. Song, Jpn. J. Appl. Phys. 39, 6339 (2000). 141. X. P. Jiang, Q. Yang, C. Chen, N. Tu, Z. D. Yu and Y. M. Li, J. Inorg. Mater. 25, 1169 (2010). 142. Q. Y. Tang, Y. M. Kan, Y. G. Li, G. J. Zhang and P. L. Wang, Scr. Mater. 54, 2075 (2006). 143. J. G. Hou, Y. F. Qu, R. Vaish, K. B. R. Varma, D. Krsmanovic and R. V. Kumar, J. Am. Ceram. Soc. 93, 1414 (2010). 144. Q. Tang, Y. Kan, Y. Li, G. Zhang and P. Wang, Solid State Commun. 142, 1 (2007). 145. X. Q. Chen, F. J. Yang, W. Q. Cao, H. Wang, C. P. Yang, D. Y. Wang and K. Chen, Solid State Commun. 150, 1221 (2010). 146. M. Chen, Z. L. Liu, Y. Wang, C. C. Wang, X. S. Yang and K. L. Yao, Phys. Status Solidi A 200, 446 (2003). 147. L. Zhao, J. X. Xu, N. Yin, H. C. Wang, C. J. Zhang and J. F. Wang, Phys. Status Solidi A 2, 111 (2008). 148. C. M. Wang, L. Zhao, J. F. Wang, S. J. Zhang and T. R. Shrout, Phys. Status Solidi 3, 7 (2009). 149. J. T. Zeng, Y. Wang, Y. X. Li, Q. B. Yang and Q. R. Yin, J. Electroceram. 21, 305 (2008). 150. G. Li, L. Zheng, Q. Yin, B. Jiang and W. Cao, J. Appl. Phys. 98, 064108 (2005). 151. J. Zeng, Y. Li, Q. Yang and Q. Yin, Mater. Sci. Eng. B 117, 241 (2005). 152. J. Zeng, Y. Li, D. Wang and Q. Yin, Solid State Commun. 133, 553 (2005). 153. Z. G. Yi, Y. X. Li, Y. Wang and Q. R. Yin, Appl. Phys. Lett. 88, 152909 (2006). 154. Y. X. Li, Q. B. Yang, J. T. Zeng and Zh. G. Yi, J. Sichuan Univ. (Natural Science Edition) 42, 226 (2005).

288

Y.-Q. Lu & Y.-X. Li

155. H. F. Yu, H. R. Zeng, L. N. Zhang, R. Q. Chu, G. R. Li and Q. R. Yin, Mater. Lett. 59, 1538 (2005). 156. Z. G. Yi, Y. X. Li, Y. Wang and Q. R. Yin, Appl. Phys. Lett. 88, 162908 (2006). 157. Z. G. Yi, Y. X. Li, Z. Y. Wen, S. R. Wang, J. T. Zeng and Q. R. Yin, Appl. Phys. Lett. 86, 192906 (2005). 158. Z. G. Yi, Y. X. Li, J. T. Zeng, Q. B. Yang, D. Wang, Y. Q. Lu and Q. R. Yin, Appl. Phys. Lett. 87, 202901 (2005). 159. Z. G. Yi, Y. Wang, Y. X. Li and Q. R. Yin, J. Appl. Phys. 99, 114101 (2006). 160. Q. Y. Tang, Y. G. Li, Y. M. Kan, G. J. Mang and P. L. Wang, J. Inorg. Mater. 22, 595 (2007). 161. Z. H. Chen, J. F. Qiu, C. Liu, J. N. Ding and Y. Y. Zhu, Ceram. Int. 36, 241 (2010). 162. H. Hao, H. X. Liu and S. X. Ouyang, J. Wuhan Univ. Technol. Mater. Sci. Ed. 20, 52 (2005). 163. Z. Zhang, H. X. Yan, P. H. Xiang, X. L. Dong and Y. L. Wang, J. Am. Ceram. Soc. 87, 602 (2004). 164. J. T. Zeng, Y. X. Li, Q. B. Yang, X. Z. Jing and Q. R. Yin, J. Eur. Ceram. Soc. 25, 2727 (2005). 165. Y. X. Li, J. T. Zeng, X. Z. Jing and Q. R. Yin, J. Electroceram. 21, 314 (2008). 166. M. J. Wu, Y. X. Li, D. Wang and Q. R. Yin, Ceram. Int. 34, 753 (2008). 167. M. J. Wu, Y. X. Li, D. Wang, J. T. Zeng and Q. R. Yin, J. Electroceram. 22, 131 (2009). 168. C. W. Cui, J. L. Huang, L. H. Gao, X. H. Yang and X. Wang, in Advanced Materials and Processing, eds. Y. W. Chang, N. J. Kim and C. S. Lee (Trans Tech Publications Ltd, Stafa-Zurich, 2007), Vols. 2628, p. 239. 169. W. Zhao, H. P. Zhou and Y. K. Yan, Mater. Lett. 62, 1219 (2008). 170. F. Gao, C. S. Zhang, X. C. Liu, L. H. Cheng and C. S. Tian, J. Eur. Ceram. Soc. 27, 3453 (2007). 171. Y. K. Yan, H. P. Zhou, W. Zhao and D. Liu, J. Electroceram. 21, 246 (2008). 172. Y. M. Kan, P. L. Wang, Y. X. Li, Y. B. Cheng and D. S. Yan, J. Eur. Ceram. Soc. 23, 2163 (2003). 173. Y. M. Kan, P. L. Wang, Y. B. Cheng, Y. X. Li and D. S. Yan, Euro Ceram. VIII, Pts. 13 264{268, 1317 (2004).

174. W. Zhao, J. Ya, Y. Xin, L. E, D. Zhao and H. P. Zhou, J. Am. Ceram. Soc. 92, 1607 (2009). 175. W. K. Tam, K. W. Kwok, J. T. Zeng and H. L. W. Chan, J. Phys. D: Appl. Phys. 41, 045402 (2008). 176. F. Gao, R. Z. Hong, J. J. Liu, Y. H. Yao and C. S. Tian, J. Electroceram. 24, 145 (2010). 177. F. Gao, L. H. Cheng, R. Z. Hong, J. J. Liu, Y. H. Yao and C. S. Tian, J. Mater. Sci.: Mater. Electron. 19, 1228 (2008). 178. Y. F. Chang, S. F. Poterala, Z. P. Yang, S. TrolierMcKinstry and G. L. Messing, J. Mater. Res. 25, 687 (2010). 179. Y. F. Chang, S. F. Poterala, Z. P. Yang, S. TrolierMcKinstry and G. L. Messing, Appl. Phys. Lett. 95, 232905 (2009). 180. Q. X. Bao, L. H. Zhu, Q. W. Huang and J. Xv, Ceram. Int. 32, 745 (2006). 181. Q. W. Huang, L. H. Zhu, J. Xu, P. L. Wang, H. Gu and Y. B. Cheng, J. Eur. Ceram. Soc. 25, 957 (2005). 182. J. Zhao, F. J. Wang, W. Li, H. Li, D. X. Zhou, S. P. Gong, Y. X. Hu and Q. Y. Fu, J. Appl. Phys. 108, 073535 (2010). 183. Q. H. Zhang, Y. Y. Zhang, F. F. Wang, Y. J. Wang, D. Lin, X. Y. Zhao, H. S. Luo, W. W. Ge and D. Viehland, Appl. Phys. Lett. 95, 102904 (2009). 184. W. W. Ge, H. Cao, J. F. Li, D. Viehland, Q. H. Zhang and H. S. Luo, Appl. Phys. Lett. 95, 162903 (2009). 185. K. Chen, G. S. Xu, D. F. Yang, X. F. Wang and J. B. Li, J. Appl. Phys. 101, 044103 (2007). 186. D. B. Lin, Z. R. Li, S. J. Zhang, Z. Xu and X. Yao, J. Am. Ceram. Soc. 93, 941 (2010). 187. W. W. Ge, J. F. Li, D. Viehland and H. S. Luo, J. Am. Ceram. Soc. 93, 1372 (2010). 188. X. J. Yi, H. C. Chen, W. W. Cao, M. L. Zhao, D. M. Yang, G. P. Ma, C. H. Yang and J. R. Han, J. Cryst. Growth 281, 364 (2005). 189. Q. H. Zhang, Y. Y. Zhang, F. F. Wang, D. Lin, X. B. Li, X. Y. Zhao and H. S. Luo, J. Cryst. Growth 312, 457 (2010). 190. D. B. Lin, Z. R. Li, S. J. Zhang, Z. Xu and X. Yao, Solid State Commun. 149, 1646 (2009).