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Dielectric and piezoelectric properties of lead-free

crystals grown by the Bridgman method
Kai Chen, , Guisheng Xu, , Danfeng Yang, and , Xiaofeng Wang, and Junbao Li

Citation: Journal of Applied Physics 101, 044103 (2007); doi: 10.1063/1.2562464
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Published by the American Institute of Physics

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95共K0.6 mm/ h.5Na0.07兲 共 © 2007 American Institute of Physics.5Na0.95共K0.4– 0. However. Shanghai Institute of Ceramics. = 0. Li兲NbO3 ceramics. ducers. K2CO3. Then. and TC charged in the platinum crucibles.5兲NbO3 and LiNbO3 binary starting materials for crystal growth.1–3 Saito et al. electronic mail: gradient of 30– 50 ° C / cm was used near the solid-liquid in- gshxu@mail. The purpose of this paper is to grow 共1 − x兲 be an excellent candidate for lead-free piezoelectric materi.5Na0. and Xiaofeng Wang R&D Center of Synthetic Crystals. However. People’s Republic of China 共Received 9 October 2006.05LiNbO3 single crystal is a good lead-free piezoelectric material. good ferro. and the as PbTiO3 – PbZrO3 共PZT兲 are most used in acoustic trans. 关DOI: 10. until now. they were ceramics 共PZT-4兲. Recently. kt ⬃ 48%.5兲NbO3 – 0. Chinese Academy of Sciences. the increase in attention using flux methods. These materials were solid solution system. However. In the Bridgman method might have piezoelectricity that is even better than their tex. to environment protection results in an urgent demand to find no dopants were added to establish a composition with MPB some lead-free materials to replace PZT ceramics in different features. 0021-8979/2007/101共4兲/044103/4/$23.2562464兴 I. 044103-1 © 2007 American Institute of Physics . previous researches on lead oxide. The temperature a兲 Author to whom correspondence should be addressed. Chinese Academy of Sciences.5兲NbO3 – xLiNbO3 关共1 − x兲KNN-xLN兴 single crys- als. most studies of alkaline niobate Lead-based ferroelectric and piezoelectric materials such materials have concentrated on the ceramic form. and the obtained KNN crystals were always below applications due to their high content 共60%–70%兲 of toxic 3 mm in size.2 Meanwhile. 2兲 of 共1 − x兲KNN-xLN system. EXPERIMENT The obtained ceramics show excellent piezoelectric proper- ties. used different methods to synthesize compacted 共Na. II. 044103 共2007兲 Dielectric and piezoelectric properties of lead-free 0. large thickness electromechanical coupling factor kt = 61%. d33 ⬃ 416 pC/ N.05LiNbO3 crystals grown by the Bridgman method Kai Chen. the platinum crucibles tured ceramics counterpart since the optimal crystallographic were maintained at 1330 ° C for more than 10 h and then descended at the rate of 0. d33 ⬃ 245 pC/ N. single crystal form of these materials is reported rarely.05– 0.5Na0. and high Curie temperature. The orthorhombic-tetragonal and tetragonal-cubic phase transition temperatures of the single crystal appear at 192 and 426 ° C according to the dielectric constant versus temperature loops. which were sealed to sup- ⬃ 253 ° C. medical ultrasonic probes.5兲NbO3 – 0. People’s Republic of China Junbao Li Institute of Acoustics. These excellent properties show that the 0. piezoelectric properties. ders were calcined in air at 830 ° C for 2 h before being ezoelectricity very similar to those available from some PZT pressed at cold isostatic of 200 MPa. Li2CO3. and the 共001兲 plates show good piezoelectric properties with piezoelectric constant d33 as high as 405 pC/ N. com- compositions are at the vicinity of the morphotropic phase prising Na2CO3. k p ⬃ 61%. respectively.a兲 Danfeng Yang. KNN crystals mostly focused on their structures or optical electricity.sic.5Na0. and Nb2O5. Shanghai 201800. a great breakthrough was made in alkaline nio- bate ceramics. and Guo et al. INTRODUCTION orientation and domain engineering can be realized in single crystals.00 101. accepted 2 January 2007. were used as boundary 共MPB兲 of 共K0. ⫻共K0. The pow- Some textured Ta:KNN ceramics even exhibit the strong pi.05LiNbO3 have been grown by Bridgman method and their dielectric and piezoelectric properties were studied. With higher piezoelectric response.5兲NbO3 – 0. and low dielectric constant of 185 at room temperature. On the other hand.95共K0. Na1−x兲NbO3 single crystals were grown electromechanical fields. where the The oxide powders with purities better than 99.05LiNbO3 that is near the MPB 共x achieved when the ceramics were textured and/or Ta doped. K .5Na0. and TC ⬃ 460 ° C.1 It is anticipated that KNN-based single crystals press the volatilization of melts. it is difficult to obtain compacted ceramics of tals with the compositions near the MPB by using the Bridg- alkaline niobate in conventional oxide sintering method be. alkaline niobate properties while their piezoelectricity has never been inves- 共K .4–8 the x value did not surpass 40 mol %. JOURNAL OF APPLIED PHYSICS 101.95„K0. Guisheng Xu.5…NbO3 – 0. growth of 共1 − x兲KNN-xLN crystals. Beijing 100080. man growth technique and to investigate their dielectric and cause of their severe volatility at high temperature. published online 22 February 2007兲 Lead-free potassium sodium niobate piezoelectric single crystals substituted with lithium 0. solid actuators. and other Though some 共Kx .1063/1. they found that much mixed according to the composition formula of better piezoelectric and ferroelectric properties could be 0. Na兲NbO3 共KNN兲-based solid solutions are considered to terface in the growth furnace.9%.

and c = 3. Lattice parameters a = 3.3% below the temperature TO-T.05LN single crystal single crystal plates. Their dielectric properties were predominant. and 100 kHz兲. 1兲 from temperature TO-T to TC. b = 3.05LN crystals are shown in Fig. The x-ray diffrac- tion 共XRD兲 results 共Fig.044103-2 Chen et al.05LN single crystals at different frequencies. they are not typical relaxor ferroelectrics.05LN crystals is room temperature by using a ferroelectric tester 共Trek 664 1. an empirical expression was employed. X-ray diffraction pattern of the 0. piezoelectric measurements. 1. respectively. which is approximately consistent with the state of their unpoled ceramics counterpart. The crystal structures were determined by x-ray powder Therefore. Besides. and the ␥ value is between The piezoelectric constant d33 is measured with Berlincourt- 1 and 2. 3. were milk white and semitransparent before pol- quencies 共Fig. The two dielectric loss peaks appearing at ing and become transparent after poling. Two dielectric peaks appear at 192 and 426 ° C at all frequencies 共100 Hz. samples were polished and painted with silver typical relaxor ones. primary. 共Color online兲 Typical unpoled 共001兲 oriented 0.11 The logarithm of 共1 / ␧ − 1 / ␧max兲 was and antiresonance method with Agilent 4294A impedance plotted against the logarithm of 共T − tm兲 and the curves are analyzer. which shows that the normal ferroelectric property is system兲 at 10 Hz. 2兲 show that the crystals have pure perovskite structures and have an orthorhombic phase with- out second phase. after TC increases rapidly especially at low fre- ⫻ 0. The peaks at 192 and 426 ° C should be attributed to the phase transition of orthorhombic-tetragonal 共at TO-T兲 and tetragonal-cubic 共at TC兲. 4.24.1% at 100 kHz and does not exceed 2.95KNN–0. . the unpoled 0. 101. the dielectric loss at room temperature of the III. 5兲. Chinese Academy of Sciences. and reaches a peak near the Curie crystal boules. The ferroelectric hysteresis loops were measured at shown in Fig. The ␥ value of 0. Phys.95KNN–0.3 The crystals behave like relaxor ferroelectrics in that the dielectric constants decrease with the increase of frequencies. The electrome- and to the quadratic law valid for an ideal relaxor ferroelec- chanical coupling factor kt was determined by a resonance tric.95KNN–0. 1 kHz. 2. It can be seen that the position and half-width FIG. with the size of about 4 ⫻ 6 temperature. Before 1 1 共T − Tm兲␥ − = .95KNN–0. transitional ferroelectrics between typical normal ones and acterization. In order to determine which ones are paste on the sample surfaces.941 Å are calculated from the Bragg for- mula. 3. Appl.5 mm3.9 measured using an Agilent 4294A precision impedance ana- lyzer in the temperature range from 30 to 450 ° C. 共Colr online兲 Temperature dependence of the dielectric constant of of the transition peak at TC do not vary with frequencies.95KNN–0. powder.939 Å. For electrical char.05LN crystals are diffraction analysis using a Cu K␣ filter.10.95KNN–0. respectively. slowly increases from the We obtained some 共001兲-cut crystal plates 共Fig. 044103 共2007兲 FIG.05LN FIG. The curves of the temperature dependence of dielectric constants for unpoled 0. RESULT AND DISCUSSION crystals is as low as 1. On the other hand. The limiting values ␥ = 1 and ␥ = 2 correspond to the type quasistatic meter of ZJ-4A type made by Institute of Curie-Weiss law valid for the case of normal ferroelectric Acoustics. J. 10 kHz. These plates. the samples were poled by ␧ ␧max C 40 kV/ cm dc field at 140 ° C for 30 min within silicon oil. it can be said that 0.919 Å. where ␥ and C are all constants.

05LN single crystals in comparison with other fine lead-free materials.5关共Zr0. The increase of conductance accompanying the generation and 0. 180 and 410 ° C can be correlated to the orthorhombic. 共Color online兲 Loss of the unpoled 0.53兲兴O3 ce. 6兲.05LN single crystal does not show a typical movement of oxygen and potassium vacancies. This rapid remanent polarization 共Pr兲 were 2.05 ␮C / cm2 共average value兲. Because the ferroelectric polarization hysteresis loop 共Fig.5K0. Single crystal Ceramic Constant KNN-LN BNTK30a BNT-BTb KNN-LNc LF4Td TC 共°C兲 426 365 330 460 253 d33 共pC/N兲 405 160 160 240 416 kt 共%兲 61 49 ¯ 51 kp 61 Loss 共%兲 1.95KNN–0.95KNN–0.95KNN–0. c Reference 3. the crystals exhibit better piezoelectric properties.05LN single crystal at room 0. cation and annealing process should be done in future work cies is not evident in low temperature. The loop is crystal is grown in a sealed and anoxic atmosphere and po.52Li0.5兲NbO3 ceram- of potassium ion being small occupies the center of the oxy.13 properties of 0. which suggests that the leak- tassium oxide severely volatilizes at high temperature. For com- vacancies. where LF4T: textured 共K0. J. 4. ⫻共Nb0. single crystal and Pb关共Zn1/3Nb2/3兲兴0. potas. Phys.04兲 measured at different frequencies and temperatures.47Ti0. The coercive electric field 共Ec兲 and the tetragonal and tetragonal-cubic phase transitions.10Sb0. Hysteresis loops of 0. 5.4 ¯ a Reference 15. The result is sium and oxygen vacancies easily engender. It can be seen that the main piezoelectric ramics annealed in Ar atmosphere. The log共1 / ␧ − 1 / ␧max兲 as a function of log共T − Tm兲 at 100 kHz for FIG.2 kV/ mm 共average value兲 increase of loss with temperature seems to result from the and about 9.1 ¯ ¯ 8. ceramics or crystals.95KNN–0.4%. are listed as well. The crystals present the excellent pi- ezoelectric properties that are almost comparable with the TABLE I.1% – 8.05LN single crystal d Reference 1. the same parameters of some other lead-free structure systems such as 共1 − x兲Pb共In1/2Nb1/2兲O3 – xPbTiO3 perovskite-type ferroelectric materials. dielectric constant ␧ ionic conduction formed by oxygen vacancies is high even at and dielectric loss tan ␦. When oxygen ions to decrease the oxide vacancies. being relatively large occupy the corners of the octahedra. round shaped and not saturated. Since the radius in good agreement with the loop of 共Na0.86Ta0. 101. temperature.05LN single is due to the conduction effect of both oxygen and potassium crystal at room temperature are shown in Table I. and tan ␦ ⬃ 1. d33 ⬃405– 240 pC/ N.12. 044103 共2007兲 FIG.95KNN–0.95KNN–0. age current induced by oxide vacancies is large. The rapid increase of loss factor after TC tromechanical coupling factor kt of 0. ionic conduction formed by potassium vacan. 6. respectively. . Optimum piezoelectric constant d33. wave form at 10 Hz. FIG.04兲O3. Compared electric field of 25 kV/ cm applied using an amplified bipolar with the best results of the ceramics counterpart with the same compositions. Curie temperature TC and the elec- room temperature. Similar phenomena are found in some perovskite parison.44Na0.05LN.14 Some growth modifi- gen octahedra. ics with insufficient annealing time. b Reference 16.044103-3 Chen et al. Dielectric and piezoelectric properties of 0.95KNN–0. kt ⬃ 61% – 51%. Appl.05LN crystals are superior to those Ferroelectric measurement is carried out at a maximum of other lead-free piezoelectric single crystals.

S. 4121 共2004兲. Phys. these lead-free ma- 共K0. Ceram. 89. 1380 共1958兲. Zhang. 581 共1954兲. R. CONCLUSION M. Rev. Setter. F. 857 共2003兲. Kakimoto. Fan. Pan. Yin. The curves of temperature 11 G. Z. Q. 178 共1958兲. Phys. Growth 46. He. Phys. combinations of relaxor and normal ferroelectrics. 5 L. Yang. Phys. and H.52Li0. The to replace the PZT ceramics. Phys. Choi. 0.. Lett. Mater. method. Cryst. 044103 共2007兲 best results of the textured ceramics doped with Ta and Sb their high Curie temperature of 426 ° C. Ma. Am. 3. G. M. Li. 10 sition at about 190 ° C. P.04兲共Nb0.. Takatori. G. but the former have terials are suitable for some electromechanical applications the Curie temperature of 174 ° C higher than the latter. and L. Smolenski.05LN single crystals 1 may become excellent piezoelectric materials and potential Y. Park. Lett. 84 共2004兲. Wang. Jpn.044103-4 Chen et al. Phys. Yang. and Z. onal to cubic phase at 426 ° C. P. 96. and R. The 共001兲-cut crystals undergo the O-T phase tran.2 kV/ mm are J. Zhao.. P. G. M. Wang. Cryst. Guo. Pr 9. K. H. . K. 85. Growth 281. Appl. ous special shapes and orientations. Nature 共London兲 181. Newnham. Ferroelectr. Appl. Gen. 182905 共2005兲. Res. J. T. candidates to replace PZT ceramics even though the entire Nagaya. J. D. P. Sect. J. 2 piezoelectric parameters are not given here because of the Y. Chen. but nor. E. T. D. Theor. Agranovskaya. 26 共1970兲.44Na0. C. B. Yin. 364 共2005兲. Soc.05 ␮C / cm2 and Ec 2.05LN single crystals near MPB composi. 55 共1982兲. Phys. 38. Growth 275. 486 共2003兲. 3 E. Guo. Luo.95KNN–0. M. and N. Raevski et al. high d33 405 pC/ N as well as a high kt61%. Cryst. Considering 113 共2005兲. and the phase transition from tetrag. The loss increases 13 Y. Lett. rapidly after TC because of the coeffect of potassium and Bull. Q. W. Homma. Tani. H. T. Nakamura. F. 14 oxygen vacancies. 1658 共2001兲. 706 共2006兲. Crystallogr. W.1% at 100 kHz.. and J. J. respectively. M.. room temperature dielectric constants and loss are 185 and H. Sect. and M. Stroz. mal ferroelectric property is predominant. 4 G. The 15 X.95KNN–0. temporary difficulties in acquiring crystal samples with vari- 87. Soc. J. Hollenstein. 9 K.04兲O3. 44. Yang. E. Badurski and K. obtained from ferroelectric polarization hysteresis loop. 274 共1979兲. Takao. 1. 28. The single crystals show a 16 G. Diffr. Smolenski and A. above data indicate that 0. X. J. C. T. T. X. and D. Nomura. T. Duan. Cross. Glazer. Ohsato. 48. M. L. Damjanovic. I. A: Cryst. 32. Sov. Appl. Phys. 79. Kim. P. Saito.10Sb0. 6 IV. 434 共1976兲. A. Zhang. 101. Han. R. Cao. F. H. K. Pepinsky. Appl. W. H. J. Crystallogr.86Ta0. J. dependence of dielectric constants show that crystals are 12 H. Xu. Lett. Rep. Shiarane. tion were grown directly from their melt by the Bridgman 8 I. S. M. and H. Acta Crystallogr. Tech. Nonoyama. 7 M. Nature 共London兲 42. J. Uchino and S. A. Phys. Ahtee and A. Davis.