Ceramics based on (Na1/2B1/2)TiO3 are promising candidates for actuator applications because of large strains generated by an electric field-induced phase transition. For example, the (1−x)(Na1/2Bi1/2)TiO3-xSrTiO3 system exhibits a morphotropic phase boundary at x = 0.2–0.3, leading to high values of inverse piezoelectric constant d*33, which can be further improved by the use of single crystals. In our previous work, single crystals of (Na1/2B1/2)TiO3-SrTiO3 and (Na1/2B1/2)TiO3-CaTiO3 were grown by the solid state crystal growth technique. Growth in the (Na1/2B1/2)TiO3-SrTiO3 system was sluggish whereas the (Na1/2B1/2)TiO3-CaTiO3 single crystals grew well. In the present work, 0.8(Na1/2Bi1/2)TiO3-0.2(Sr1−xCax)TiO3 single crystals (with x = 0.0, 0.1, 0.2, 0.3, 0.4) were produced by the solid state crystal growth technique in an attempt to improve crystal growth rate. The dependence of mean matrix grain size, single crystal growth distance, and electrical properties on the Ca concentration was investigated in detail. These investigations indicated that at x = 0.3 the matrix grain growth was suppressed and the driving force for single crystal growth was enhanced. Replacing Sr with Ca increased the shoulder temperature Ts and temperature of maximum relative permittivity Tmax, causing a decrease in inverse piezoelectric properties and a change from normal to incipient ferroelectric behavior.
Rödel J, Jo W, Seifert KTP, et al. Perspective on the development of lead-free piezoceramics. J Am Ceram Soc 2009, 92: 1153–1177.
Koruza J, Bell AJ, Frömling T, et al. Requirements for the transfer of lead-free piezoceramics into application. J Materiomics 2018, 4: 13–26.
Reichmann K, Feteira A, Li M. Bismuth sodium titanate based materials for piezoelectric actuators. Materials 2015, 8: 8467–8495.
Hiruma Y, Imai Y, Watanabe Y, et al. Large electrostrain near the phase transition temperature of (Bi0.5Na0.5)TiO3-SrTiO3 ferroelectric ceramics. Appl Phys Lett 2008, 92: 262904.
Rout D, Moon KS, Kang SJL, et al. Dielectric and Raman scattering studies of phase transitions in the (100−x)Na0.5Bi0.5TiO3-xSrTiO3 system. J Appl Phys 2010, 108: 084102.
Acosta M, Jo W, Rödel J. Temperature- and frequency-dependent properties of the 0.75Bi1/2Na1/2TiO3-0.25SrTiO3 lead-free incipient piezoceramic. J Am Ceram Soc 2014, 97: 1937–1943.
Lee D, Vu H, Sun HY, et al. Growth of (Na0.5Bi0.5)TiO3-SrTiO3 single crystals by solid state crystal growth. Ceram Int 2016, 42: 18894–18901.
Sun HY, Fisher JG, Moon SH, et al. Solid-state-growth of lead-free piezoelectric (Na1/2Bi1/2)TiO3-CaTiO3 single crystals and their characterization. Mater Sci Eng: B 2017, 223: 109–119.
Fisher JG, Benčan A, Godnjavec J, et al. Growth behaviour of potassium sodium niobate single crystals grown by solid-state crystal growth using K4CuNb8O23 as a sintering aid. J Eur Ceram Soc 2008, 28: 1657–1663.
Krauss W, Schütz D, Mautner FA, et al. Piezoelectric properties and phase transition temperatures of the solid solution of (1−x)(Bi0.5Na0.5)TiO3-xSrTiO3. J Eur Ceram Soc 2010, 30: 1827–1832.
Yi JY, Lee JK, Hong KS. Dependence of the microstructure and the electrical properties of lanthanum-substituted (Na1/2Bi1/2)TiO3 on cation vacancies. J Am Ceram Soc 2002, 85: 3004–3010.
Jo W, Ollagnier JB, Park JL, et al. CuO as a sintering additive for (Bi1/2Na1/2)TiO3-BaTiO3-(K0.5Na0.5)NbO3 lead-free piezoceramics. J Eur Ceram Soc 2011, 31: 2107–2117.
Moon KS. Effect of Na2CO3 addition on grain growth behavior and solid-state single crystal growth in the Na0.5Bi0.5TiO3-BaTiO3 system. J Korean Powder Metall Inst 2018, 25: 104–108.
Lee DK, Vu H, Fisher JG. Growth of (Na0.5Bi0.5)TiO3-Ba(Ti1−xZrx)O3 single crystals by solid state single crystal growth. J Electroceramics 2015, 34: 150–157.
Le PG, Fisher JG, Moon WJ. Effect of composition on the growth of single crystals of (1−x)(Na1/2Bi1/2)TiO3-xSrTiO3 by solid state crystal growth. Materials 2019, 12: 2357.
Han HS, Hong IK, Kong YM, et al. Effect of Nb doping on the dielectric and strain properties of lead-free 0.94(Bi1/2Na1/2)TiO3-0.06BaTiO3 ceramics. J Korean Ceram Soc 2016, 53: 145–149.
Cao J, Wang YF, Li Z. Effect of La doping on the electrical behaviors of BNT-BT based ceramics. Ferroelectrics 2017, 520: 224–230.
Praharaj S, Rout D, Kang SJL, et al. Large electric field induced strain in a new lead-free ternary Na0.5Bi0.5TiO3-SrTiO3-BaTiO3 solid solution. Mater Lett 2016, 184: 197–199.
Moon KS, Kang SJL. Coarsening behavior of round-edged cubic grains in the Na1/2Bi1/2TiO3-BaTiO3 system. J Am Ceram Soc 2008, 91: 3191–3196.
Le PG, Jo GY, Ko SY, et al. The effect of sintering temperature and time on the growth of single crystals of 0.75(Na0.5Bi0.5)TiO3-0.25SrTiO3 by solid state crystal growth. J Electroceramics 2018, 40: 122–137.
Park JH, Kang SJL. Solid-state conversion of (94−x)(Na1/2Bi1/2)TiO3-6BaTiO3-x(K1/2Na1/2)NbO3 single crystals and their enhanced converse piezoelectric properties. AIP Adv 2016, 6: 015310.
Smolenskii GA, Isupov VA, Agranovskaya AI, et al. New ferroelectrics of complex composition. Soviet Physics Solid State 1961, 2: 2651–2654.
Zvirgzds JA, Kapostin PP, Zvirgzde JV, et al. X-ray study of phase transitions in ferroelectric Na0.5Bi0.5TiO3. Ferroelectrics 1982, 40: 75–77.
Jones GO, Thomas PA. Investigation of the structure and phase transitions in the novel A-site substituted distorted perovskite compound Na05Bi05TiO3. Acta Crystallogr Sect B 2002, 58: 168–178.
Dorcet V, Trolliard G. A transmission electron microscopy study of the A-site disordered perovskite Na0.5Bi0.5TiO3. Acta Mater 2008, 56: 1753–1761.
Gorfman S, Thomas PA. Evidence for a non-rhombohedral average structure in the lead-free piezoelectric material Na0.5Bi0.5TiO3. J Appl Crystallogr 2010, 43: 1409–1414.
Gorfman S, Glazer AM, Noguchi Y, et al. Observation of a low-symmetry phase in Na0.5Bi0.5TiO3 crystals by optical birefringence microscopy. J Appl Crystallogr 2012, 45: 444–452.
Rao BN, Fitch AN, Ranjan R. Ferroelectric-ferroelectric phase coexistence in Na1/2Bi1/2TiO3. Phys Rev B 2013, 87: 060102.
Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A 1976, 32: 751–767.
Hiruma Y, Nagata H, Takenaka T. Detection of morphotropic phase boundary of (Bi1/2Na1/2)TiO3-Ba(Al1/2Sb1/2)O3 solid-solution ceramics. Appl Phys Lett 2009, 95: 052903.
Hiruma Y, Nagata H, Takenaka T. Formation of morphotropic phase boundary and electrical properties of (Bi1/2Na1/2)TiO3-Ba(Al1/2Nb1/2)O3 solid solution ceramics. Jpn J Appl Phys 2009, 48: 09KC08.
Bai WF, Li LY, Li W, et al. Phase diagrams and electromechanical strains in lead-free BNT-based ternary perovskite compounds. J Am Ceram Soc 2014, 97: 3510–3518.
Bai W, Shen B, Zhai J, et al. Phase evolution and correlation between tolerance factor and electromechanical properties in BNT-based ternary perovskite compounds with calculated end-member Bi(Me0.5Ti0.5)O3 (Me = Zn, Mg, Ni, Co). Dalton Trans 2016, 45: 14141–14153.
Chung SY, Yoon DY, Kang SJL. Effects of donor concentration and oxygen partial pressure on interface morphology and grain growth behavior in SrTiO3. Acta Mater 2002, 50: 3361–3371.
Kang SJL, Lee MG, An SM. Microstructural evolution during sintering with control of the interface structure. J Am Ceram Soc 2009, 92: 1464–1471.
Jung YI, Yoon DY, Kang SJL. Coarsening of polyhedral grains in a liquid matrix. J Mater Res 2009, 24: 2949–2959.
Park YJ, Hwang NM, Yoon DY. Abnormal growth of faceted (WC) grains in a (Co) liquid matrix. Metall Mater Trans A 1996, 27: 2809–2819.
Markov II. Crystal-ambient phase equilibrium. In: Crystal Growth for Beginners: Fundamentals of Nucleation, Crystal Growth and Epitaxy, 2nd edn. Singapore: World Scientific, 2003: 1–76.
Kang SJL, Jung YI, Jung SH, et al. Interface structure-dependent grain growth behavior in polycrystals. In: Microstructural Design of Advanced Engineering Materials. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, 2013: 299–322.
Markov II. Crystal growth. In: Crystal Growth for Beginners: Fundamentals of Nucleation, Crystal Growth and Epitaxy, 2nd edn. Singapore: World Scientific, 2003: 181–351.
Peteves SD, Abbaschian R. Growth kinetics of solid-liquid Ga interfaces: Part I. Experimental. Metall Trans A 1991, 22: 1259–1270.
Markov II. Nucleation. In: Crystal Growth for Beginners: Fundamentals of Nucleation, Crystal Growth and Epitaxy, 2nd edn. Singapore: World Scientific, 2003: 77–180.
Peteves SD, Abbaschian R. Growth kinetics of solid-liquid Ga interfaces: Part II. Theoretical. Metall Trans A 1991, 22: 1271–1286.
Choi SY, Kang SJL. Sintering kinetics by structural transition at grain boundaries in barium titanate. Acta Mater 2004, 52: 2937–2943.
Zandvliet HJW, Gurlu O, Poelsema B. Temperature dependence of the step free energy. Phys Rev B 2001, 64: 073402.
Choi K, Hwang NM, Kim DY. Effect of grain shape on abnormal grain growth in liquid-phase-sintered Nb1−xTixC-Co alloys. J Am Ceram Soc 2002, 85: 2313–2318.
Fisher JG, Kang SJL. Strategies and practices for suppressing abnormal grain growth during liquid phase sintering. J Am Ceram Soc 2019, 102: 717–735.
Yang J, Yang QB, Li YX, et al. Growth mechanism and enhanced electrical properties of K0.5Na0.5NbO3-based lead-free piezoelectric single crystals grown by a solid-state crystal growth method. J Eur Ceram Soc 2016, 36: 541–550.
Van Beijeren H. Exactly solvable model for the roughening transition of a crystal surface. Phys Rev Lett 1977, 38: 993.
Moon KS, Rout D, Lee HY, et al. Solid state growth of Na1/2Bi1/2TiO3-BaTiO3 single crystals and their enhanced piezoelectric properties. J Cryst Growth 2011, 317: 28–31.
Kizuka T. Atomic processes of grain-boundary migration and phase transformation in zinc oxide nanocrystallites. Philos Mag Lett 1999, 79: 417–422.
Lee BK, Chung SY, Kang SJL. Grain boundary faceting and abnormal grain growth in BaTiO3. Acta Mater 2000, 48: 1575–1580.
Koo JB, Yoon DY. Abnormal grain growth in bulk Cu—The dependence on initial grain size and annealing temperature. Metall Mater Trans A 2001, 32: 1911–1926.
Merkle KL, Thompson LJ. Atomic-scale observation of grain boundary motion. Mater Lett 2001, 48: 188–193.
Merkle KL, Thompson LJ, Phillipp F. Collective effects in grain boundary migration. Phys Rev Lett 2002, 88: 225501.
Lee SB, Choi SY, Kang SJL, et al. TEM observations of singular grain boundaries and their roughening transition in TiO2-excess BaTiO3. Zeitschrift Für Met 2003, 94: 193–199.
Lee SB, Kim YM. Kinetic roughening of a Σ5 tilt grain boundary in SrTiO3. Acta Mater 2009, 57: 5264–5269.
Lee SB, Kim YM, Ko DS, et al. Kinetic roughening of a ZnO grain boundary. Appl Phys Lett 2010, 96: 191906.
Fisher JG, Choi SY, Kang SJL. Influence of sintering atmosphere on abnormal grain growth behaviour in potassium sodium niobate ceramics sintered at low temperature. J Korean Ceram Soc 2011, 48: 641–647.
An SM, Yoon BK, Chung SY, et al. Nonlinear driving force-velocity relationship for the migration of faceted boundaries. Acta Mater 2012, 60: 4531–4539.
Lee SB, Yoo SJ, van Aken PA. Roughening of a stepped GaN grain boundary with increasing driving force for migration. EPL Europhys Lett 2017, 120: 16002.
Rottman C, Wortis M. Statistical mechanics of equilibrium crystal shapes: Interfacial phase diagrams and phase transitions. Phys Rep 1984, 103: 59–79.
Jo W, Hwang NM, Kim DY. Effect of crystal shape on the grain growth during liquid phase sintering of ceramics. J Korean Ceram Soc 2006, 43: 728–733.
Wortis M. Equilibrium crystal shapes and interfacial phase transitions. In: Chemistry and Physics of Solid Surfaces VII. Berlin, Heidelberg: Springer Berlin Heidelberg, 1988: 367–405.
An SM, Kang SJL. Boundary structural transition and grain growth behavior in BaTiO3 with Nd2O3 doping and oxygen partial pressure change. Acta Mater 2011, 59: 1964–1973.
Rheinheimer W, Altermann FJ, Hoffmann MJ. The equilibrium crystal shape of strontium titanate: Impact of donor doping. Scripta Mater 2017, 127: 118–121.
West AR. Crystal defects, non-stoichiometry and solid solutions. In: Solid State Chemistry and its Applications, 2nd edn. Chichester: John Wiley & Sons Ltd., 2014: 87–124.
Luo YR. Comprehensive Handbook of Chemical Bond Energies. Boca Raton, FL: CRC Press, 2007.
Shvartsman VV, Lupascu DC. Lead-free relaxor ferroelectrics. J Am Ceram Soc 2012, 95: 1–26.
Jo W, Schaab S, Sapper E, et al. On the phase identity and its thermal evolution of lead free (Bi1/2Na1/2)TiO3-6 mol% BaTiO3. J Appl Phys 2011, 110: 074106.
Liu G, Dong J, Zhang LY, et al. Phase evolution in (1−x)(Na0.5Bi0.5)TiO3-xSrTiO3 solid solutions: A study focusing on dielectric and ferroelectric characteristics. J Materiomics 2020, 6: 677–691.
Weyland F, Acosta M, Vögler M, et al. Electric field-temperature phase diagram of sodium bismuth titanate-based relaxor ferroelectrics. J Mater Sci 2018, 53: 9393–9400.
Jo W, Dittmer R, Acosta M, et al. Giant electric-field-induced strains in lead-free ceramics for actuator applications—Status and perspective. J Electroceramics 2012, 29: 71–93.
Liu X, Shen B, Zhai JW. Designing novel sodium bismuth titanate lead-free incipient perovskite for piezoactuator applications. J Am Ceram Soc 2019, 102: 6751–6759.
Tu CS, Huang SH, Ku CS, et al. Phase coexistence and Mn-doping effect in lead-free ferroelectric (Na1/2Bi1/2)TiO3 crystals. Appl Phys Lett 2010, 96: 062903.
Ge WW, Luo CT, Zhang QH, et al. Ultrahigh electromechanical response in (1−x)(Na0.5Bi0.5)TiO3-xBaTiO3 single-crystals via polarization extension. J Appl Phys 2012, 111: 093508.
Lee HY, Wang K, Yao FZ, et al. Identifying phase transition behavior in Bi1/2Na1/2TiO3-BaTiO3 single crystals by piezoresponse force microscopy. J Appl Phys 2017, 121: 174103.
Craciun F, Galassi C, Birjega R. Electric-field-induced and spontaneous relaxor-ferroelectric phase transitions in (Na1/2Bi1/2)1−xBaxTiO3. J Appl Phys 2012, 112: 124106.
Hiruma Y, Nagata H, Takenaka T. Phase diagrams and electrical properties of (Bi1/2Na1/2)TiO3-based solid solutions. J Appl Phys 2008, 104: 124106.
Wang K, Hussain A, Jo W, et al. Temperature-dependent properties of (Bi1/2Na1/2)TiO3-(Bi1/2k1/2)TiO3-SrTiO3 lead-free piezoceramics. J Am Ceram Soc 2012, 95: 2241–2247.
Han HS, Ahn CW, Kim IW, et al. Destabilization of ferroelectric order in bismuth perovskite ceramics by A-site vacancies. Mater Lett 2012, 70: 98–100.
Ishchuk VM, Kuzenko DV, Sobolev VL. Dimensional t-factor variation and increase of stability of the ferroelectric state in (Na0.5Bi0.5)TiO3-based solid solutions. J Adv Dielec 2017, 7: 1750030.
Lee JK, Hong KS, Kim CK, et al. Phase transitions and dielectric properties in A-site ion substituted (Na1/2Bi1/2)TiO3 ceramics (A = Pb and Sr). J Appl Phys 2002, 91: 4538.
Jin L, Li F, Zhang S. Decoding the fingerprint of ferroelectric loops: Comprehension of the material properties and structures. J Am Ceram Soc 2014, 97: 1–27.
Le PG, Pham TL, Nguyen DT, et al. Solid state crystal growth of single crystals of 0.75(Na1/2Bi1/2)TiO3-0.25SrTiO3 and their characteristic electrical properties. J Asian Ceram Soc 2021, 9: 63–74.
Luo C, Ge W, Zhang Q, et al. Crystallographic direction dependence of direct current field induced strain and phase transitions in Na0.5Bi0.5TiO3-x%BaTiO3 single crystals near the morphotropic phase boundary. Appl Phys Lett 2012, 101: 141912.
Wang YJ, Luo CT, Wang SH, et al. Large piezoelectricity in ternary lead-free single crystals. Adv Electron Mater 2020, 6: 1900949.
Park JH, Lee HY, Kang SJL. Solid-state conversion of (Na1/2Bi1/2)TiO3-BaTiO3-(K1/2Na1/2)NbO3 single crystals and their piezoelectric properties. Appl Phys Lett 2014, 104: 222910.
Chen C, Zhao XY, Wang YJ, et al. Giant strain and electric-field-induced phase transition in lead-free (Na0.5Bi0.5)TiO3-BaTiO3-(K0.5Na0.5)NbO3 single crystal. Appl Phys Lett 2016, 108: 022903.
Chen C, Wang YJ, Jiang XP, et al. Orientation dependence of electric field induced phase transitions in lead-free (Na0.5Bi0.5)TiO3-based single crystals. J Am Ceram Soc 2019, 102: 4306–4313.
Hinterstein M, Knapp M, Hölzel M, et al. Field-induced phase transition in Bi1/2Na1/2TiO3-based lead-free piezoelectric ceramics. J Appl Crystallogr 2010, 43: 1314–1321.
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Education under Grant No. 2015R1D1A1A01057060. Jong-Sook Lee acknowledges the support of the National Research Foundation (NRF) of Korea funded by the Ministry of Science and ICT (MSIT) (Grant No. NRF-2018R1A5A1025224).
The authors would like to thank Kyeong-Kap Jeong (Chonnam Centre for Research Facilities, Chonnam National University) for operating the XRD and Hey-Jeong Kim (Centre for Development of Fine Chemicals, Chonnam National University) for operating the SEM.
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Le, P.G., Tran, H.T., Lee, JS. et al. Growth of single crystals in the (Na1/2Bi1/2)TiO3–(Sr1–xCax)TiO3 system by solid state crystal growth. J Adv Ceram (2021). https://doi.org/10.1007/s40145-021-0481-2
- lead-free piezoelectric
- single crystal
- electrical properties