Growth and Property of Aurivillius Structure Bi2MoxW1-xO6 Series Ferroelectric Functional Single Crystals

Abstract

Abstract: Synthesis conditions of Aurivillius structure Bi₂Mo_xW_1-xO₆ series and the composition range of solid solution were explored by solid phase reaction method, and the flux growth system of Bi₂Mo_xW_1-xO₆ crystal was explored. The structure, variable temperature dielectric property and resistivity of the crystal were measured and analyzed. Due to their large spontaneous polarization and high Curie temperatures, ferroelectric Aurivillius Bi₂Mo_xW_1-xO₆ have attracted tremendous research attention in petroleum mining industries, communication equipments, meidcal ultrsonic diagnostics, structural health monitoring, et al. In this study, the composition variation range of n(Mo)∶n(W) ratio in Bi₂Mo_xW_1-xO₆ solid solution were studied in detail through changing the sintering temperature and dewelling time. According to the synthetic results, the proportion(x) of Mo in the solid solution can be continuously tuned in the range of 0 to 1, and the pure ferroelectric phase of Bi₂Mo_xW_1-xO₆ can be synthesized under different temperatures in the range of 500 ℃ to 870 ℃. Growth of the Bi₂Mo_xW_1-xO₆ single crystals through the high temperature solution method were also explored systematically. By employing Li₂B₄O₇-Bi₂O₃ (molar ratio 2∶1) as a flux, centimeter-sized Bi₂WO₆ single domain crystals were grown with the thickness of about 2 mm and the maximum dimension reaching as large as 40 mm. Centimeter-sized single domain crystals of Bi₂Mo_0.15W_0.85O₆ with the thickness of about 1 mm were also grown in n(Bi₂O₃)∶n(MoO₃)∶n(WO₃)∶n(Li₂B₄O₇)=1∶1∶1∶1 (molar ratio) flux system. Structural refinement reveals that Bi₂Mo_0.15W_0.85O₆ crystallizes into the orthorhombic system, Aba2 (No.41) space group. Variable temperature dielectric measurements show that the dielectric constant ε₃₃ increases from 70 of Bi₂WO₆ crystal to 102, and the temperature at which the dielectric relaxation occurs decreases from 430 ℃ of Bi₂WO₆ crystal to around 330 ℃. The temperature varying resistivity shows that the resistivity of Bi₂WO₆ and Bi₂Mo_0.15W_0.85O₆ crystals both decrease with the increase of temperature. Below 100 ℃, the resistivity of Bi₂WO₆ is higher than that of Bi₂Mo_0.15W_0.85O₆ crystal, and with the increase of temperature, the difference of resistivity between the two crystals is gradually narrowing.

Key words: Bi₂Mo_xW_1-xO₆, Aurivillius structure, flux method, crystal structure, dielectric property, ferroelectric crystal, resistivity

CLC Number:

O782
O73

DING Xiaonan, TIAN Xiangxin, ZHAO Peng, GAO Zeliang, LIU Jingquan. Growth and Property of Aurivillius Structure Bi₂Mo_xW_1-xO₆ Series Ferroelectric Functional Single Crystals[J]. Journal of Synthetic Crystals, 2022, 51(11): 1858-1870.

References

[1] 吴金根,高翔宇,陈建国,等.高温压电材料、器件与应用[J].物理学报,2018,67(20):10-39.
WU J G, GAO X Y, CHEN J G, et al. Review of high temperature piezoelectric materials, devices, and applications[J]. Acta Physica Sinica, 2018, 67(20): 10-39(in Chinese).
[2] 张大龙,陈志伟,黄伟川,等.层状类钙钛矿多铁性材料研究进展[J].硅酸盐学报,2017,45(12):1707-1720.
ZHANG D L, CHEN Z W, HUANG W C, et al. Development of multiferroic layered-perovskite-like oxides[J]. Journal of the Chinese Ceramic Society, 2017, 45(12): 1707-1720(in Chinese).
[3] DE ARAUJO C A P, CUCHIARO J D, MCMILLAN L D, et al. Fatigue-free ferroelectric capacitors with platinum electrodes[J]. Nature, 1995, 374(6523): 627-629.
[4] DING Y, LIU J S, QIN H X, et al. Why lanthanum-substituted bismuth titanate becomes fatigue free in a ferroelectric capacitor with platinum electrodes[J]. Applied Physics Letters, 2001, 78(26): 4175-4177.
[5] HA S D, RAMANATHAN S. Adaptive oxide electronics: a review[J]. Journal of Applied Physics, 2011, 110(7): 071101.
[6] PAN Z, WANG P, HOU X, et al. Fatigue-free Aurivillius phase ferroelectric thin films with ultrahigh energy storage performance[J]. Advanced Energy Materials, 2020, 10 (31), 2001536.
[7] WU Q, WU X, ZHAO Y S, et al. Design of lead-free films with high energy storage performance via inserting a single perovskite into Bi₄Ti₃O₁₂[J]. Chinese Physics Letters, 2020, 37(11): 123-130.
[8] WU Q, CHEN X H, ZHAO L, et al. The relaxor properties and energy storage performance of Aurivillius compounds with different number of perovskite-like layers[J]. Journal of Alloys and Compounds, 2022, 911: 165081.
[9] YANG B B, GUO M Y, TANG X W, et al. Lead-free A₂Bi₄Ti₅O₁₈ thin film capacitors (A=Ba and Sr) with large energy storage density, high efficiency, and excellent thermal stability[J]. Journal of Materials Chemistry C, 2019, 7(7): 1888-1895.
[10] SCOTT J F, ROSS F M, DE ARAUJO C A P, et al. Structure and device characteristics of SrBi₂Ta₂O₉-based nonvolatile random-access memories[J]. MRS Bulletin, 1996, 21(7): 33-39.
[11] SUBBARAO E C. A family of ferroelectric bismuth compounds[J]. Journal of Physics and Chemistry of Solids, 1962, 23(6): 665-676.
[12] AURIVILLIUS B. Mixed bismuth oxides with layer lattices. 1. The structure type of CaNb₂Bi₂O₉[J]. Arkiv for Kemi, 1950,1(5): 463-480.
[13] AURIVILLIUS B. Mixed bismuth oxides with layer lattices. 2. Structure of Bi₄Ti₃O₁₂[J]. Arkiv for Kemi, 1950, 1(6): 499-512.
[14] AURIVILLIUS B. Mixed oxides with layer lattices. 3. Structure of BaBi₄Ti₄O₁₅[J]. Arkiv for Kemi, 1951, 2(6): 519-527.
[15] ZOU H, HUI X W, WANG X S, et al. Luminescent, dielectric, and ferroelectric properties of Pr doped Bi₇Ti₄NbO₂₁ multifunctional ceramics[J]. Journal of Applied Physics, 2013, 114(22): 223103.
[16] MERCURIO D, TROLLIARD G, HANSEN T, et al. Crystal structure of the ferroelectric mixed Aurivillius phase Bi₇Ti₄NbO₂₁[J]. International Journal of Inorganic Materials, 2000, 2(5): 397-406.
[17] TELLIER J, BOULLAY P, CRÉON N, et al. The crystal structure of the mixed-layer Aurivillius phase Bi₅Ti_1.5W_1.5O₁₅[J]. Solid State Sciences, 2005, 7(9): 1025-1034.
[18] NOGUCHI Y, MIYAYAMA M, KUDO T. Ferroelectric properties of intergrowth Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅ ceramics[J]. Applied Physics Letters, 2000, 77(22): 3639-3641.
[19] RAMESH R, SCHLOM D G. Creating emergent phenomena in oxide superlattices[J]. Nature Reviews Materials, 2019, 4(4): 257-268.
[20] FU Y P, JIANG X Y, LI X T, et al. Cation engineering in two-dimensional ruddlesden-popper lead iodide perovskites with mixed large A-site cations in the cages[J]. Journal of the American Chemical Society, 2020, 142(8): 4008-4021.
[21] OK K M, HALASYAMANI P S, CASANOVA D, et al. Distortions in octahedrally coordinated d⁰ transition metal oxides: a continuous symmetry measures approach[J]. Chemistry of Materials, 2006, 18(14): 3176-3183.
[22] HALASYAMANI P S. Asymmetric cation coordination in oxide materials: influence of lone-pair cations on the intra-octahedral distortion in d⁰ transition metals[J]. Chemistry of Materials, 2004, 16(19): 3586-3592.
[23] ETXEBARRIA I, PEREZ-MATO J M, BOULLAY P. The role of trilinear couplings in the phase transitions of aurivillius compounds[J]. Ferroelectrics, 2010, 401(1): 17-23.
[24] BENEDEK N A, RONDINELLI J M, DJANI H, et al. Understanding ferroelectricity in layered perovskites: new ideas and insights from theory and experiments[J]. Dalton Transactions, 2015, 44(23): 10543-10558.
[25] WOLFE R W, NEWNAHM R E, KAY M I. Crystal structure of Bi₂WO₆[J]. Solid State Communications, 1969, 7(24): 1797-1801.
[26] TELLER R G, BRAZDIL J F, GRASSELLI R K, et al. The structure of γ-bismuth molybdate, Bi₂MoO₆, by powder neutron diffraction[J]. Acta Crystallographica Section C Crystal Structure Communications, 1984, 40(12): 2001-2005.
[27] TIAN X X, GAO Z L, CHEN F F, et al. Insights into the polymorphism of Bi₂W₂O₉: single crystal growth and a complete survey of the variable-temperature thermal and dielectric properties[J]. CrystEngComm, 2018, 20(19): 2669-2680.
[28] ETOGO A, LIU R, REN J B, et al. Facile one-pot solvothermal preparation of Mo-doped Bi₂WO₆ biscuit-like microstructures for visible-light-driven photocatalytic water oxidation[J]. Journal of Materials Chemistry A, 2016, 4(34): 13242-13250.
[29] VORONKOVA V I, KHARITONOVA E P, RUDNITSKAYA O G. Refinement of Bi₂WO₆ and Bi₂MoO₆ polymorphism[J]. Journal of Alloys and Compounds, 2009, 487(1/2): 274-279.
[30] DJANI H, BOUSQUET E, KELLOU A, et al. First-principles study of the ferroelectric Aurivillius phase Bi₂WO₆[J]. Physical Review B, 2012, 86(5): 054107.
[31] NOGUCHI Y, MURATA K, MIYAYAMA M. Defect control for polarization switching in Bi₂WO₆-based single crystals[J]. Applied Physics Letters, 2006, 89(24): 242916.
[32] WANG C S, KE X X, WANG J J, et al. Ferroelastic switching in a layered-perovskite thin film[J]. Nature Communications, 2016, 7: 10636.
[33] CASTRO A, BEGUE P, JIMENEZ B, et al. New Bi₂Mo_1-xW_xO₆ solid solution: mechanosynthesis, structural study, and ferroelectric properties of the x=0.75 member[J]. Chemistry of Materials, 2003, 15 (17): 3395-3401.
[34] MURAMATSU K, WATANABE A, GOTO M. Flux growth of Bi₂WO₆ single crystal below the transformation temperature[J]. Journal of Crystal Growth, 1978, 44(1): 50-52.
[35] DE L'EPREVIER A G, SHUKLA V N, PAYNE D A. Crystal growth of bismuth tungstate[J]. Ferroelectrics, 1980, 28(1): 383-386.
[36] TAKEDA H, NISHIDA T, OKAMURA S, et al. Crystal growth of bismuth tungstate Bi₂WO₆ by slow cooling method using borate fluxes[J]. Journal of the European Ceramic Society, 2005, 25(12): 2731-2734.
[37] TAKEDA H, HAN J S, NISHIDA M, et al. Growth and piezoelectric properties of ferroelectric Bi₂WO₆[J]. Solid State Communications, 2010, 150(17/18): 836-839.
[38] KANIA A, NIEWIADOMSKI A, KUGEL G E. Dielectric and Raman scattering studies of Bi₂WO₆ single crystals[J]. Phase Transitions, 2013, 86(2/3): 290-300.
[39] THOMPSON J G, SCHMID S, WITHERS R L, et al. Comparison of the crystal structures of γ-Bi₂MoO₆ and Bi₂WO₆[J]. Journal of Solid State Chemistry, 1992, 101(2): 309-321.
[40] GOODENOUGH J B. Jahn-teller phenomena in solids[J]. Annual Review of Materials Science, 1998, 28: 1-27.
[41] HALASYAMANI P S, POEPPELMEIER K R. Noncentrosymmetric oxides[J]. Chemistry of Materials, 1998, 10(10): 2753-2769.
[42] ZHANG J J, ZHANG Z H, ZHANG W G, et al. Polymorphism of BaTeMo₂O₉: a new polar polymorph and the phase transformation[J]. Chemistry of Materials, 2011, 23(16): 3752-3761.
[43] GALY J, MEUNIER G, ANDERSSON S, et al. Stéréochimie des eléments comportant des paires non liées: Ge (Ⅱ), As (Ⅲ), Se (Ⅳ), Br (V), Sn (Ⅱ), Sb (Ⅲ), Te (Ⅳ), I (Ⅴ), Xe (Ⅵ), Tl (Ⅰ), Pb (Ⅱ), et Bi (Ⅲ) (oxydes, fluorures et oxyfluorures)[J]. Journal of Solid State Chemistry, 1975, 13(1/2): 142-159.

Growth and Property of Aurivillius Structure Bi₂Mo_xW_1-xO₆ Series Ferroelectric Functional Single Crystals

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