溶胶-凝胶法制备Au-BaTiO3纳米复合薄膜及其介电性能

doi:10.15541/jim20140271

摘要/Abstract

摘要：

采用溶胶-凝胶法在Pt/Ti/SiO₂/Si基板上制备了Au-BaTiO₃纳米复合薄膜, 并且对其晶体结构、微观组织和介电性能进行了研究。结果表明, Au在复合薄膜中以直径为5 ~ 22 nm的Au纳米粒子弥散地分布在BaTiO₃基体中。Au的添加量对复合薄膜的介电性能和表面形貌有很大影响, 其最佳添加量约为5mol%。复合薄膜经过550℃的低温退火已经完全结晶为钙钛矿相, 其介电常数与700℃退火的纯BaTiO₃薄膜的相当。在Au-BaTiO₃复合薄膜的结晶过程中, 一方面, Au纳米粒子可能促进了中间相的分解; 另一方面, Au纳米粒子诱发了钙钛矿相的异质形核, 促进了BaTiO₃的结晶化。因此, Au纳米粒子大幅度地降低了复合薄膜的退火温度, 并显著提高了复合薄膜的介电性能。

关键词: BaTiO3, 纳米复合薄膜, 溶胶-凝胶法, 介电性能, 结晶化

Abstract:

Au-BaTiO₃ nanocomposite thin films were prepared on Pt/Ti/SiO₂/Si substrates by a Sol-Gel method and their crystal structure, microstructure and dielectric properties were investigated. Au nanoparticles with diameter of 5-22 nm are distributed in the BaTiO₃matrix. Au concentration has great effects on the surface morphology and dielectric properties of the composite thin films, and the optimal concentration of Au is about 5mol%. The composite thin films have crystallized into the perovskite phase after annealing at 550℃, and their dielectric constant is equivalent with that of the pure BaTiO₃ thin films annealed at 700℃. The enhanced crystallization of Au-BaTiO₃ composite film is attributed to the addition of Au nanoparticles, which can promote the decomposition of the intermediate phase and induce a heterogeneous nucleation of the perovskite phase. Thus, the annealing temperature of the composite films is drastically reduced and their dielectric properties are improved significantly with the addition of Au nanoparticles.

Key words: BaTiO3, nanocomposite thin films, Sol-Gel method, dielectric property, crystallization

中图分类号:

O469

武英杰，王海玲，宁兴坤，王占杰，王强. 溶胶-凝胶法制备Au-BaTiO₃纳米复合薄膜及其介电性能[J]. 无机材料学报, 2015, 30(2): 207-213.

WU Ying-Jie, WANG Hai-Ling, NING Xing-Kun, WANG Zhan-Jie, WANG Qiang. Dielectric Properties of Au-BaTiO₃ Nanocomposite Films Prepared by Sol-Gel Method[J]. Journal of Inorganic Materials, 2015, 30(2): 207-213.

图/表 8

图1 在SiO2/Si基板上制备的Au含量为10mol%的Au-BTO复合薄膜和在Pt/Ti/SiO2/Si基板上制备的纯BTO薄膜的XRD图谱

Fig. 1 XRD patterns of Au-BTO composite films with 10mol% Au prepared on the SiO2/Si substrate and pure BTO film prepared on the Pt/Ti/SiO2/Si substrate Both films were annealed at 700℃for 1 h

图2 Au含量为5mol%的Au-BTO复合薄膜断面的STEM高角度环形暗场照片

Fig. 2 High-angle annular dark-field STEM image of the Au-BTO composite film with 5mol% Au annealed at 700℃for 1 h

图3 Au含量为5mol%的Au-BTO复合薄膜的HRTEM照片

Fig. 3 HRTEM image of Au-BTO composite film with 5mol% Au

图4 不同 Au含量的Au-BTO复合薄膜其(a)介电常数和(b)介电损耗随频率的变化关系

Fig. 4 Dielectric constant (a) and dissipation factor (b) of Au-BTO composite films with different concentrations of gold as a function of frequency

图5 不同Au含量的Au-BTO复合薄膜的SEM表面形貌

Fig. 5 SEM surface morphologies of Au-BTO composite films with different concentrations of gold (a) Pure BTO; (b) 1mol%; (c) 5mol% ; (d) 10mol%

图6 不同Au含量的Au-BTO复合薄膜的电流密度随电压的变化关系及拟合线(红线)(a); 介电常数随Au体积分数的变化关系及拟合线(蓝线)(b)

Fig. 6 Leakage current density of Au-BTO composite films with different gold concentrations as a function of voltage and fitting line (red line) (a); dielectric constant as a function of Au volume fraction and fitting line (blue line) (b)

图7 不同温度退火的纯BTO薄膜和Au含量为5mol%的Au-BTO复合薄膜的XRD图谱

Fig. 7 XRD patterns of pure BTO films and Au-BTO composite films with 5mol% Au annealed at different temperatures

图8 1 kHz下, 纯BTO薄膜和Au含量为5mol%的Au-BTO复合薄膜的介电常数随退火温度的变化关系

Fig. 8 Dielectric constant of pure BTO film and Au-BTO composite film with 5mol% Au at 1 kHz as a function of annealing temperature

参考文献 29

[1]	SHARMA H B.Structure and properties of BT and BST thin films.Ferroelectrics, 2013, 453(1): 113-121.
[2]	WEBER U, GREUEL G, BOETTGER U, et al.Dielectric propeties of Ba(Zr,Ti)O3-based ferroelectrics for capacitor applications.Journal of the American Ceramic Society, 2001, 84(4): 759-766.
[3]	殷江,袁国亮,刘治国. 铁电材料的研究进展. 中国材料进展. 2012, 31(3): 26-38.
[4]	WANG Z, HU T, TANG L, et al. Ag nanoparticle dispersed PbTiO3 percolative composite thin film with high permittivity. Applied Physics Letters, 2008, 93(22): 222901-1-3.
[5]	WANG Z, HU T, LI X, et al. Nano conductive particle dispersed percolative thin film ceramics with high permittivity and high tunability. Applied Physics Letters, 2012, 100(13): 132909-1-4.
[6]	KUMAR P, AGRAWAL D C.Dielectric and optical properties of CaCu3Ti4O12 thin films containing Ag nanoparticles.Materials Letters, 2010, 64(3): 350-352.
[7]	BRETOS I, SCHNELLER T, WASER R, et al.Compositional substitutions and aliovalent doping of BaTiO3-based thin films on nickel foils prepared by chemical solution deposition.Journal of the American Ceramic Society, 2010, 93(2): 506-515.
[8]	TANG B, ZHANG S, ZHOU X, et al.Doping effects of Mn2+ on the dielectric properties of glass-doped BaTiO3-based X8R materials.Journal of Materials Science: Materials in Electronics, 2007, 18(5): 541-545.
[9]	HO C S, HUANG C W, HUNG D S.Dielectric properties of Cu- doped (Ba0.6Sr0.4)TiO3 high frequency materials.Ferroelectrics, 2012, 434(1): 52-57.
[10]	CAO S, MAO C L, YAO C H, et al.Dielectric and pyroelectric properties of Y-doped Ba0.6Sr0.3Ca0.1TiO3 ceramics by solid-state reaction technique.Journal of Inorganic Materials, 2013, 28(4): 447-452.
[11]	QIN W F, ZHU J, XIONG J, et al.Electrical behavior of Y-doped Ba0.6Sr0.4TiO3 thin films.Journal of Materials Science: Materials in Electronics, 2007, 18(12): 1217-1220.
[12]	DUAN N, TEN ELSHOF J E, VERWEIJ H, et al. Enhancement of dielectric and ferroelectric properties by addition of Pt particles to a lead zirconate titanate matrix.Applied Physics Letters, 2000, 77(20): 3263-3265.
[13]	YANG S, ZHANG H, ZHANG S W, et al.Electrical properties tailoring in Ni-particle-dispersed (Ba0.95Ca0.05)(Ti0.96Zr0.04)O3 composites.Materials Chemistry and Physics, 2011, 126(3): 729-733.
[14]	PANTENY S, BOWEN C R, STEVENS R.Characterisation of barium titanate-silver composites part II: Electrical properties.Journal of Materials Science, 2006, 41(12): 3845-3851.
[15]	WANG H W, NIEN S W, LEE K C, et al.Improvement in crystallization and electrical properties of barium strontium titanate thin films by gold doping using metal-organic deposition method.Thin Solid Films, 2005, 489(1): 31-36.
[16]	WANG H W, NIEN S W, LEE K C.Enhanced tunability and electrical properties of barium strontium titanate thin films by gold doping in grains.Applied Physics Letters, 2004, 84(15): 2874-2876.
[17]	LI J F, TAKAGI K, TERAKUBO N, et al.Electrical and mechanical properties of piezoelectric ceramic/metal composites in the Pb(Zr,Ti)O3/Pt system.Applied Physics Letters, 2001, 79(15): 2441-2443.
[18]	OTSUKI S, NISHIO K, KINERI T, et al.Optical properties of gold dispersed barium titanate thin films prepared by Sol-Gel processing.Journal of the American Ceramic Society, 1999, 82(7): 1676-1680.
[19]	DAI SHU-GANG, YANG YONG, HUANG WEI-MIN, et al.Preparation and optical properties of Au/BaTiO3 nanoparticle composite thin films.Journal of Inorganic Materials, 2003, 18(2): 421-426.
[20]	YANG Y, SHI J, HUANG W, et al.Preparation and optical properties of barium titanate thin films dispersed with Au nanoparticles.Materials Letters, 2002, 56(6): 1048-1052.
[21]	YANG Y, SHI J, HUANG W, et al.Preparation and optical properties of gold nanoparticles embedded in barium titanate thin films.Journal of Materials Science, 2003, 38(6): 1243-1248.
[22]	WANG W, SHI C, SU X, et al.Optical nonlinearities of BaTiO3 matrix-embedded Au nanoparticles. Materials Research Bulletin, 2006, 41(11): 2018-2023.
[23]	HUANG J, CAO Y, HONG M, et al. Ag-Ba0.75Sr0.25TiO3 composites with excellent dielectric properties. Applied Physics Letters, 2008, 92(2): 022911-1-3.
[24]	MASAKI Y, KOUTZAROV I P, RUDA H E, et al.Gold-particle-enhanced crystallite growth of thin films of Brium titanate prepared by the Sol-Gel process.Journal of the American Ceramic Society, 1998, 81(4): 1074-1076.
[25]	DURAN P, GUTIERREZ D, TARTAJ J, et al.On the formation of an oxycarbonate intermediate phase in the synthesis of BaTiO3 from (Ba, Ti)-polymeric organic precursors.Journal of the European Ceramic Society, 2002, 22(6): 797-807.
[26]	GUST M C, EVANS N D, MOMODA L A, et al.In-situ transmission electron microscopy crystallization studies of Sol-Gel-derived Barium titanate thin films.Journal of the American Ceramic Society, 1997, 80(11): 2828-2836.
[27]	WANG C, HU J, CHOW G M, et al.Structural and optical properties of Sol-Gel-derived Au/BaTiO3 nanocomposite thin films.Journal of the American Ceramic Society, 2005, 88(3): 758-767.
[28]	常方高, 宋桂林, 房坤, 等. 氧含量对BiFeOδ多晶陶瓷介电特性的影响. 物理学报, 2007, 56(10): 6068-6074.
[29]	DISSADO L A, FOTHERGILL J.Electrical Degradation and Breakdown in Polymers. London: Peter Peregrinus Publishing, 1992.

溶胶-凝胶法制备Au-BaTiO₃纳米复合薄膜及其介电性能

Dielectric Properties of Au-BaTiO₃ Nanocomposite Films Prepared by Sol-Gel Method

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