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基于纳米尺寸下复合铁电材料和反铁磁性材料是一个探索多铁性材料有效的方法. 利用激光脉冲沉积制备出LaFeO3-YMnO3人工超晶格和掺入不同层LaFeO3, BiFeO3的Bi4Ti3O12的外延薄膜. 通过系统的X射线衍射、透射电子显微术、扫描透射电子显微术下的能量损失谱表征证明这些样品具有原子尺寸上清晰的界面和完整的层状结构. 磁性测试证明这些材料具有亚铁磁性. 特别是在0.5和1.5LaFeO3-Bi4Ti3O12中的亚铁磁性甚至能保持到室温. 就铁电性而言, 铁电性测试显示出LaFeO3-YMnO3和插入BiFeO3的Bi4Ti3O12样品中存在较大的漏电流, 而在0.5LaFeO3-Bi4Ti3O12样品中存在铁电性. 因此在0.5LaFeO3-Bi4Ti3O12中能够实现亚铁磁和铁电共存. 其次发现当掺入多层的钙钛矿(3层SrTiO3或2.5层LaFeO3)后, Bi4Ti3O12 的层状结构将出现结构失稳现象. 这些工作对于利用纳米复合开发新颖多铁性提供一些实例.Combining ferroelectric with antiferromagentic materials in nanometer scale is an effective method for exploring multiferroic materials. We preflent two kinds of systems to show the possibility of multiferroic properties in such nanometer composites. One is the artificial superlattice LaFeO3-YMnO3, and the other is the natural layered Aurivillius material Bi4Ti3O12 doped with different layers of LaFeO3, BiFeO3. Both materials were synthesized by pulsed laser deposition method on SrTiO3 substrates. Microstructural charterizations with XRD, TEM, and EELS in scanning transmission electron microscopy mode substantiate that the samples have atomically sharp interfaces between neighboring layers; this is important for producing possible magneto-electric coupling in multiferroic materials. Magnetic characterization proves that these materials have ferrimagnetic properties, in spite of their anti-ferromagnetic nature before coupling. Magnetic characterization also proves that there is 0.55-0.9 B remanant magnetization generated at LaFeO3-YMnO3 interface. And the 0.5 and 1.5LaFeO3-Bi4Ti3O12 samples show ferrimagnetism which can remain even up to room temperature. Ferroelectric tests prove that there is a large leakage current in LaFeO3-YMnO3 superlattice and BiFeO3-inserted Bi4Ti3O12, but 0.5LaFeO3-Bi4Ti3O12 shows ferroelectric hysteresis loops. It can be therefore concluded that 0.5LaFeO3-Bi4Ti3O12 is a multiferroic material. If more perovskite layers (3-layer SrTiO3 or 2.5-layer LaFeO3) are inserted, the Aurivillius structure of Bi4Ti3O12 may appear structural instability that can be observed in our HRTEM measureflent. Our first principles calculations show that the degeneracy of formation enthalpies is the reason why the intergrowth in these materials forms and their structures are not stable. Our work may provide some examples for exploring new multiferroics by means of nano-meter composite.
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Keywords:
- multiferroic materials /
- nanometer engineering multiferroics /
- epitaxial thin films /
- microstructure-property relationship
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[15] Dong X W, Wang K F, Wan J G, Zhu J S, Liu J M 2008 J. Appl. Phys. 103 094101
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[18] Chen X Q, Yang F J, Cao W Q, Wang D Y, Chen K 2010 J. Phys. D: Appl. Phys. 43 065001
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[21] Singh R S 1996 Ph. D. Dissertation (Hyderabad: Osmania University)
[22] Prasad N V, Kumar G S 2000 J. Magn. Magn. Mater. 213 349
[23] Zurbuchen M A, Freitas R S, Wilson M J, Schiffer P, Roeckerath M, Schubert J, Biegalski M D, Mehta G H, Comstock D J, Lee J H, Jia Y, Schlom D G 2007 Appl. Phys. Lett. 91 033113
[24] Peña O, Guizouarn T, Moure C, Gil V, Tartaj J 2008 Bol. Soc. Esp. Ceram. Vidrio. 47 129
[25] James A R, Kumar G S, Suryanarayana S V, Bhimasankaram T 1996 Ferroelectrics 189 81
[26] Wu F X, Chen Z, Chen Y B, Zhang S T, Zhou J, Zhu Y Y, Chen Y F 2011 Appl. Phys. Lett. 98 212501
[27] Chen Y B, Zhou J, Zhang S T, Wu F X, Yao S H, Gu Z B, Wu D, Chen Y F 2013 Appl. Phys. Lett. 102 042403
[28] Wu F X 2012 Ph. D. Dissertation (Nanjing: Nanjing University) (in Chinese) [吴飞翔 2012 博士学位论文 (南京: 南京大学)]
[29] Zhou J, Wu F X, Chen Y B, Zhang S T, Chen Y F 2012 J. Mater. Res. 27 2956
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[1] Spaldin N, Cheong S W, Ramesh R 2010 Phys. Today. 63 38
[2] Eerenstein W, Mathur N D, Scott J F 2006 Nature 442 759
[3] Wang K F, Liu J M, Wang Y 2008 Chin. Sci. Bull. 53 1098 (in Chinese) [王克锋, 刘俊明, 王雨 2008 科学通报 53 1098]
[4] Catalan G, Scott J F 2009 Adv. Mater. 21 2463
[5] Kimura T, Goto T, Shintani H, Ishizaka K, Arima T, Tokura Y 2003 Nature 426 55
[6] Fiebig M 2005 J. Phys. D: Appl. Phys. 38 123
[7] Wadati H, Okamoto J, Garganourakis M, Scagnoli V, Staub U, Yamasaki Y, Nakao H, Murakami Y, Mochizuki M, Nakamura M, Kawasaki M, Tokura Y 2012 Phys. Rev. Lett 108 047203
[8] Peterlin-Neumaier T, Steichele E 1986 J. Mag. Mag. Mater. 59 351
[9] Jardiel T, Caballero A C, Villegas M 2008 J. Ceram. Soc. Jpn. 116 511
[10] Joshi P C, Krupanidhi S B 1993 Appl. Phys. Lett. 62 1928
[11] Kuima T, Satoh S, Matsunaga H, Koba M 1996 Jpn. J. Appi. Phys. 35 1246
[12] Dietl T 2010 Nature Mater. 23 965
[13] Singh R S, Bhimasankaram T, Kumar G S, Suryanarayana S V 1994 Solid State Commun. 91 567
[14] Srinivas A, Kim D W, Hong K S, Suryanarayana S V 2004 Mater. Res. Bull. 39 55
[15] Dong X W, Wang K F, Wan J G, Zhu J S, Liu J M 2008 J. Appl. Phys. 103 094101
[16] Suryanarayana S 1994 Bull. Mater. Sci. 17 1259
[17] Coey J M D, Douvalis A P, Fitzgerald C B, Venkatesan M 2004 Appl. Phys. Lett. 84 1332
[18] Chen X Q, Yang F J, Cao W Q, Wang D Y, Chen K 2010 J. Phys. D: Appl. Phys. 43 065001
[19] Jeon M K, Woo S I, Kim Y I, Nahm S H 2004 J. Korean Phys. Soc. 45 1240
[20] Silva J, Reyes A, Esparza H, Camacho H, Fuentes L 2011 Integr. Ferroelectr. 126 47
[21] Singh R S 1996 Ph. D. Dissertation (Hyderabad: Osmania University)
[22] Prasad N V, Kumar G S 2000 J. Magn. Magn. Mater. 213 349
[23] Zurbuchen M A, Freitas R S, Wilson M J, Schiffer P, Roeckerath M, Schubert J, Biegalski M D, Mehta G H, Comstock D J, Lee J H, Jia Y, Schlom D G 2007 Appl. Phys. Lett. 91 033113
[24] Peña O, Guizouarn T, Moure C, Gil V, Tartaj J 2008 Bol. Soc. Esp. Ceram. Vidrio. 47 129
[25] James A R, Kumar G S, Suryanarayana S V, Bhimasankaram T 1996 Ferroelectrics 189 81
[26] Wu F X, Chen Z, Chen Y B, Zhang S T, Zhou J, Zhu Y Y, Chen Y F 2011 Appl. Phys. Lett. 98 212501
[27] Chen Y B, Zhou J, Zhang S T, Wu F X, Yao S H, Gu Z B, Wu D, Chen Y F 2013 Appl. Phys. Lett. 102 042403
[28] Wu F X 2012 Ph. D. Dissertation (Nanjing: Nanjing University) (in Chinese) [吴飞翔 2012 博士学位论文 (南京: 南京大学)]
[29] Zhou J, Wu F X, Chen Y B, Zhang S T, Chen Y F 2012 J. Mater. Res. 27 2956
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