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VO2金属-绝缘体相变机理的研究进展

罗明海 徐马记 黄其伟 李派 何云斌

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VO2金属-绝缘体相变机理的研究进展

罗明海, 徐马记, 黄其伟, 李派, 何云斌

Research progress of metal-insulator phase transition mechanism in VO2

Luo Ming-Hai, Xu Ma-Ji, Huang Qi-Wei, Li Pai, He Yun-Bin
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  • VO2是一种热致相变金属氧化物. 在341 K附近, VO2发生由低温绝缘体相到高温金属相的可逆转变, 同时伴随着光学、电学和磁学等性质的可逆突变, 这种独特的性质使得VO2在光电开关材料、智能玻璃、存储介质材料等领域有着广阔的应用前景. 因此, VO2金属-绝缘体可逆相变一直是人们的研究热点, 但其相变机理至今未有定论. 首先, 简要概述了VO2相变时晶体结构和能带结构的变化情况: 从晶体结构来讲, 相变前后VO2从低温时的单斜相VO2(M)转变为高温稳定的金红石相VO2(R), 在一定条件下此过程也可能伴随着亚稳态单斜相VO2(B)与四方相VO2(A)的产生; 从能带结构来看, VO2处于低温单斜相时, 其d//能带和*能带之间存在一个禁带, 带宽约为0.7 eV, 费米能级恰好落在禁带之间, 表现出绝缘性, 而在高温金红石相时, 其费米能级落在*能带与d//能带之间的重叠部分, 因此表现出金属导电性. 其次, 着重总结了VO2相变物理机理的研究现状. 主要包括: 电子关联驱动相变、结构驱动相变以及电子关联和结构共同驱动相变的3种理论体系以及支撑这些理论体系的实验结果. 文献报道争论的焦点在于, VO2是否是Mott绝缘体以及结构相变与MIT相变是否精确同时发生. 最后, 展望了VO2材料研究的发展方向.
    VO2 is a metal oxide that has a thermally-induced phase-transition. In the vicinity of 341 K, VO2 undergoes a reversible transition from the high-temperature metal phase to the low-temperature insulator phase. Associated with the metal-insulator transition (MIT), there are drastic changes in its optical, electrical and magnetic characteristics. These make VO2 an attractive material for various applications, such as optical and/or electrical switches, smart glass, storage media, etc. Thus, the reversible metal-insulator phase transition in VO2 has long been a research hotspot. However, the metal-insulator transition mechanism in VO2 has been a subject of debate for several decades, and yet there is no unified explanation. This paper first describes changes of the crystal structure and the energy band structure during VO2 phase transition. With regard to the crystal structure, VO2 transforms from the low-temperature monoclinic phase VO2(M) into the high-temperature stable rutile phase VO2(R), and in some special cases, this phase transition process may also involve a metastable monoclinic VO2(B) phase and a tetragonal VO2(A) phase. In respect of the energy band structure, VO2 undergoes a transition from the low-temperature insulator phase into a high-temperature metal phase. In the band structure of low-temperature monoclinic phase, there is a band gap of about 0.7 eV between d// and * bands, and the Fermi level falls exactly into the band gap, which makes VO2 electronically insulating. In the band structure of high-temperature rutile phase, the Fermi level falls into the overlapping portion of the * and d// bands, which makes VO2 electronically metallic. Next, this paper summarizes the current research status of the physical mechanism underlying the VO2 MIT. Three kinds of theoretical perspectives, supported by corresponding experimental results, have been proposed so far, which includes electron-correlation-driven MIT, Peierls-like structure-driven MIT, and MIT driven by the interplay of both electron-correlation and Peierls-like structural phase transition. It is noted that recent reports mostly focus on the controversywhether VO2 is a Mott insulator, and whether the structural phase transition and the MIT accurately occur simultaneously in VO2. Finally, the paper points out the near-future development direction of the VO2 research.
      通信作者: 李派, paili@hubu.edu.cn;ybhe@hubu.edu.cn ; 何云斌, paili@hubu.edu.cn;ybhe@hubu.edu.cn
    • 基金项目: 国家自然科学基金(批准号: 51572073, 61274010, 51202062, 11574074)资助的课题.
      Corresponding author: Li Pai, paili@hubu.edu.cn;ybhe@hubu.edu.cn ; He Yun-Bin, paili@hubu.edu.cn;ybhe@hubu.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51572073, 61274010, 51202062, 11574074).
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    Kim H T, Kim B J Lee Y W Chae B G, Yun S J, Kang K Y 2007 Physica C 460-462 1076

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    [29]

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    Kim H T, Lee Y W, Kim B J, Chae B G, Yun S J, Kang K Y, Han K J, Yee K J, Lim Y S 2006 Phys. Rev. Lett. 97 266401

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    Cavalleri A, Dekorsy T, Chong H H W, Kieffer J C, Schoenlein R W 2004 Phys. Rev. B 70 161102

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    Biermann S, Poteryaev A, Lichtenstein A I, Georges A 2005 Phys. Rev. Lett. 94 026404

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    [34]

    Yao T, Zhang X D, Sun Z H, Liu S J, Huang Y Y Xie Y, Wu C Z, Yuan X, Zhang W Q, Wu Z Y, Pan G Q, Hu F C, Wu L H, Liu Q H, Wei S Q 2010 Phys. Rev. Lett. 105 226405

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    Hou J W, Zhang J W, Wang Z P, Zhang Z M, Ding Z J 2013 J. Nanosci. Nanotechnol. 13 1543

    [36]

    Tan X G, Yao T, Long R, Sun Z H, Feng Y J, Cheng H, Yuan X, Zhang W Q, Liu Q H, Wu C Z, Xie Y, Wei S Q 2012 Sci. Rep. 2 466

    [37]

    Cao J, Ertekin E, Srinivasan V, Fan W, Huang S, Zheng H, Yim J W L, Khanal D R, Ogletree D F, Grossman J C, Wu J 2009 Nat. Nanotechnol. 4 732

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    Sohn J I, Joo H J, Ahn D, Lee H H, Porter A E, Kim K, Kang D J, Welland M E 2009 Nano Lett. 9 3392

    [39]

    Wu J Q, Gu Q, Guiton B S, de Leon N P, Ouyang L, Park H 2006 Nano Lett. 6 2313

  • [1]

    Morin F J 1959 Phys. Rev. Lett. 3 34

    [2]

    Chain E E 1991 Appl. Opt. 30 2782

    [3]

    Mott N F 1968 Rev. Mod. Phys. 40 677

    [4]

    Adler D 1968 Rev. Mod. Phys. 40 714

    [5]

    Lysenko S, Rua A J, Vikhnin V, Jimenez J, Fernandez F, Liu H 2006 Appl. Surf. Sci. 252 5512

    [6]

    Soltani M, Chaker M, Haddad E, Kruzelesky R 2006 Meas. Sci. Technol. 17 1052

    [7]

    Manning T D, Parkin I P, Pemble M E, Sheel D, Vernardou D 2004 Chem. Mater. 16 744

    [8]

    Lee J S, Ortolani M, Schade U, Chang Y J, Noh T W 2007 Appl. Phys. Lett. 91 133509

    [9]

    Li J G, Hui L F, Feng H, Qin L J, Gong T, An Z W 2015 Chin. J. Vac. Sci. Technol. 35 243 (in Chinese) [李建国, 惠龙飞, 冯昊, 秦利军, 龚婷, 安忠维 2015 真空科学与技术学报 35 243]

    [10]

    Zhu H Q, Li Y, Ye W J, Li C B 2014 Acta Phys. Sin. 63 238101 (in Chinese) [朱慧群, 李毅, 叶伟杰,李春波 2014 物理学报 63 238101]

    [11]

    Aetukuri N B, Gray A X, Drouard M, Cossale M, Gao L, Reid A H, Kukreja R, Ohldag H, Jenkins C A, Arenholz E, Roche K P, Drr H A, Samant M G, Parkin S S P 2013 Nat. Phys. 9 661

    [12]

    Budai J D, Hong J W, Manley M E, Specht E D, Li C W, Tischler J Z, Abernathy D L, Said A H, Leu B M, Boatner L A, McQueeney R J, Delaire O 2014 Nature 515 535

    [13]

    Zylbersztejn A, Mott N F 1975 Phys. Rev. B 11 4383

    [14]

    Gervais F, Kress W 1985 Phys. Rev. B 31 4809

    [15]

    Haverkort M W, Hu Z, Tanaka A, Reichelt W, Streltsov S V, Korotin M A Anisimov V I Hsieh H H Lin H J Chen C T Khomskii D I Tjeng L H 2005 Phys. Rev. Lett. 95 196404

    [16]

    Koethe T C, Hu Z, Haverkort M W, Schler-Langeheine C Venturini F, Brookes N B Tjernberg O Reichelt W Hsieh H H, Lin H J Chen C T, Tjeng L H 2006 Phys. Rev. Lett. 97 116402

    [17]

    Fillingham P J 1967 J Appl Phys 38 4823

    [18]

    Becker M F, Buckman A B, Walser R M 1994 Appl. Phys. Lett. 65 1507

    [19]

    Theobald F 1977 J. Less-Comm. Met. 53 55

    [20]

    Guinneton F, Sauques L, Valmalette J C, Cros F, Gavarri J R 2005 J. Phys. Chem. Solids 66 63

    [21]

    Eyert V 2002 Ann. Phys. 11 650

    [22]

    Mott N F 1949 Proc. Phys. Soc. A 62 416

    [23]

    Goodenough J B, Hong H Y P 1973 Phys. Rev. B 8 1323

    [24]

    Kim H T, Kim B J Lee Y W Chae B G, Yun S J, Kang K Y 2007 Physica C 460-462 1076

    [25]

    Qazilbash M M, Burch K S, Whisler D, Shrekenhamer D, Chae B G, Kim H T, Basov D N 2006 Phys. Rev. B 74 205118

    [26]

    Zhang S X, Chou J Y, Lauhon L J 2009 Nano Lett. 9 4527

    [27]

    Kittiwatanakul S, Wolf S A, Lu J W 2014 Appl. Phys. Lett. 105 073112

    [28]

    Nag J, Haglund Jr. R F, Payzant E A, More K L 2012 J. Appl. Phys. 112 103532

    [29]

    Qazilbash M M, Brehm M, Chae B G, Ho P C, Andreev G O, Kim B J, Yun S J, Balatsky A V, Maple M B, Keilmann F, Kim H T, Basov D N 2007 Science 318 1750

    [30]

    Kim H T, Lee Y W, Kim B J, Chae B G, Yun S J, Kang K Y, Han K J, Yee K J, Lim Y S 2006 Phys. Rev. Lett. 97 266401

    [31]

    Cavalleri A, Dekorsy T, Chong H H W, Kieffer J C, Schoenlein R W 2004 Phys. Rev. B 70 161102

    [32]

    Biermann S, Poteryaev A, Lichtenstein A I, Georges A 2005 Phys. Rev. Lett. 94 026404

    [33]

    Tanaka A 2004 J. Phys. Soc. Jpn. 73 152

    [34]

    Yao T, Zhang X D, Sun Z H, Liu S J, Huang Y Y Xie Y, Wu C Z, Yuan X, Zhang W Q, Wu Z Y, Pan G Q, Hu F C, Wu L H, Liu Q H, Wei S Q 2010 Phys. Rev. Lett. 105 226405

    [35]

    Hou J W, Zhang J W, Wang Z P, Zhang Z M, Ding Z J 2013 J. Nanosci. Nanotechnol. 13 1543

    [36]

    Tan X G, Yao T, Long R, Sun Z H, Feng Y J, Cheng H, Yuan X, Zhang W Q, Liu Q H, Wu C Z, Xie Y, Wei S Q 2012 Sci. Rep. 2 466

    [37]

    Cao J, Ertekin E, Srinivasan V, Fan W, Huang S, Zheng H, Yim J W L, Khanal D R, Ogletree D F, Grossman J C, Wu J 2009 Nat. Nanotechnol. 4 732

    [38]

    Sohn J I, Joo H J, Ahn D, Lee H H, Porter A E, Kim K, Kang D J, Welland M E 2009 Nano Lett. 9 3392

    [39]

    Wu J Q, Gu Q, Guiton B S, de Leon N P, Ouyang L, Park H 2006 Nano Lett. 6 2313

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出版历程
  • 收稿日期:  2015-11-02
  • 修回日期:  2015-12-02
  • 刊出日期:  2016-02-05

VO2金属-绝缘体相变机理的研究进展

    基金项目: 国家自然科学基金(批准号: 51572073, 61274010, 51202062, 11574074)资助的课题.

摘要: VO2是一种热致相变金属氧化物. 在341 K附近, VO2发生由低温绝缘体相到高温金属相的可逆转变, 同时伴随着光学、电学和磁学等性质的可逆突变, 这种独特的性质使得VO2在光电开关材料、智能玻璃、存储介质材料等领域有着广阔的应用前景. 因此, VO2金属-绝缘体可逆相变一直是人们的研究热点, 但其相变机理至今未有定论. 首先, 简要概述了VO2相变时晶体结构和能带结构的变化情况: 从晶体结构来讲, 相变前后VO2从低温时的单斜相VO2(M)转变为高温稳定的金红石相VO2(R), 在一定条件下此过程也可能伴随着亚稳态单斜相VO2(B)与四方相VO2(A)的产生; 从能带结构来看, VO2处于低温单斜相时, 其d//能带和*能带之间存在一个禁带, 带宽约为0.7 eV, 费米能级恰好落在禁带之间, 表现出绝缘性, 而在高温金红石相时, 其费米能级落在*能带与d//能带之间的重叠部分, 因此表现出金属导电性. 其次, 着重总结了VO2相变物理机理的研究现状. 主要包括: 电子关联驱动相变、结构驱动相变以及电子关联和结构共同驱动相变的3种理论体系以及支撑这些理论体系的实验结果. 文献报道争论的焦点在于, VO2是否是Mott绝缘体以及结构相变与MIT相变是否精确同时发生. 最后, 展望了VO2材料研究的发展方向.

English Abstract

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