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外场对拓扑相变氧化物薄膜物性的调控研究进展

孙雨婷 李明明 王玲瑞 樊贞 郭尔佳 郭海中

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外场对拓扑相变氧化物薄膜物性的调控研究进展

孙雨婷, 李明明, 王玲瑞, 樊贞, 郭尔佳, 郭海中

Research progress of control of physical properties of topological phase change oxide films by external field

Sun Yu-Ting, Li Ming-Ming, Wang Ling-Rui, Fan Zhen, Guo Er-Jia, Guo Hai-Zhong
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  • 钙钛矿型过渡金属氧化物在外场激励下可以通过得失氧离子发生显著的结构拓扑相变, 同时伴随着输运、磁性、光学等物性的巨大变化, 是近年来被重点关注的研究体系, 在固态氧化物燃料电池、氧气传感器、催化活性、智能光学窗口以及神经形态计算器件中具有巨大的应用前景. 本工作回顾了近年来国内外研究小组在拓扑相变氧化物薄膜及其物性调控方面的工作进展, 详细介绍了这类典型薄膜材料在应力场、电场、光场、温度场等外场激励下呈现出的新奇物性, 并讨论了其基本物理机制. 本综述旨在进一步认识此类材料中的电荷、晶格、轨道等量子序之间的微观耦合机制及其与宏观物性的关联, 相关研究有望为基于功能氧化物的高灵敏度、弱场响应的电子器件提供新材料、新途径和新思路.
    Perovskite transition-metal oxides can undergo significant structural topological phase transition between perovskite structure, brownmillerite structure, and infinite-layer structure under the external field through the gain and loss of the oxygen ions, accompanied with significant changes in physical properties such as transportation, magnetism, and optics. Topotactic phase transformation allows structural transition without losing the crystalline symmetry of the parental phase and provides an effective platform for utilizing the redox reaction and oxygen diffusion within transition metal oxides, and establishing great potential applications in solid oxide fuel cells, oxygen sensors, catalysis, intelligent optical windows, and neuromorphic devices. In this work, we review the recent research progress of manipulating the topological phase transition of the perovskite-type oxide films and regulating their physical properties, mainly focusing on tuning the novel physical properties of these typical films through strong interaction between the lattice and electronic degrees of freedom by the action of external fields such as strain, electric field, optical field, and temperature field. For example, a giant photoinduced structure distortion in SrCoO2.5 thin film excited by photons is observed to be higher than any previously reported results in the other transition metal oxide films. The SrFeO2 films undergo an insulator-to-metal transition when the strain state changes from compressive state to tensile state. It is directly observed that perovskite SrFeO3 nanofilament is formed under the action of electric field and extends almost through the brownmillerite SrFeO2.5 matrix in the ON state and is ruptured in the OFF state, unambiguously revealing a filamentary resistance switching mechanism. Utilizing in situ electrical scanning transmission electron microscopy, the transformation from brownmillerite SrFeO2.5 to infinite-layer SrFeO2 under electric field can be directly visualized with atomic resolution. We also clarify the relationship between the microscopic coupling mechanism and the macroscopic quantum properties of charges, lattices, orbits, spin, etc. Relevant research is expected to provide a platform for new materials, new approaches and new ideas for developing high-sensitivity and weak-field response electronic devices based on functional oxides. These findings about the topological phase transition in perovskite oxide films can expand the research scope of material science, and have important significance in exploring new states of matters and studying quantum critical phenomena.
      通信作者: 郭海中, hguo@zzu.edu.cn
    • 基金项目: 国家重点研发计划(批准号: 2021YFA1400204, 2021YFA0718701)、国家自然科学基金(批准号: 12174347, 11904322, U2032127)、河南省科技厅杰出青年基金(批准号: 202300410356)和广州市科技计划(批准号: 202201000008)资助的课题.
      Corresponding author: Guo Hai-Zhong, hguo@zzu.edu.cn
    • Funds: Project supported by the National Key Research and Development Program of China (Grant Nos. 2021YFA1400204, 2021YFA0718701), the National Natural Science Foundation of China (Grant Nos. 12174347, 11904322, U2032127), the Science and Technology Department Fund for Distinguished Young Scholars of Henan Province, China (Grant No. 202300410356), and the Science and Technology Program Project of Guangzhou, China (Grant No. 202201000008).
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  • 图 1  钙钛矿型氧化物基本构型及其衍生结构 (a)钙钛矿结构ABO3; (b)钙铁石结构ABO2.5; (c)无限层结构ABO2

    Fig. 1.  Perovskite structure and its derived structures: (a) Perovskite ABO3; (b) brownmillerite ABO2.5; (c) infinite-layer structure ABO2.

    图 2  不同应力情况下SrFeO2薄膜的输运性质和电子结构[19] (a) SrFeO2薄膜面外晶格常数与晶格失配的线性关系; (b)生长在 DyScO3 (DSO)和SrTiO3 (STO) 衬底上的 SrFeO2 膜的ρ-T 曲线; (c) 不同应力衬底上SrFeO2薄膜的X光吸收光谱(XAS), 实线和虚线分别代表光束分别以90°和30°入射; (d) 不同衬底上SrFeO2薄膜的X射线线性二色性(XLD)

    Fig. 2.  Transport properties and electronic states of SrFeO2 films[19]: (a) The out-of-plane lattice constants of SrFeO2 films as a function of the misfit strain; (b) ρ-T curves of SrFeO2 films grown on DSO and STO substrate; (c) XAS and (d) XLD for SrFeO2 films grown on various substrates. The solid and dashed lines in (c) represent the XAS measured with X-ray beam aligned with angles of 90° and 30° respect to the sample’s surface normal, respectively.

    图 3  超快激光激发诱导SrCoO2.5薄膜超大晶格膨胀[46] (a) 3.1 eV脉冲激光激发时SrCoO2.5薄膜的(008)衍射强度分布; (b) 激光激发前后SrCoO2.5薄膜(008)反射的θ-2θ扫描; (c) 在不同的泵浦注量和光子能量下, 获得的(008)峰的角位移和对应的应力与时间的关系曲线, 其中一个根据经验拟合为双指数衰减函数; (d) τ = 150 ps时的光致应力与3.1 eV和1.55 eV脉冲激光激发时入射通量的关系曲线, 并线性拟合数据结果

    Fig. 3.  Superlarge lattice expansion of SrCoO2.5 films is induced by ultrafast laser excitation[46]: (a) Diffraction intensity distribution upon the excitation of 3.1 eV laser pulses; (b) θ-2θ scans of the SrCoO2.5 (008) reflection before and after excitation; (c) the extracted angular shift of (008) peak and the corresponding strain as a function of time at different pump fluence and photon energies, one of which is empirically fitted to a biexponential decay function; (d) photoinduced strain at τ = 150 ps as a function of incident fluence upon excitation of 3.1 eV and 1.55 eV laser pulses, together with a linear fit to the data.

    图 4  实时观察电场调控下形成无限层SrFeO2的演化过程[52] (a)加电场不同时间下的高分辨率TEM图像显示SrFeO2的逐层转变过程; (b)图(a)电镜图对应的快速傅里叶变换图, SrFeO2.5的(002)和(006)衍射点用黄色虚线圆圈标记, 新形成的SrFeO2衍射点由红色箭头标记; (c)对应于图(a)中TEM图所展示的SrFeO2.5到SrFeO2相变过程的结构图示图

    Fig. 4.  Real-time tracking of the electrically controlled formation of infinite-layer SrFeO2 and its atomic process[52]: (a) Time-lapse high-resolution TEM images showing the further layer-by-layer transition to SrFeO2 under the electric field; (b) the corresponding fast Fourier transform (FFT) of the TEM images in (a), the (002) and (006) diffraction spots in SrFeO2.5 are marked by dashed yellow circles. The newly formed diffraction spots of SrFeO2 were marked by the red arrows; (c) structure illustration of the phase transition from SrFeO2.5 to SrFeO2 corresponding to the TEM images in (a).

    图 5  SrFeO2.5基阻变器件的微观机制和细丝模型的示意图 (a)加电场状态下SrFeO2.5薄膜的透射电子显微镜暗场图像, 显示一些典型的SrFeO3纳米丝产生并沿电场方向延伸几乎穿过整个SrFeO2.5薄膜; (b) Pt/SrFeO2.5/SrRuO3阻变器件的I-V特性显示了典型的双极电阻开关行为. 细丝模型的示意图: (c)初始状态下SrFeO2.5膜; (d)电场下SrFeO3相的导电细丝的形成; (e)以及复位后SrFeO3相的导电细丝断裂的示意图[54]

    Fig. 5.  Micromechanics of the SrFeO2.5 based resistance switching devices and filamentary resistance switching mechanism[54]: (a) STEM-HAADF image of the SrFeO2.5 film in the electroformed state, showing some typical SrFeO3 nanofilaments almost extending through the SrFeO2.5 matrix; (b) typical I-V characteristics showing bipolar resistive switching behavior with an electroforming process of the Pt/SrFeO2.5/SrRuO3 devices. Schematics illustrating of (c) the pristine SrFeO2.5 film with the SrFeO2.5 matrix, (d) the formation of SrFeO3 conductive filaments after the electroforming, and (e) the rupture of SrFeO3 conductive filaments after the reset.

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    Kroemer H 2001 Rev. Mod. Phys. 73 783Google Scholar

    [2]

    Moreo A, Yunoki S, Dagotto E 1999 Science 283 2034Google Scholar

    [3]

    Habermeier H U 2007 Mater. Today 10 34Google Scholar

    [4]

    Ohtomo A, Hwang H Y 2004 Nature 427 423Google Scholar

    [5]

    Guo H Z, Wang J O, He X, Yang Z Z, Zhang Q H, Jin K J, Ge C, Zhao R Q, Gu L, Feng Y Q, Zhou W J, Li X L, Wan Q, He M, Hong C H, Guo Z Y, Wang C, Lu H B, Ibrahim K, Meng S, Yang H, Yang G Z Z 2016 Adv. Mater. Interfaces 3 1500753Google Scholar

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    [7]

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    [8]

    Maekawa S, Tohyama T, Barnes S E, Ishihara S, Koshibae W, Khaliullin G 2004 Physics of Transition Metal Oxides (Vol. 144) (Berlin, Heidelberg: Springer) pp167−239

    [9]

    Mou X, Tang J S, Lyu Y J, Zhang Q T, Yang S Y, Xu F, Liu W, Xu M H, Zhou Y, Sun W, Zhong Y N, Gao B, Yu P, Qian H, Wu H Q 2021 Sci. Adv. 7 eabh0648Google Scholar

    [10]

    Kim Y M, He J, Biegalski M D, Ambaye H, Lauter V, Christen H M, Pantelides S T, Pennycook S J, Kalinin S V, Borisevich A Y 2012 Nat. Mater. 11 888Google Scholar

    [11]

    Wang Z, Huang H M, Guo X 2021 Adv. Electron. Mater. 7 2001243Google Scholar

    [12]

    Ge C, Liu C X, Zhou Q L, Zhang Q H, Du J Y, Li J K, Wang C, Gu L, Yang G Z, Jin K J 2019 Adv. Mater. 31 1900379Google Scholar

    [13]

    Gallagher P K, MacChesney J B, Buchananb D N E 1964 J. Chem. Phys. 41 2429Google Scholar

    [14]

    Takeda T, Yamaguchi Y, Watanabe H 1972 J. Phys. Soc. Jpn. 33 967Google Scholar

    [15]

    Lebon A, Adler P, Bernhard C, Boris A V, Pimenov A V, Maljuk A, Lin C T, Ulrich C, Keimer B 2004 Phys. Rev. Lett. 92 037202Google Scholar

    [16]

    Tsujimoto Y, Tassel C, Hayashi N, Watanabe T, Kageyama H, Yoshimura K, Takano M, Ceretti M, Ritter C, Paulus W 2007 Nature 450 1062Google Scholar

    [17]

    Siegrist T, Zahurak S M, Murphy D W, Roth R S 1988 Nature 334 231Google Scholar

    [18]

    Li D F, Lee K, Wang B Y, Osada M, Crossley S, Lee H R, Cui Y, Hikita Y, Hwang H Y 2019 Nature 572 624Google Scholar

    [19]

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出版历程
  • 收稿日期:  2022-11-26
  • 修回日期:  2023-03-20
  • 上网日期:  2023-03-23
  • 刊出日期:  2023-05-05

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