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Open AccessOpen Access JUSTC Physics 18 January 2023

Controlled properties of perovskite oxide films by engineering oxygen octahedral rotation

  • National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230026, China

Cite this:
https://doi.org/10.52396/JUSTC-2022-0101
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  • Author Bio:

    Junhua Liu is currently a Ph.D. student, and his research interests focus on emergent phenomena of transition metal oxides interface

    Zhaoliang Liao is a Professor at the University of Science and Technology of China. He received his Ph.D. degree from the Institute of Physics, CAS and Louisiana State University. He is supported by the Hundred-Talent Program Funding CAS and Youth Funding of Chinese National Innovative Talents Program. He focuses on the preparation and characterization of epitaxial quantum functional thin film materials and is committed to the design and function tailoring of oxides heterostructure utilizing advanced epitaxial growth technology. He has published several papers in high-level international journals, including Nat. Mater., Nat. Commun., PNAS, Nano Lett., PRL, Adv. Funct. Mater., Adv. Mater., and Sci. Adv.

  • Corresponding author: E-mail: zliao@ustc.edu.cn
  • Received Date: 11 July 2022
  • Accepted Date: 02 October 2022
    • Available Online: 18 January 2023
    Abstract

  • Abstract

    Complex perovskite oxides exhibit extremely rich physical properties in terms of magnetism, electrical transport, and electrical polarization characteristics due to the competition and coupling of many degrees of freedom. The B-site ions and O ions in perovskite form six-coordinated octahedral units, which are connected at a common vertex toward the basic framework of the perovskite oxide, providing a crucial platform to tailor physical properties. The rotation or distortion of the oxygen octahedra will tip the competing balance, leading to many emergent ground states. To further clarify the subtle relationship between emergent properties and oxide octahedral behavior, this article reviews the structure of perovskite oxides, the characterization methods of oxygen octahedral rotation and the response of transport, electrical polarization and magnetism of several typical perovskite heterostructures to oxygen octahedral rotation modes. With knowledge of how to manipulate the octahedral rotation behavior and regulate the physical properties of perovskite oxides, rationally designing the sample manufacturing process can effectively guide the development and application of novel electronic functional materials and devices.

    Graphical abstract

    Interaction between oxygen octahedral rotation (lattice) and many degrees of freedom including spin, orbit, and charge.

    Abstract

    Complex perovskite oxides exhibit extremely rich physical properties in terms of magnetism, electrical transport, and electrical polarization characteristics due to the competition and coupling of many degrees of freedom. The B-site ions and O ions in perovskite form six-coordinated octahedral units, which are connected at a common vertex toward the basic framework of the perovskite oxide, providing a crucial platform to tailor physical properties. The rotation or distortion of the oxygen octahedra will tip the competing balance, leading to many emergent ground states. To further clarify the subtle relationship between emergent properties and oxide octahedral behavior, this article reviews the structure of perovskite oxides, the characterization methods of oxygen octahedral rotation and the response of transport, electrical polarization and magnetism of several typical perovskite heterostructures to oxygen octahedral rotation modes. With knowledge of how to manipulate the octahedral rotation behavior and regulate the physical properties of perovskite oxides, rationally designing the sample manufacturing process can effectively guide the development and application of novel electronic functional materials and devices.

    • Public Summary

    • We review and summarize the structure of perovskite oxides, the characterization methods of oxygen octahedral rotation, as well as the response for transport, electrical polarization, and magnetism.
    • Half-order X-ray diffraction and STEM (HAADF and ABF) are two most common techniques to characterize the octahendral rotation.
    • Several key issues that need to be solved urgently are proposed to facilitate breakthroughs in octahedral-rotation-based devices.

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    • References(97)
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    Figure  1.  Schematic diagram of octahedral network in perovskite. (a) The definition of the rotation sign of an individual octahedron in an ABO3 perovskite unit cell with clockwise (+) and anticlockwise (–), the view direction is along the pseudocubic axis a, b, or c. (b) Rotation sign and pattern of octahedra in a shared rotation axis normal the plane. (c), (d), and (e) indicate a series of possible octahedral rotation structure network for simple (a+a0a0)/ (a−a0a0) modes and complex (a+a–a–)/ (a–a–a–) modes. Figure taken from Ref. [31].

    Figure  2.  Oxygen octahedral coupling at the heterointerface between perovskite oxides. (a) Schematic diagram of octahedral rotation in LSMO and NGO interface. (b) Layer-position-dependent mean octahedral tilt angle (β) in LSMO/NGO heterostructures with and without a STO buffer layer. The data for the non-buffered sample are shifted upwards by 6° for clarity. (c) It shows ABF-STEM images of LSMO/NGO, LSMO/STO9/NGO and LSMO/STO1/NGO heterostructures. Figure taken from Ref. [33].

    Figure  3.  RSM characterization of oxygen octahedral rotation. (a) The sketches of the RSM with symmetric and asymmetric reflections, where rOA, rOB, rOC and rOD represent reciprocal vectors. (b) and (c) display different half-order X-ray diffraction spectrum corresponding to the heterostructures, and the blue part in (b) is obtained by peak fitting. (d) The RSMs of LSMO/PTO/LSMO/NGO along different diffraction faces. Figure taken from Ref. [42].

    Figure  4.  MIT in nickelate superlattices triggered by oxygen octahedral coupling. (a) ρ-T curves of LFO­1-SNOn (n = 4–10) superlattices and 30 u.c. SNO film, and the inset shows the first derivative dlnp/(d(1/T)) of the SNO30 film. (b) ρ-T curves of SNO4 superlattices constructing with LFO, LCO and LNO. (c) Temperature dependent intensity of (1/4, 1/4, 1/4) magnetic Bragg reflection peak. (d) X-ray absorption spectra (XAS) of Ni L2,3 edge of nickelate superlattices with different thicknesses at 22 K. (e) Temperature phase diagram of nickelate superlattices as a function of the mean Ni—O—Ni bond angle. Figure taken from Ref. [72].

    Figure  5.  Octahedral rotation tailoring topological Hall effect. (a) The left figure shows the sketch of the octahedra configuration at the SRO/STO hetero-interface and the statistical results of rotation angle, and the inset respectively show the [RuO6] octahedral-rotation ABF image at the first layer of the interface and the simulation results. The figure on the right of the panel shows the statistics result of the rotation angle of the octahedron after inserting the 4 u.c. BTO. (b) The left picture shows the anomalous Hall resistance (AHR) of SRO (8 u.c.)/STO heterostructure at different temperatures, and the right one shows the AHR curve of SRO8/BTON (N = 2, 3)/STO at varying temperatures. Figure taken from Ref. [78].

    Figure  6.  Rotation of electric polarization induced by oxygen octahedral rotation. (a) HAADF-STEM image of the 1.6 nm thick PTO film and the electric polarization distribution. (b) are the ABF-STEM results. (c) Magnitude (δTi—O) of Ti4+ deviated from the oxygen octahedra center in- and out-of- plane of the 3.2 nm PTO film, respectively. (d) First-principles calculation results, where Model A and Model B give the relaxed atomic configuration with and without AFD, respectively. And the results of the electrical polarization simulation are shown on the right. Figure taken from Ref. [39].

    Figure  7.  Magnetic anisotropy in the magnetic heterojunctions. (a)–(c) show the M-H curves of the LSMO film along the a-axis and b-axis of the NGO substrate, where (a), (b), and (c) show the results of inserting 0 u.c., 1 u.c., and 9 u.c. STO buffer layers, respectively. (d) RXR measurements of 6 u.c. LSMO films with (top panel) and without (bottom panel) a 9 u.c. STO buffer layer showing depth profiles of the Ga, Ti, and Mn atomic concentration (green, red, and blue lines, respectively) and Mn magnetization (M, purple line with shaded area) at 20 K. The schematic on the left shows the experimental set-up used to perform RXR measurements, where a 0.6 T magnetic field was applied in-plane along the magnetic easy axis during the measurement. Figure taken from Ref. [33].

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