Binary Controls on Interfacial Magnetism in Manganite Heterostructures

The complex interfacial correlations provide new routes toward tunable functionalities. Here, the wide range of tunabilities for magnetic properties are presented, including Curie temperature (from 245 to 320 K), coercive field (from 2 to 205 Oe), and saturated magnetic moment (from 0.9 to 2.8 µ_B Mn^?1), in a 9‐unit‐cell La_2/3Sr_1/3MnO₃ (LSMO) layer via modifying interfacial boundary conditions. Moreover, the LSMO/PbTiO₃‐based multilayers and superlattices that consist of PbTiO₃/LSMO/NdGaO₃ and PbTiO₃/LSMO/PbTiO₃ interfaces are characterized by two distinct Curie temperatures and coercive fields. The results reveal the feasibility of the interface‐resolved strategy based on boundary modification in fabricating potential devices with multiple accessible states for information storage. The wide‐range modulations on magnetic properties at LSMO/titanate interfaces are explained in terms of binary controls arising from the oxygen octahedral coupling (OOC) and magnetoelectric coupling (MEC). The results not only shed some light on understanding interfacial correlations in oxide heterostructures, but also pave an alternative path for exploring multiple accessible states in all‐oxide‐based electronic devices.     

Multi‐Nonvolatile State Resistive Switching Arising from Ferroelectricity and Oxygen Vacancy Migration

Resistive switching phenomena form the basis of competing memory technologies. Among them, resistive switching, originating from oxygen vacancy migration (OVM), and ferroelectric switching offer two promising approaches. OVM in oxide films/heterostructures can exhibit high/low resistive state via conducting filament forming/deforming, while the resistive switching of ferroelectric tunnel junctions (FTJs) arises from barrier height or width variation while ferroelectric polarization reverses between asymmetric electrodes. Here the authors demonstrate a coexistence of OVM and ferroelectric induced resistive switching in a BaTiO₃ FTJ by comparing BaTiO₃ with SrTiO₃ based tunnel junctions. This coexistence results in two distinguishable loops with multi‐nonvolatile resistive states. The primary loop originates from the ferroelectric switching. The second loop emerges at a voltage close to the SrTiO₃ switching voltage, showing OVM being its origin. BaTiO₃ based devices with controlled oxygen vacancies enable us to combine the benefits of both OVM and ferroelectric tunneling to produce multistate nonvolatile memory devices.     

Correlated Lattice Instability and Emergent Charged Domain Walls at Oxide Heterointerfaces

Charged domain walls provide possibilities in effectively manipulating electrons at nanoscales for developing next‐generation electronic devices. Here, using the atom‐resolved imaging and spectroscopy on LaAlO₃/SrTiO₃//NdGaO₃ heterostructures, the evolution of correlated lattice instability and charged domain walls is visualized crossing the conducting LaAlO₃/SrTiO₃ heterointerface. When increasing the SrTiO₃ layer thickness to 20 unit cells and above, both LaAlO₃ and SrTiO₃ layers begin to exhibit measurable polar displacements to form a tail‐to‐tail charged domain wall at the LaAlO₃/SrTiO₃ interface, resulting in the charged redistribution within the 2‐nm‐thick SrTiO₃ layer close to the LaAlO₃/SrTiO₃ interface. The mobile charges in different heterostructures can be estimated by summing up Ti³⁺ concentrations in the conducting channel, which is sandwiched by SrTiO₃ layers with interdiffusion and/or oxygen octahedral rotations. Those estimated mobile charges are quantitatively consistent with results from Hall measurements. The results not only shed light on complex oxide heterointerfaces, but also pave a new path to nanoscale charge engineering.     

Oxygen Stoichiometry Effect on Polar Properties of LaAlO3/SrTiO3

Discovery of a ferroelectric‐like behavior of the LaAlO₃/SrTiO₃ (LAO/STO) interfaces provides an attractive platform for the development of nanoelectronic devices with functionality that can be tuned by electrical or mechanical means. However, further progress in this direction critically depends on deeper understanding of the physicochemical mechanism of this phenomenon. In this report, this problem by testing the electronic properties of the LAO/STO heterostructures with oxygen stoichiometry used as a variable is addressed. Local probe measurements in conjunction with interface electrical characterization allow to establish the field‐driven reversible migration of oxygen vacancies as the origin of the ferroelectric‐like behavior in LAO/STO. In addition, it is shown that oxygen deficiency gives rise to the formation of micrometer‐long atomically sharp boundaries with robust piezoelectricity stemming from a significant strain gradient across the boundary region. These boundaries are not ferroelectric but they can modulate the local electronic characteristics at the interface. The obtained results open a possibility to design and engineer electromechanical functionality in a wide variety of nominally nonpolar and non‐piezoelectric complex oxide heterostructures and thin films.     

Enhanced Magnetic Anisotropy and Orbital Symmetry Breaking in Manganite Heterostructures

Manipulating magnetic anisotropy in complex oxide heterostructures has attracted much attention. Here, three interface‐engineering approaches are applied to address two general issues with controlling magnetic anisotropy in the La_2/3Sr_1/3MnO₃ heterostructure. One is the paradox arising from the competition between Mn_3d–O_2p orbital hybridization and MnO₆ crystal field. The other is the interfacial region where the nonuniform Mn? O bond length d and Mn? O? Mn bond angle θ disturb the structural modulation. When the interfacial region is suppressed in the interface‐engineered samples, the lateral magnetic anisotropy energy is increased eighteen times. The d‐mediated anisotropic crystal filed that overwhelms the orbital hybridization causes the lateral symmetry breaking of the Mn 3d_x²_?y² orbital, resulting in enhanced magnetic anisotropy. This is different from the classic Jahn–Teller effect where the lateral symmetry is always preserved. Moreover, the quantitative analysis on X‐ray linear dichroism data suggests a direct correlation between Mn 3d_x²_?y² orbital symmetry breaking and magnetic anisotropy energy. The findings not only advance the understanding of magnetic anisotropy in manganite heterostructures but also can be extended to other complex oxides and perovskite materials with correlated degrees of freedom.     

Interfacial Oxygen-Driven Charge Localization and Plasmon Excitation in Unconventional Superconductors

Charge localization is critical to the control of charge dynamics in systems such as perovskite solar cells, organic-, and nanostructure-based photovoltaics. However, the precise control of charge localization via electronic transport or defect engineering is challenging due to the complexity in reaction pathways and environmental factors. Here, charge localization in optimal-doped La_1.85Sr_0.15CuO₄ thin-film on SrTiO₃ substrate (LSCO/STO) is investigated, and also a high-energy plasmon is observed. Charge localization manifests as a near-infrared mid-gap state in LSCO/STO. This is ascribed to the interfacial hybridization between the Ti3d-orbitals of the substrate and O2p-orbitals of the film. The interfacial effect leads to significant changes in the many-body correlations and local-field effect. The local-field effect results in an inhomogeneous charge distribution, and due to perturbation by an external field, the high polarizability of this nonuniform charge system eventually generates the high-energy plasmon. Transformation of the electronic correlations in LSCO/STO is further demonstrated via temperature-dependent spectral-weight transfer. This study of charge localization in cuprates and interfacial hybridization provides important clues to their electronic structures and superconductive properties.     

Room-Temperature Colossal Magnetoresistance in Terraced Single-Layer Graphene

Disorder-induced magnetoresistance (MR) effect is quadratic at low perpendicular magnetic fields and linear at high fields. This effect is technologically appealing, especially in 2D materials such as graphene, since it offers potential applications in magnetic sensors with nanoscale spatial resolution. However, it is a great challenge to realize a graphene magnetic sensor based on this effect because of the difficulty in controlling the spatial distribution of disorder and enhancing the MR sensitivity in the single-layer regime. Here, a room-temperature colossal MR of up to 5000% at 9 T is reported in terraced single-layer graphene. By laminating single-layer graphene on a terraced substrate, such as TiO₂-terminated SrTiO₃, a universal one order of magnitude enhancement in the MR compared to conventional single-layer graphene devices is demonstrated. Strikingly, a colossal MR of >1000% is also achieved in the terraced graphene even at a high carrier density of ≈10¹² cm⁻². Systematic studies of the MR of single-layer graphene on various oxide- and non-oxide-based terraced surfaces demonstrate that the terraced structure is the dominant factor driving the MR enhancement. The results open a new route for tailoring the physical property of 2D materials by engineering the strain through a terraced substrate.