Highly Energy-Efficient Spin Current Generation in SrIrO3 by Manipulating the Octahedral Rotation.

Materials with strong spin-orbit coupling (SOC) have been continuously attracting intensive attention due to their promising application in energy-efficient, high-density, and nonvolatile spintronic devices. Particularly, transition-metal perovskite oxides with strong SOC have been demonstrated to exhibit efficient charge-spin interconversion. In this study, we systematically investigated the impact of epitaxial strain on the spin-orbit torque (SOT) efficiency in the SrIrO3(SIO)/Ni81Fe19(Py) bilayer. The results reveal that the SOT efficiency is strongly related to the octahedral rotation around the in-plane axes of the single-crystal SIO. By modulating the epitaxial strain using different substrates, the SOT efficiency can be remarkably improved from 0.15 to 1.45. This 10-fold enhancement of SOT efficiency suggests that modulating the epitaxial strain is an efficient approach to control the SOT efficiency in complex oxide-based heterostructures. Our work may have the potential to advance the application of complex oxides in energy-efficient spintronic devices.

Modulation of Spin-Orbit Torque from SrRuO3 by Epitaxial-Strain-Induced Octahedral Rotation.

Spin-orbit torque (SOT), which arises from the spin-orbit coupling of conduction electrons, is believed to be the key route for developing low-power, high-speed, and nonvolatile memory devices. Despite the theoretical prediction of pronounced Berry phase curvatures in certain transition-metal perovskite oxides, which lead to considerable intrinsic spin Hall conductivity, SOT from this class of materials has rarely been reported until recently. Here, the SOT generated by epitaxial SrRuO3 of three different crystal structures is systematically studied. The results of both spin-torque ferromagnetic resonance and in-plane harmonic Hall voltage measurements concurrently reveal that the intrinsic SOT efficiency of SrRuO3 decreases when the epitaxial strain changes from tensile to compressive. The X-ray diffraction data demonstrate a strong correlation between the magnitude of SOT and octahedral rotation around the in-plane axes of SrRuO3 , consistent with the theoretical prediction. This work offers new possibilities of tuning SOT with crystal structures and novel opportunities of integrating the unique properties of perovskite oxides with spintronic functionalities.

Hole-Trapping-Induced Stabilization of Ni4 + in SrNiO3 /LaFeO3 Superlattices.

Creating new functionality in materials containing transition metals is predicated on the ability to control the associated charge states. For a given transition metal, there is an upper limit on valence that is not exceeded under normal conditions. Here, it is demonstrated that this limit of 3+ for Ni and Fe can be exceeded via synthesis of (SrNiO3 )m /(LaFeO3 )n superlattices by tuning n and m. The Goldschmidt tolerance constraints are lifted, and SrNi4+ O3 with holes on adjacent O anions is stabilized as a perovskite at the single-unit-cell level (m = 1). Holding m = 1, spectroscopy reveals that the n = 1 superlattice contains Ni3+ and Fe4+ , whereas Ni4+ and Fe3+ are observed in the n = 5 superlattice. It is revealed that the B-site cation valences can be tuned by controlling the magnitude of the FeO6 octahedral rotations, which, in turn, determine the energy balance between Ni3+ /Fe4+ and Ni4+ /Fe3+ , thus controlling emergent electrical properties such as the band alignment and resulting hole confinement. This approach can be extended to other systems for synthesizing novel, metastable layered structures with new functionalities.

Tuning Irreversible Magnetoresistance in Pr0.67Sr0.33MnO3 Film via Octahedral Rotation.

The oxygen octahedral rotation around the out-of-plane axis is explored to study its effect on metastable status, magnetic cluster glass in manganite. The antiphase rotation around the out-of-plane axis (TiO6 a0a0c-) of SrTiO3 enhances the Mn-O bond anisotropy along in-plane and out-of-plane directions and weakens the ferromagnetic interactions in a 12 nm Pr0.67Sr0.33MnO3 film on the (001) SrTiO3 substrate, which together promote the formation of magnetic cluster-glassiness and enlarges the irreversible magnetoresistance (MR) effect with enhanced relaxation time of charge carriers. The effect of TiO6 a0a0c- in the SrTiO3 substrate on material properties is obvious with a large irreversible MR effect for thin films, which fades away with the increase in film thickness. At 10 K, the irreversible MR is 0.91 for the 12 nm film and 0.22 for the 30 nm film. This work extends current understanding on interfacial coupling to metastable status and could help explore other systems in the perovskite structure with octahedral rotation.

Electric field control of ordered oxygen vacancy planes and antiferromagnetic structures in strontium cobaltite.

The polarized ionic liquids (ILs) could generate intense electric fields on the surface of solid-state materials and create functional defects by ion migration within them, resulting in phase transitions of metal-insulator or paramagnet-ferromagnet, etc. Such a strong electric field even provides an opportunity for the control of spin ordering in antiferromagnetic (AFM) crystal which is difficult to be manipulated due to the strong exchange coupling between antiparallel spins in the whole bulk. Here we find that the ferromagnetic SrCoO3of 40 nm could be transformed to AFM SrCoO2.5with ordered oxygen vacancy planes either vertical (V-SrCoO2.5) or parallel (P-SrCoO2.5) to the surface by IL gating. The spin Hall magnetoresistances suggest that the AFM easy axes of V- and P-SrCoO2.5are along [010] and11¯0, respectively. The orientations of gating induced oxygen vacancy planes are related to the oxygen framework rotation in the parent SrCoO3and could be controlled by the strain engineering. Our results not only supply a novel way to manipulate the AFM spins by creating functional ordered defects, but also reveal the effect of oxygen framework rotation on the formation of oxygen vacancies under ionic liquid gating.

Designing Optimal Perovskite Structure for High Ionic Conduction.

Solid-oxide fuel/electrolyzer cells are limited by a dearth of electrolyte materials with low ohmic loss and an incomplete understanding of the structure-property relationships that would enable the rational design of better materials. Here, using epitaxial thin-film growth, synchrotron radiation, impedance spectroscopy, and density-functional theory, the impact of structural parameters (i.e., unit-cell volume and octahedral rotations) on ionic conductivity is delineated in La0.9 Sr0.1 Ga0.95 Mg0.05 O3- δ . As compared to the zero-strain state, compressive strain reduces the unit-cell volume while maintaining large octahedral rotations, resulting in a strong reduction of ionic conductivity, while tensile strain increases the unit-cell volume while quenching octahedral rotations, resulting in a negligible effect on the ionic conductivity. Calculations reveal that larger unit-cell volumes and octahedral rotations decrease migration barriers and create low-energy migration pathways, respectively. The desired combination of large unit-cell volume and octahedral rotations is normally contraindicated, but through the creation of superlattice structures both expanded unit-cell volume and large octahedral rotations are experimentally realized, which result in an enhancement of the ionic conductivity. All told, the potential to tune ionic conductivity with structure alone by a factor of ≈2.5 at around 600 °C is observed, which sheds new light on the rational design of ion-conducting perovskite electrolytes.

Interfacial Engineering of Ferromagnetism in Epitaxial Manganite/Ruthenate Superlattices via Interlayer Chemical Doping.

Interfacial charge transfer and structural proximity effects are the two essential routes to trigger and tune numerous functionalities of perovskite oxide heterostructures. However, the cooperation and competition of these two interfacial effects in one epitaxial system have not been fully understood. Herein, we fabricate a series of La0.67Ca0.33MnO3/CaRuO3 superlattices and introduce various chemical doping in the nonmagnetic CaRuO3 interlayers. We found that Ti, Sr, and La doping in the CaRuO3 layer can effectively tune the interfacial charge transfer and octahedral rotation, thus modulating the ferromagnetism of the superlattices. Specifically, the B-site Ti doping depletes the Ru 4d band and suppresses the interfacial charge transfer, leading to a decay of ferromagnetic Curie temperature ( TC). In contrast, the A-site Sr doping maintains a sizable charge transfer and meanwhile suppresses the octahedral rotation, which facilitates ferromagnetism and significantly enhances the TC up to 291 K. The La doping turns out to localize the itinerant electrons in the CaRuO3 layer, which suppresses both the interfacial charge transfer and ferromagnetism. The observed intriguing interfacial engineering of magnetism would pave a new way to understand the collective effects of interfacial charge transfer and structural proximity on the physical properties of oxide heterostructures.

Dynamic Field Modulation of the Octahedral Framework in Metal Oxide Heterostructures.

Control over the oxygen octahedral framework is widely recognized as key to the design of functional properties in perovskite oxide heterostructures. Although the oxygen octahedral framework can be manipulated during synthesis, the as-grown oxygen octahedra generally remain fixed, preventing the development of adaptive behavior in electronic and ionotronic systems. Here, it is demonstrated that the oxygen octahedral framework can be dynamically and reversibly manipulated by an electric field through the coupling with oxygen vacancies. Studying model WO3 heterostructures during ionic liquid gating with a combination of in situ X-ray scattering and spectroscopy, it is shown that large changes in electronic properties can arise due to the increased flexibility of the octahedral network at high vacancy concentrations. The results describe a generic framework for the construction of dynamic systems and devices with an array of field-tunable properties.

Metal-insulator-transition engineering by modulation tilt-control in perovskite nickelates for room temperature optical switching.

In transition metal perovskites ABO3, the physical properties are largely driven by the rotations of the BO6 octahedra, which can be tuned in thin films through strain and dimensionality control. However, both approaches have fundamental and practical limitations due to discrete and indirect variations in bond angles, bond lengths, and film symmetry by using commercially available substrates. Here, we introduce modulation tilt control as an approach to tune the ground state of perovskite oxide thin films by acting explicitly on the oxygen octahedra rotation modes-that is, directly on the bond angles. By intercalating the prototype SmNiO3 target material with a tilt-control layer, we cause the system to change the natural amplitude of a given rotation mode without affecting the interactions. In contrast to strain and dimensionality engineering, our method enables a continuous fine-tuning of the materials' properties. This is achieved through two independent adjustable parameters: the nature of the tilt-control material (through its symmetry, elastic constants, and oxygen rotation angles), and the relative thicknesses of the target and tilt-control materials. As a result, a magnetic and electronic phase diagram can be obtained, normally only accessible by A-site element substitution, within the single SmNiO3 compound. With this unique approach, we successfully adjusted the metal-insulator transition (MIT) to room temperature to fulfill the desired conditions for optical switching applications.

Interfacial Octahedral Rotation Mismatch Control of the Symmetry and Properties of SrRuO3.

Epitaxial strain can be used to tune the properties of complex oxides with perovskite structure. Beyond just lattice mismatch, the use of octahedral rotation mismatch at heterointerfaces could also provide an effective route to manipulate material properties. Here, we examine the evolution of the structural motif (i.e., lattice parameters, symmetry, and octahedral rotations) of SrRuO3 films grown on substrates engineered to have the same lattice parameters, but different octahedral rotations. SrRuO3 films grown on SrTiO3 (001) (no octahedral rotations) and GdScO3-buffered SrTiO3 (001) (with octahedral rotations) substrates are found to exhibit monoclinic and tetragonal symmetry, respectively. Electrical transport and magnetic measurements reveal that the tetragonal films exhibit higher resistivity, lower magnetic Curie temperatures, and more isotropic magnetism as compared to those with monoclinic structure. Synchrotron-based quantification of the octahedral rotation network reveals that the tilting pattern in both film variants is the same (albeit with slightly different magnitudes of in-plane rotation angles). The abnormal rotation pattern observed in tetragonal SrRuO3 indicates a possible decoupling between the internal octahedral rotation and lattice symmetry, which could provide new opportunities to engineer thin-film structure and properties.