Orbital reconstructions and covalent bonding must be considered as important factors in the rational design of oxide heterostructures with engineered physical properties. We have investigated the interface between high-temperature superconducting (Y,Ca)Ba(2)Cu3O7 and metallic La(0.67)Ca(0.33)MnO3 by resonant x-ray spectroscopy. A charge of about -0.2 electron is transferred from Mn to Cu ions across the interface and induces a major reconstruction of the orbital occupation and orbital symmetry in the interfacial CuO2 layers. In particular, the Cu d(3z(2)-r(2)) orbital, which is fully occupied and electronically inactive in the bulk, is partially occupied at the interface. Supported by exact-diagonalization calculations, these data indicate the formation of a strong chemical bond between Cu and Mn atoms across the interface. Orbital reconstructions and associated covalent bonding are thus important factors in determining the physical properties of oxide heterostructures.

Topological insulators are insulating materials that display conducting surface states protected by time-reversal symmetry, wherein electron spins are locked to their momentum. This unique property opens up new opportunities for creating next-generation electronic, spintronic and quantum computation devices. Introducing ferromagnetic order into a topological insulator system without compromising its distinctive quantum coherent features could lead to the realization of several predicted physical phenomena. In particular, achieving robust long-range magnetic order at the surface of the topological insulator at specific locations without introducing spin-scattering centres could open up new possibilities for devices. Here we use spin-polarized neutron reflectivity experiments to demonstrate topologically enhanced interface magnetism by coupling a ferromagnetic insulator (EuS) to a topological insulator (Bi2Se3) in a bilayer system. This interfacial ferromagnetism persists up to room temperature, even though the ferromagnetic insulator is known to order ferromagnetically only at low temperatures (<17 K). The magnetism induced at the interface resulting from the large spin-orbit interaction and the spin-momentum locking of the topological insulator surface greatly enhances the magnetic ordering (Curie) temperature of this bilayer system. The ferromagnetism extends ~2 nm into the Bi2Se3 from the interface. Owing to the short-range nature of the ferromagnetic exchange interaction, the time-reversal symmetry is broken only near the surface of a topological insulator, while leaving its bulk states unaffected. The topological magneto-electric response originating in such an engineered topological insulator could allow efficient manipulation of the magnetization dynamics by an electric field, providing an energy-efficient topological control mechanism for future spin-based technologies.

Ferroelectric ferromagnets are exceedingly rare, fundamentally interesting multiferroic materials that could give rise to new technologies in which the low power and high speed of field-effect electronics are combined with the permanence and routability of voltage-controlled ferromagnetism. Furthermore, the properties of the few compounds that simultaneously exhibit these phenomena are insignificant in comparison with those of useful ferroelectrics or ferromagnets: their spontaneous polarizations or magnetizations are smaller by a factor of 1,000 or more. The same holds for magnetic- or electric-field-induced multiferroics. Owing to the weak properties of single-phase multiferroics, composite and multilayer approaches involving strain-coupled piezoelectric and magnetostrictive components are the closest to application today. Recently, however, a new route to ferroelectric ferromagnets was proposed by which magnetically ordered insulators that are neither ferroelectric nor ferromagnetic are transformed into ferroelectric ferromagnets using a single control parameter, strain. The system targeted, EuTiO(3), was predicted to exhibit strong ferromagnetism (spontaneous magnetization, approximately 7 Bohr magnetons per Eu) and strong ferroelectricity (spontaneous polarization, approximately 10 microC cm(-2)) simultaneously under large biaxial compressive strain. These values are orders of magnitude higher than those of any known ferroelectric ferromagnet and rival the best materials that are solely ferroelectric or ferromagnetic. Hindered by the absence of an appropriate substrate to provide the desired compression we turned to tensile strain. Here we show both experimentally and theoretically the emergence of a multiferroic state under biaxial tension with the unexpected benefit that even lower strains are required, thereby allowing thicker high-quality crystalline films. This realization of a strong ferromagnetic ferroelectric points the way to high-temperature manifestations of this spin-lattice coupling mechanism. Our work demonstrates that a single experimental parameter, strain, simultaneously controls multiple order parameters and is a viable alternative tuning parameter to composition for creating multiferroics.

The interaction between the transition metal 3d and the oxygen 2p states via hybridization underpins many of the phenomena in transition metal oxide materials. We report the empirical trend of this interaction using the pre-edge feature of the O Kedge X-ray absorption spectrum. Our assessment method is built on the dipole approximation and the configuration interaction between the transition metal 3d and the oxygen 2p states. We found that hybridization increases with the number of 3d electrons, consistent with the expected electronegativity trend. We support this analysis with density functional calculations, which reveal a systematic increase in the transition metal 3d and the oxygen 2p state mixing with increasing 3d-electron number. Oxidation of the transition metal was also found to increase hybridization, which we believe reflects the reduced transition metal 3d and oxygen 2p energy difference, causing increased covalency. We compare the analysis from the surface-sensitive electron-yield and the bulk-sensitive fluorescence-yield spectra, revealing that either method can be used to study the hybridization trend. We finally compare and discuss the influence of the lanthanide ions and the influence of the covalency on oxygen electrocatalysis. Our study describes an efficient and simple approach to understand the hybridization trend in transition metal oxides, which has considerable implications for electrochemical energy conversion processes.

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Abstract

ABSTRACT:Strain is known to greatly influence low temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. However, its catalytic impact on transition metal oxide (TMO) thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO 3 to systematically determine its influence on both the oxygen reduction (ORR) and oxygen evolution reaction (OER). Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to straininduced splitting of the e g orbitals, which can customize orbital asymmetry at the surface. Analogous to straininduced shifts in the d-band center of noble metals relative to Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides. Advancements in energy storage are essential for driving the development of more sophisticated mobile technologies as well as continuing the trend towards a greener economy. At the forefront of this push are high energy density devices, such as regenerative fuel cells and metal-air batteries. 1 In these and related electrochemical systems, both the oxygen reduction and oxygen evolution reactions (ORR and OER, respectively) are crucial towards successful operation. 2 Traditionally, conductive catalysts incorporating noble metals (e.g., Pt and IrO 2 ) have been used to facilitate these reactions near room temperature. 3 To alleviate costs and poor stabilities during OER in alkaline solutions, significant efforts have focused on transition metal oxides (TMOs) with multivalent Ni, Fe, Co, and Mn, such as NiFeO x .4 Similar to alloying in noble metals, the majority of research into increasing oxygen activities of TMOs involves cationic doping, which often promotes either the ORR or OER but not bifunctionality. 5Here, we explore how another factor, i.e. strain, can influence bifunctionality in TMOs. Contemporary work on high-temperature (>500 C) oxide catalysis in an aprotic environment (e.g. ORR: O 2 + 4e -→ 2O 2-) has emphasized the importance of tensile strain for activating defects to improve catalytic reactions. 6 In an alkaline environment (e. . Among TMOs, the ABO 3 perovskites, in which A is traditionally from Groups I-III and B is a transition metal ion with six-fold octahedral coordination, also have electronic structures that are sensitive to strain. Due to strong hybridization between the O 2p and the transition metal d z 2 and d x 2 -y 2 lobes in the BO 6 octahedra, the σ* states near E F consist of e g orbitals. 10,10b Similar to the Jahn-Teller distortion, strain is known to lift the degeneracy in these symmetry-localized d z 2 and d x 2 -y 2 orbitals, yielding changes in the orbital occupancy, or polarization.7a, 11 By using strain to control the degree of this ...

Fast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for enhancing the overall performance and lifetime of many energy materials and devices. However, the robust nature of the cation's oxidation state and the high thermodynamic barrier have hindered the realization of fast catalysis and bulk diffusion at low temperatures. Here, we report a significant lowering of the redox temperature by epitaxial stabilization of strontium cobaltites (SrCoO(x)) grown directly as one of two distinct crystalline phases, either the perovskite SrCoO(3-δ) or the brownmillerite SrCoO(2.5). Importantly, these two phases can be reversibly switched at a remarkably reduced temperature (200-300 °C) in a considerably short time (< 1 min) without destroying the parent framework. The fast, low-temperature redox activity in SrCoO(3-δ) is attributed to a small Gibbs free-energy difference between two topotatic phases. Our findings thus provide useful information for developing highly sensitive electrochemical sensors and low-temperature cathode materials.