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.

Oxygen stoichiometry is one of the most important elements in determining the physical properties of transition metal oxides (TMOs). A small change in the oxygen content results in the variation of valence state of the transition metal, drastically modifying the materials functionalities. The latter includes, for instance, (super-)conductivity, magnetism, ferroelectricity, bulk ionic conduction, and catalytic surface reactions. [1][2][3][4][5] In particular, among those applications, TMOs with mixed valence states have attracted attention for many environmental and renewable energy applications, including catalysts, hydrogen generation from water splitting, cathodes in rechargeable batteries and solid oxide fuel cells, and oxygen separation membranes. [6][7][8] For example, previous studies have shown that the ability to control the number of d-band electron population and detailed spin configuration in TMOs is critical for improved catalytic performance of TMOs. [9,10] In this context, SrCoO x (2.5 ≤ x ≤ 3.0) is an ideal class of materials to study the evolution of the physical properties by modifying the valence state in TMOs, due to the existence of two structurally distinct topotactic phases, i.e. the brownmillerite SrCoO 2.5 (BM-2 SCO) (see Figure 1a) and the perovskite SrCoO 3 . [11,12] Especially, BM-SCO has atomicallyordered one-dimensional vacancy channels (see Figure 1a), which can accommodate additional oxygen when the valence state of Co is changed. Moreover, SrCoO x exhibits a wide spectrum of physical properties from antiferromagnetic insulator to ferromagnetic metal depending on the oxygen stoichiometry. [11][12][13] Since SrCoO x has only a single control knob, i.e. the oxygen contentx, to modify the Co valence state without cation doping, it is straightforward to study the valence state (i.e. oxygen content) dependent physical properties. However, so far, the growth of high quality single crystalline materials has not been as successful due to difficulty in controlling the right oxidation state.In this work, we report on the epitaxial growth of high quality BM-SCO single crystalline films on SrTiO 3 (STO) substrates by pulsed laser epitaxy (PLE). In order to examine the topotactic phase transformation to the perovskite SrCoO 3- (P-SCO), some of the samples were subsequently in-situ annealed at various oxygen pressure (P(O 2 )) to fill the oxygen vacancies.While the direct growth of P-SCO films with x = 3.0 was an arduous task, we found that postannealing in high P(O 2 ) (> several hundreds of Torr) could fill sufficient amount of oxygen vacancies, yielding systematic evolution in electronic, magnetic, and thermoelectric properties. (Figure 1b) demonstrate that the films are of high quality. X-ray rocking curve ω-scans revealed a full width half maximum (FWHM) of < 0.04º, demonstrating the excellent crystallinity (cf., FWHM of the 002 STO peak was ~0.02º) of our films (data not shown).While we have shown the XRD data from a well-optimized, high quality thin film, it is worthwhile to mention tha...

Epitaxial strain imposed in complex oxide thin films by heteroepitaxy is recognized as a powerful tool for identifying new properties and exploring the vast potential of materials performance. A particular example is LaCoO(3), a zero spin, nonmagnetic material in the bulk, whose strong ferromagnetism in a thin film remains enigmatic despite a decade of intense research. Here, we use scanning transmission electron microscopy complemented by X-ray and optical spectroscopy to study LaCoO(3) epitaxial thin films under different strain states. We observed an unconventional strain relaxation behavior resulting in stripe-like, lattice modulated patterns, which did not involve uncontrolled misfit dislocations or other defects. The modulation entails the formation of ferromagnetically ordered sheets comprising intermediate or high spin Co(3+), thus offering an unambiguous description for the exotic magnetism found in epitaxially strained LaCoO(3) films. This observation provides a novel route to tailoring the electronic and magnetic properties of functional oxide heterostructures.

The ability to manipulate oxygen anion defects rather than metal cations in complex oxides is facilitating new functionalities critical for emerging energy and device technologies.However, the difficulty in activating oxygen at reduced temperatures hinders the deliberate control of an important defect, oxygen vacancies. Here, strontium cobaltite (SrCoO x ) is used to demonstrate that epitaxial strain is a powerful tool for manipulating the oxygen vacancy concentration even under highly oxidizing environments and at annealing temperatures as low as 300 °C. By applying a small biaxial tensile strain (2%), the oxygen activation energy barrier decreases by ~30%, resulting in a tunable oxygen deficient steady-state under conditions that would normally fully oxidize unstrained cobaltite. These strain-induced changes in oxygen stoichiometry drive the cobaltite from a ferromagnetic metal towards an antiferromagnetic insulator. The ability to decouple the oxygen vacancy concentration from its typical dependence on the operational environment is useful for effectively designing oxides materials with a specific oxygen stoichiometry.2

The slow kinetics of the oxygen reduction and evolution reactions (ORR, OER) hinder energy conversion and storage in alkaline fuel cells and electrolyzers employing abundant transition metal oxide catalysts. Systematic studies linking material properties to catalytic activity are lacking, in part due to the heterogeneous nature of powder-based electrodes. We demonstrate, for the first time, that epitaxial strain can tune the activity of oxygen electrocatalysis in alkaline solutions, focusing on the model chemistry of LaCoO3, where moderate tensile strain can further induce changes in the electronic structure leading to increased activity. The resultant decrease in charge transfer resistance to the electrolyte reduces the overpotential in the ORR more notably than the OER and suggests a different dependence of the respective rate-limiting steps on electron transfer. This provides new insight into the reaction mechanism applicable to a range of perovskite chemistries, key to the rational design of highly active catalysts.

We investigated the temperature-dependent evolution of the electronic structure of the J eff = 1 2 Mott insulator Sr 2 IrO 4 using optical spectroscopy. The optical conductivity spectra ͑ ͒ of this compound has recently been found to exhibit two d-d transitions associated with the transition between the J eff = 1 2 and J eff = 3 2 bands due to the cooperation of the electron correlation and spin-orbit coupling. As the temperature increases, the two peaks show significant changes resulting in a decrease in the Mott gap. The experimental observations are compared with the results of first-principles calculation in consideration of increasing bandwidth. We discuss the effect of the temperature change in the electronic structure of Sr 2 IrO 4 in terms of local lattice distortion, excitonic effect, electron-phonon coupling, and magnetic ordering.

The ferroelectric (FE) control of electronic transport is one of the emerging technologies in oxide heterostructures. Many previous studies in FE tunnel junctions (FTJs) exploited solely the differences in the electrostatic potential across the FTJs that are induced by changes in the FE polarization direction. Here, we show that in practice the junction current ratios between the two polarization states can be further enhanced by the electrostatic modification in the correlated electron oxide electrodes, and that FTJs with nanometer thin layers can effectively produce a considerably large electroresistance ratio at room temperature. To understand these surprising results, we employed an additional control parameter, which is related to the crossing of electronic and magnetic phase boundaries of the correlated electron oxide. The FE-induced phase modulation at the heterointerface ultimately results in an enhanced electroresistance effect. Our study highlights that the strong coupling between degrees of freedom across heterointerfaces could yield versatile and novel applications in oxide electronics.