Inverted orbital polarization in strained correlated oxide films

Manipulating the orbital occupation of valence electrons via epitaxial strain in an effort to induce new functional properties requires considerations of how changes in the local bonding environment affect the band structure at the Fermi level. Using synchrotron radiation to measure the x-ray linear dichroism of epitaxially strained films of the correlated oxide CaFeO3, we demonstrate that the orbital polarization of the Fe valence electrons is opposite from conventional understanding. Although the energetic ordering of the Fe 3d orbitals is confirmed by multiplet ligand field theory analysis to be consistent with previously reported strain-induced behavior, we find that the nominally higher energy orbital is more populated than the lower. We ascribe this inverted orbital polarization to an anisotropic bandwidth response to strain in a compound with nearly filled bands. These findings provide an important counterexample to the traditional understanding of strain-induced orbital polarization and reveal a new method to engineer otherwise unachievable orbital occupations in correlated oxides

Magnetism and Faraday Rotation in Oxygen-Deficient Polycrystalline and Single-Crystal Iron-Substituted Strontium Titanate

Both polycrystalline and single-crystal films of iron-substituted strontium titanate, Sr(Ti[subscript 0.65]Fe[subscript 0.35])O[subscript 3−δ], prepared by pulsed laser deposition, show room-temperature magnetism and Faraday rotation, with the polycrystalline films exhibiting higher saturation magnetization and Faraday rotation. The magnetic properties vary with the oxygen pressure at which the films are grown, showing a maximum at pressures of approximately 4  μ Torr at which the unit-cell volume is largest. The results are discussed in terms of the oxygen stoichiometry and corresponding Fe valence states, the structure and strain state, and the presence of small-volume fractions of metallic Fe in single-crystal films grown at the optimum deposition pressure. Integration of magneto-optical polycrystalline films on an optical-waveguide device demonstrates a nonreciprocal phase shift.National Science Foundation (U.S.) (Grants DMR1419807 and ECCS1607865)Semiconductor Research Corporation. Function Accelerated nanoMaterial Engineerin

Emergent electric field control of phase transformation in oxide superlattices.

Electric fields can transform materials with respect to their structure and properties, enabling various applications ranging from batteries to spintronics. Recently electrolytic gating, which can generate large electric fields and voltage-driven ion transfer, has been identified as a powerful means to achieve electric-field-controlled phase transformations. The class of transition metal oxides provide many potential candidates that present a strong response under electrolytic gating. However, very few show a reversible structural transformation at room-temperature. Here, we report the realization of a digitally synthesized transition metal oxide that shows a reversible, electric-field-controlled transformation between distinct crystalline phases at room-temperature. In superlattices comprised of alternating one-unit-cell of SrIrO3 and La0.2Sr0.8MnO3, we find a reversible phase transformation with a 7% lattice change and dramatic modulation in chemical, electronic, magnetic and optical properties, mediated by the reversible transfer of oxygen and hydrogen ions. Strikingly, this phase transformation is absent in the constituent oxides, solid solutions and larger period superlattices. Our findings open up this class of materials for voltage-controlled functionality

Chemomechanics of ionically conductive ceramics for electrical energy conversion and storage

Functional materials for energy conversion and storage exhibit strong coupling between electrochemistry and mechanics. For example, ceramics developed as electrodes for both solid oxide fuel cells and batteries exhibit cyclic volumetric expansion upon reversible ion transport. Such chemomechanical coupling is typically far from thermodynamic equilibrium, and thus is challenging to quantify experimentally and computationally. In situ measurements and atomistic simulations are under rapid development to explore how this coupling can be used to potentially improve both device performance and durability. Here, we review the commonalities of coupling between electrochemical and mechanical states in fuel cell and battery materials, illustrating with specific cases the progress in materials processing, in situ characterization, and computational modeling and simulation. We also highlight outstanding questions and opportunities in these applications – both to better understand the limiting mechanisms within the materials and to significantly advance the durability and predictability of device performance required for renewable energy conversion and storage.United States. Dept. of Energy (Basic Energy Sciences Division of Materials Sciences and Engineering, grant DE-SC0002633)United States. Dept. of Energy (Office of Science, Graduate Fellowship Program (DOE SCGF))United States. American Recovery and Reinvestment Act of 2009 (ORISE-ORAU, contract no. DE-AC05-06OR23100))United States. Dept. of Energy. Division of Materials Sciences and Engineering (MIT/DMSE Salapatas Fellowship)United States. Air Force Office of Scientific Research (Presidential Early Career Award in Science and Engineering (PECASE)

Coherent Fe-rich nano-scale perovskite oxide phase in epitaxial Sr2FeMoO6 films grown on cubic and scandate substrates

We report the growth of high-quality epitaxial Sr2FeMoO6 (SFMO) thin films on various unconventional oxide substrates, such as TbScO3, DyScO3, and Sr2Al0.3Ga0.7TaO6 (SAGT) as well as on the most commonly used one, SrTiO3 (STO), by pulsed laser deposition. The films were found to contain a foreign nano-scale phase coherently embedded inside the SFMO film matrix. Through energy dispersive X-ray spectroscopy and scanning transmission electron microscopy, we identified the foreign phase to be Sr2−xFe1+yMo1−yO6, an off-stoichiometric derivative of the SFMO compound with Fe rich content (y ≈ 0.6) and a fairly identical crystal structure to SFMO. The films on STO and SAGT exhibited very good magnetic properties with high Curie temperature values. All the samples have fairly good conducting behavior albeit the presence of a foreign phase. Despite the relatively large number of items of the foreign phase, there is no significant deterioration in the properties of the SFMO films. We discuss in detail how magneto-transport properties are affected by the foreign phase. INT

Proton Conduction in Grain-Boundary-Free Oxygen-Deficient BaFeO2.5+δ_{2.5+δ} Thin Films

Reduction of the operating temperature to an intermediate temperature range between 350 °C and 600 °C is a necessity for Solid Oxide Fuel/Electrolysis Cells (SOFC/SOECs). In this respect the application of proton-conducting oxides has become a broad area of research. Materials that can conduct protons and electrons at the same time, to be used as electrode catalysts on the air electrode, are especially rare. In this article we report on the proton conduction in expitaxially grown BaFeO2.5+δ (BFO) thin films deposited by pulsed laser deposition on Nb:SrTiO3 substrates. By using Electrochemical Impedance Spectroscopy (EIS) measurements under different wet and dry atmospheres, the bulk proton conductivity of BFO (between 200 °C and 300 °C) could be estimated for the first time (3.6 × 10−6 S cm−1 at 300 °C). The influence of oxidizing measurement atmosphere and hydration revealed a strong dependence of the conductivity, most notably at temperatures above 300 °C, which is in good agreement with the hydration behavior of BaFeO2.5 reported previously

Layer Resolved Cr Oxidation State Modulation in Epitaxial SrFe0.67Cr0.33O3−δ Thin Films

Understanding how doping influences physicochemical properties of ABO3 perovskite oxides is critical for tailoring their functionalities. In this study, SrFe0.67Cr0.33O3-δ epitaxial thin films were used to examine the effects of Fe and Cr competition on structure and B-site cation oxidation states. The films exhibit a perovskite-like structure near the film/substrate interface, while a brownmillerite-like structure with horizontal oxygen vacancy channels predominates near the surface. Electron energy loss spectroscopy shows Fe remains Fe3+, while Cr varies from ∼Cr3+ (tetrahedral layers) to ∼Cr4+ (octahedral layers) within brownmillerite phases and becomes ∼Cr4.5+ in perovskite-like phases. Theoretical simulations indicate that Cr-O bond arrangements and the way oxygen vacancies interact with Cr and Fe drive Cr charge disproportionation. High-valent Cr cations introduce additional densities of states near the Fermi level, reducing the optical bandgap from ∼2.0 eV (SrFeO2.5) to ∼1.7 eV (SrFe0.67Cr0.33O3-δ). These findings offer insights into B-site cation doping in the perovskite oxide framework