Near-Atomic-Scale Mapping of Electronic Phases in Rare Earth Nickelate Superlattices.

Nanoscale mapping of the distinct electronic phases characterizing the metal-insulator transition displayed by most of the rare-earth nickelate compounds is fundamental for discovering the true nature of this transition and the possible couplings that are established at the interfaces of nickelate-based heterostructures. Here, we demonstrate that this can be accomplished by using scanning transmission electron microscopy in combination with electron energy-loss spectroscopy. By tracking how the O K and Ni L edge fine structures evolve across two different NdNiO3/SmNiO3 superlattices, displaying either one or two metal-insulator transitions depending on the individual layer thickness, we are able to determine the electronic state of each of the individual constituent materials. We further map the spatial configuration associated with their metallic/insulating regions, reaching unit cell spatial resolution. With this, we estimate the width of the metallic/insulating boundaries at the NdNiO3/SmNiO3 interfaces, which is measured to be on the order of four unit cells.

Length scales of interfacial coupling between metal and insulator phases in oxides.

Controlling phase transitions in transition metal oxides remains a central feature of both technological and fundamental scientific relevance. A well-known example is the metal-insulator transition, which has been shown to be highly controllable. However, the length scale over which these phases can be established is not yet well understood. To gain insight into this issue, we atomically engineered an artificially phase-separated system through fabricating epitaxial superlattices that consist of SmNiO3 and NdNiO3, two materials that undergo a metal-to-insulator transition at different temperatures. We demonstrate that the length scale of the interfacial coupling between metal and insulator phases is determined by balancing the energy cost of the boundary between a metal and an insulator and the bulk phase energies. Notably, we show that the length scale of this effect exceeds that of the physical coupling of structural motifs, which introduces a new framework for interface-engineering properties at temperatures against the bulk energetics.

Valence-Ordered Thin-Film Nickelate with Tri-component Nickel Coordination Prepared by Topochemical Reduction.

The metal-hydride-based "topochemical reduction" process has produced several thermodynamically unstable phases across various transition metal oxide series with unusual crystal structures and nontrivial ground states. Here, by such an oxygen (de-)intercalation method we synthesis a samarium nickelate with ordered nickel valences associated with tri-component coordination configurations. This structure, with a formula of Sm9Ni9O22 as revealed by four-dimensional scanning transmission electron microscopy (4D-STEM), emerges from the intricate planes of {303}pc ordered apical oxygen vacancies. X-ray spectroscopy measurements and ab initio calculations show the coexistence of square planar, pyramidal, and octahedral Ni sites with mono-, bi-, and tri-valences. It leads to an intense orbital polarization, charge-ordering, and a ground state with a strong electron localization marked by the disappearance of ligand-hole configuration at low temperature. This nickelate compound provides another example of previously inaccessible materials enabled by topotactic transformations and presents an interesting platform where mixed Ni valence can give rise to exotic phenomena.

Water-hydroxide trapping in cobalt tungstate for proton exchange membrane water electrolysis.

The oxygen evolution reaction is the bottleneck to energy-efficient water-based electrolysis for the production of hydrogen and other solar fuels. In proton exchange membrane water electrolysis (PEMWE), precious metals have generally been necessary for the stable catalysis of this reaction. In this work, we report that delamination of cobalt tungstate enables high activity and durability through the stabilization of oxide and water-hydroxide networks of the lattice defects in acid. The resulting catalysts achieve lower overpotentials, a current density of 1.8 amperes per square centimeter at 2 volts, and stable operation up to 1 ampere per square centimeter in a PEMWE system at industrial conditions (80°C) at 1.77 volts; a threefold improvement in activity; and stable operation at 1 ampere per square centimeter over the course of 600 hours.

Metal-insulator transition in composition-tuned nickel oxide films.

Thin films of the solid solution Nd1-xLaxNiO3are grown in order to study the expected 0 K phase transitions at a specific composition. We experimentally map out the structural, electronic and magnetic properties as a function ofxand a discontinuous, possibly first order, insulator-metal transition is observed at low temperature whenx= 0.2. Raman spectroscopy and scanning transmission electron microscopy show that this is not associated with a correspondingly discontinuous global structural change. On the other hand, results from density functional theory (DFT) and combined DFT and dynamical mean field theory calculations produce a 0 K first order transition at around this composition. We further estimate the temperature-dependence of the transition from thermodynamic considerations and find that a discontinuous insulator-metal transition can be reproduced theoretically and implies a narrow insulator-metal phase coexistence withx. Finally, muon spin rotation (µSR) measurements suggest that there are non-static magnetic moments in the system that may be understood in the context of the first order nature of the 0 K transition and its associated phase coexistence regime.

Suppression of superconductivity at the nanoscale in chemical solution derived YBa2Cu3O7-δ thin films with defective Y2Ba4Cu8O16 intergrowths.

The analysis of the microstructure and superconducting behavior of chemical solution deposited epitaxial YBa2Cu3O7-δ films, with thickness going down to 5 nm has been carried out with the purpose to disclose the behavior of the most common intergrowth in these films, the Y2Ba4Cu8O16. The analysis of ultrathin films is a unique opportunity to investigate the superconducting behavior of these nanoscale defects because of the high concentration created as a consequence of the elastic energy associated to the misfit strain. Magnetic susceptibility and X-ray diffraction measurements evidence a strong decrease of the superconducting volume correlated with an increase of the intergrowth volume fraction. We demonstrate that these intergrowths are non-superconducting nanoscale regions where Cooper pair formation is disrupted, in agreement with their key role as artificial pinning centers for vortices in YBa2Cu3O7-δ films and coated conductors.

Local strain-driven migration of oxygen vacancies to apical sites in YBa2Cu3O7-x.

It is well known that in the high-temperature superconductor YBa2Cu3O7-x (YBCO), oxygen vacancies (VO) control the carrier concentration, its critical current density and transition temperature. In this work, it is revealed that VO also allows the accommodation of local strain fields caused by large-scale defects within the crystal. We show that the nanoscale strain associated with Y2Ba4Cu8O16 (Y124) intergrowths-that are common defects in YBCO-strongly affect the venue and concentration of VO. Local probe measurements in conjunction with density-functional-theory calculations indicate a strain-driven reordering of VO from the commonly observed CuO chains towards the bridging apical sites located in the BaO plane and bind directly to the superconducting CuO2 planes. Our findings have strong implications on the physical properties of the YBCO, as the presence of apical VO alters the transfer of carriers to the CuO2 planes, confirmed by changes in the Cu and O core-loss edge probed using electron energy loss spectroscopy, and creates structural changes that affect the Cu-O bonds in the superconducting planes. In addition, the revelation of apical VO also has implications on modulating critical current densities and enhancing vortex pinning.

Control of nanostructure and pinning properties in solution deposited YBa2Cu3O7-x nanocomposites with preformed perovskite nanoparticles.

Solution deposited YBa2Cu3O7-x (YBCO) nanocomposites with preformed nanoparticles represent a promising cost-effective approach for superior critical current properties under applied magnetic fields. Nonetheless, the majority of YBCO nanocomposites with high nanoparticle loads (>20%) suffer from nanoparticle coalescence and degraded superconducting properties. Here, we study the influence of nanoparticle concentration (0-25% mol), size (5 nm-10 nm) and composition (BaHfO3, BaZrO3) on the generation of structural defects in the epitaxial YBCO matrix, key parameter for vortex pinning. We demonstrate that flash-heated superconducting nanocomposites with 20 mol% preformed BaHfO3 or BaZrO3 perovskite secondary phases feature discrete and small (7 nm) nanoparticles and high density of YBa2Cu4O8 (Y248) intergrowths. We identify a synergy between Y248 intergrowth density and small nanoparticles to increase artificial vortex pinning centers. Also, we validate the multideposition process to successfully increase film thickness of epitaxial nanocomposites with competitive critical currents Ic at 77 K.