Understanding the dehydrogenation of transition metal oxide surfaces under electrochemical potential is critical to the control of important chemical processes such as the oxygen evolution reaction (OER). Using first principles computations, we model the thermodynamic dehydrogenation process on RuO_2(110) and compare the results to experimental cyclic voltammetry (CV) on single crystal. We use a cluster expansion model trained on *ab initio* energy data coupled with Monte Carlo (MC) sampling to derive the macroscopic electrochemical observables, i.e., experimental CV, from the energetics of different hydrogen coverage microstates on well-defined RuO_2(110). Our model reproduces the unique "two-peaks" cyclic voltammogram observed experimentally with current density peak positions and shapes in good qualitative agreement. We show that RuO_2(110) starts as a water-covered surface with hydrogen on bridge (BRG) and coordination-unsaturated sites (CUS) at low potential (less than 0.4 V vs. reversible hydrogen electrode, RHE). As the potential increases, the hydrogens on BRG desorb, becoming the main contributor to the first CV peak with smaller contributions from CUS. When all BRG hydrogens are desorbed (before 1.2 V vs. RHE), the remaining CUS hydrogens desorb abruptly in a very small potential window leading to the sharp second peak observed during CV. Our work shows that above 1.23 V, the OER proceeds on a fully dehydrogenated RuO_2(110) surface.

Advancements in materials synthesis have been key to unveil the quantum nature of electronic properties in solids by providing experimental reference points for a correct theoretical description. Here, we report hidden transport phenomena emerging in the ultraclean limit of the archetypical correlated electron system SrVO3. The low temperature, low magnetic field transport was found to be dominated by anisotropic scattering, whereas, at high temperature, we find a yet undiscovered phase that exhibits clear deviations from the expected Landau Fermi liquid, which is reminiscent of strange-metal physics in materials on the verge of a Mott transition. Further, the high sample purity enabled accessing the high magnetic field transport regime at low temperature, which revealed an anomalously high Hall coefficient. Taken with the strong anisotropic scattering, this presents a more complex picture of SrVO3 that deviates from a simple Landau Fermi liquid. These hidden transport anomalies observed in the ultraclean limit prompt a theoretical reexamination of this canonical correlated electron system beyond the Landau Fermi liquid paradigm, and more generally serves as an experimental basis to refine theoretical methods to capture such nontrivial experimental consequences emerging in correlated electron systems.

The rapid development of computing applications demands novel low‐energy consumption devices for information processing. Among various candidates, magnetoelectric heterostructures hold promise for meeting the required voltage and power goals. Here, a route to low‐voltage control of magnetism in 30 nm Fe 0.5 Rh 0.5 /100 nm 0.68PbMg 1/3 Nb 2/3 O 3 ‐0.32PbTiO 3 (PMN‐PT) heterostructures is demonstrated wherein the magnetoelectric coupling is achieved via strain‐induced changes in the Fe 0.5 Rh 0.5 mediated by voltages applied to the PMN‐PT. We describe approaches to achieve high‐quality, epitaxial growth of Fe 0.5 Rh 0.5 on the PMN‐PT films and, a methodology to probe and quantify magnetoelectric coupling in small thin‐film devices via studies of the anomalous Hall effect. By comparing the spin‐flop field change induced by temperature and external voltage, the magnetoelectric coupling coefficient is estimated to reach ≈7 × 10 −8 s m −1 at 325 K while applying a −0.75 V bias.

Magnetoelectric coupling at room temperature in multiferroic materials, such as BiFeO 3 , is one of the leading candidates to develop low-power spintronics and emerging memory technologies. Although extensive research activity has been devoted recently to exploring the physical properties, especially focusing on ferroelectricity and antiferromagnetism in chemically modified BiFeO 3 , a concrete understanding of the magnetoelectric coupling is yet to be fulfilled. We have discovered that La substitutions at the Bi-site lead to a progressive increase in the degeneracy of the potential energy landscape of the BiFeO 3 system exemplified by a rotation of the polar axis away from the 〈111〉 pc towards the 〈112〉 pc discretion. This is accompanied by corresponding rotation of the antiferromagnetic axis as well, thus maintaining the right-handed vectorial relationship between ferroelectric polarization, antiferromagnetic vector and the Dzyaloshinskii-Moriya vector. As a consequence, La-BiFeO 3 films exhibit a magnetoelectric coupling that is distinctly different from the undoped BiFeO 3 films.

Multiferroic BiFeO3 (BFO) films with spontaneously formed periodic stripe domains can generate above-gap open circuit voltages under visible light illumination; nevertheless the underlying mechanism behind this intriguing optoelectronic response has not been understood to date. Here, we make contact-free measurements of light-induced currents in epitaxial BFO films via detecting terahertz radiation emanated by these currents, enabling a direct probe of the intrinsic charge separation mechanisms along with quantitative measurements of the current amplitudes and their directions. In the periodic stripe samples, we find that the net photocurrent is dominated by the charge separation across the domain walls, whereas in the monodomain samples the photovoltaic response arises from a bulk shift current associated with the non-centrosymmetry of the crystal. The peak current amplitude driven by the charge separation at the domain walls is found to be 2 orders of magnitude higher than the bulk shift current response, indicating the prominent role of domain walls acting as nanoscale junctions to efficiently separate photogenerated charges in the stripe domain BFO films. These findings show that domain-wall-engineered BFO thin films offer exciting prospects for ferroelectric-based optoelectronics, as well as bias-free strong terahertz emitters.

The ability to tailor a new crystalline structure and associated functionalities with a variety of stimuli is one of the key issues in material design. Developing synthetic routes to functional materials with partially absorbed nonmetallic elements (i.e., hydrogen and nitrogen) can open up more possibilities for preparing novel families of electronically active oxide compounds. Fast and reversible uptake and release of hydrogen in epitaxial ABO3 manganite films through an adapted low‐frequency inductively coupled plasma technology is introduced. Compared with traditional dopants of metallic cations, the plasma‐assisted hydrogen implantations not only produce reversibly structural transformations from pristine perovskite (PV) phase to a newly found protonation‐driven brownmillerite one but also regulate remarkably different electronic properties driving the material from a ferromagnetic metal to a weakly ferromagnetic insulator for a range of manganite (La1−xSrxMnO3) thin films. Moreover, a reversible perovskite‐brownmillerite‐perovskite transition is achieved at a relatively low temperature (T ≤ 350 °C), enabling multifunctional modulations for integrated electronic systems. The fast, low‐temperature control of structural and electronic properties by the facile hydrogenation/dehydrogenation treatment substantially widens the space for exploring new possibilities of novel properties in proton‐based multifunctional materials.

The availability of native substrates is a cornerstone in the development of microelectronic technologies relying on epitaxial films. If native substrates are not available, virtual substrates - crystalline buffer layers epitaxially grown on a structurally dissimilar substrate - offer a solution. Realizing commercially viable virtual substrates requires the growth of high-quality films at high growth rates for large-scale production. We report the stoichiometric growth of SrTiO 3 exceeding 600 nm hr −1 . This tenfold increase in growth rate compared to SrTiO 3 grown on silicon by conventional methods is enabled by a self-regulated growth window accessible in hybrid molecular beam epitaxy. Overcoming the materials integration challenge for complex oxides on silicon using virtual substrates opens a path to develop new electronic devices in the More than Moore era and silicon integrated quantum computation hardware.

Applications such as solid-state waste-heat energy conversion, infrared sensing, and thermally-driven electron emission rely on pyroelectric materials (a subclass of dielectric piezoelectrics) which exhibit temperature-dependent changes in polarization. Although enhanced dielectric and piezoelectric responses are typically found at polarization instabilities such as temperature- and chemically-induced phase boundaries, large pyroelectric effects have been primarily limited in study to temperature-induced phase boundaries. Here, we directly identify the magnitude and sign of the intrinsic, extrinsic, dielectric, and secondary pyroelectric contributions to the total pyroelectric response as a function of chemistry in thin films of the canonical ferroelectric PbZr1-xTixO3 (x = 0.40, 0.48, 0.60, and 0.80) across the morphotropic phase boundary. Using phase-sensitive frequency and applied dc-bias methods, the various pyroelectric contributions were measured. It is found that the total pyroelectric response decreases systematically as one moves from higher to lower titanium contents. This arises from a combination of decreasing intrinsic response (-232 μC m-2 K-1 to -97 μC m-2 K-1) and a sign inversion (33 μC m-2 K-1 to -17 μC m-2 K-1) of the extrinsic contribution upon crossing the morphotropic phase boundary. Additionally, the measured secondary and dielectric contributions span between -70 and -29 μC m-2 K-1 and 10-115 μC m-2 K-1 under applied fields, respectively, following closely trends in the piezoelectric and dielectric susceptibility. These findings and methodologies provide novel insights into the understudied realm of pyroelectric response.

There is growing interest in the study of thin-film pyroelectric materials because of their potential for high performance thermal-energy conversion, thermal sensing, and beyond. Electrothermal susceptibilities, such as pyroelectricity, are known to be enhanced in proximity to polar instabilities, and this is conventionally accomplished by positioning the material close to a temperature-driven ferroelectric-to-paraelectric phase transition. The high Curie temperature (TC) for many ferroelectrics, however, limits the utility of these materials at room-temperature. Here, the nature of pyroelectric response in thin films of the widely studied multiferroic Bi1−xLaxFeO3 (x = 0–0.45) is probed. While BiFeO3 itself has a high TC, lanthanum substitution results in a chemically induced lowering of the ferroelectric-to-paraelectric and structural-phase transition. The effect of isovalent lanthanum substitution on the structural, dielectric, ferroelectric, and pyroelectric response is investigated using reciprocal-space-mapping studies; field-, frequency-, and temperature-dependent electrical measurements; and phase-sensitive pyroelectric measurements, respectively. While BiFeO3 itself has a rather small pyroelectric coefficient at room temperature (∼−40 µC/m2 K), 15% lanthanum substitution results in an enhancement of the pyroelectric coefficient by 100% which is found to arise from a systematic lowering of TC.

Due to the strong dependence of electronic properties on the local bonding environment, a full characterization of the structural dynamics in ultrafast experiments is critical. Here, we report the dynamics and structural refinement at nanosecond time scales of a perovskite thin film by combining optical excitation with time-resolved X-ray diffraction. This is achieved by monitoring the temporal response of both integer and half-integer diffraction peaks of LaVO3 in response to an above-band-gap 800 nm pump pulse. We find that the lattice expands by 0.1% out of plane, and the relaxation is characterized by a biexponential decay with 2 and 12 ns time scales. We analyze the relative intensity change in half-integer peaks and show that the distortions to the substructure are small: the oxygen octahedral rotation angles decrease by ∼0.3° and La displacements decrease by ∼0.2 pm, which directly corresponds to an ∼0.8° increase in the V-O-V bond-angles, an in-plane V-O bond length reduction of ∼0.3 pm, and an unchanged out-of-plane bond length. This demonstration of tracking the atomic positions in a pump-probe experiment provides experimentally accessible values for structural and electronic tunability in this class of materials and will stimulate future experiments.

Strain engineering of thin films is a conventionally employed approach to enhance material properties and to energetically prefer ground states that would otherwise not be attainable. Controlling strain states in perovskite oxide thin films is usually accomplished through coherent epitaxy by using lattice-mismatched substrates with similar crystal structures. However, the limited choice of suitable oxide substrates makes certain strain states experimentally inaccessible and a continuous tuning impossible. Here, we report a strategy to continuously tune epitaxial strains in perovskite films grown on Si(001) by utilizing the large difference of thermal expansion coefficients between the film and the substrate. By establishing an adsorption-controlled growth window for SrTiO3 thin films on Si using hybrid molecular beam epitaxy, the magnitude of strain can be solely attributed to thermal expansion mismatch, which only depends on the difference between growth and room temperature. Second-harmonic generation measurements revealed that structure properties of SrTiO3 films could be tuned by this method using films with different strain states. Our work provides a strategy to generate continuous strain states in oxide/semiconductor pseudomorphic buffer structures that could help achieve desired material functionalities.

Electric-field control of magnetism requires deterministic control of the magnetic order and understanding of the magnetoelectric coupling in multiferroics like BiFeO3 and EuTiO3. Despite this critical need, there are few studies on the strain evolution of magnetic order in BiFeO3 films. Here, in (110)-oriented BiFeO3 films, we reveal that while the polarization structure remains relatively unaffected, strain can continuously tune the orientation of the antiferromagnetic-spin axis across a wide angular space, resulting in an unexpected deviation of the classical perpendicular relationship between the antiferromagnetic axis and the polarization. Calculations suggest that this evolution arises from a competition between the Dzyaloshinskii-Moriya interaction and single-ion anisotropy wherein the former dominates at small strains and the two are comparable at large strains. Finally, strong coupling between the BiFeO3 and the ferromagnet Co0.9Fe0.1 exists such that the magnetic anisotropy of the ferromagnet can be effectively controlled by engineering the orientation of the antiferromagnetic-spin axis.

Author(s): Pandya, S; Velarde, G; Zhang, L; Martin, LW | Abstract: © 2018 American Physical Society. The emergent ferroelectricity in HfO2-based systems has attracted significant attention as this simple binary high-k dielectric now offers the possibility of nonvolatile function. In this work we employ zero-field and field-dependent pyroelectricity to show that thin films of silicon-doped HfO2 do exhibit a broken-inversion symmetry and are indeed ferroelectric. In addition, the pyroelectric response is found to exhibit a wake-up behavior akin to the wake-up phenomenon observed in the ferroelectric polarization with electric-field cycling. Using polarization-electric field hysteresis measurements, this wake-up phenomenon is attributed to the presence of defect dipoles which explains the measured pyroelectric response. Finally, direct electrocaloric measurements are performed on these silicon-doped HfO2 thin films, revealing an electrocaloric coefficient ∼4 times larger in magnitude than that expected for the measured pyroelectric coefficient. This enhancement is explained using the plausible role played by defect dipoles that contribute to additional configurational or dipolar entropy.

The diverse and fascinating properties of transition metal oxides stem from the strongly correlated electronic degrees of freedom; the scientific challenge and range of possible applications of these materials have caused fascination among physicists and materials scientists, thus capturing research efforts for nearly a century. Here, we focus on the binary VxOy and the ternary perovskite AVO(3) and review the key aspects from the underlying physical framework and their basic properties, recent strides made in thin-film synthesis, to recent efforts to implement vanadium-based oxides for practical applications that augment existing technologies, which surpass limitations of conventional materials.

The authors report on the growth of stoichiometric CaVO3 thin films on LaSrAlO4 (001) using hybrid molecular beam epitaxy approach, whereby the metalorganic vanadium oxytriisopropoxide (VTIP) and Ca was cosupplied from a gas injector and a conventional effusion cell, respectively. Films were grown using a fixed Ca flux while varying the VTIP flux. Reflection high energy electron diffraction, x-ray diffraction, atomic force microscopy, energy-dispersive x-ray spectroscopy, and high resolution transmission electron microscopy were employed to relate film quality to growth conditions. A wide growth window was discovered in which the films were stoichiometric and film lattice parameter was found independent of the Ca/VTIP flux ratio, allowing more than 10% unintentional deviation in the Ca flux while maintaining stoichiometric growth conditions. Films grown within the growth window showed atomically smooth surfaces with stepped terrace morphology and narrow rocking curves in x-ray diffraction with a full width of half maximum of 8 arc sec, similar to that of the substrate. For growth conditions outside of this window, excess Ca and V nonstoichiometric defects were incorporated into the lattice. The effect of film microstructure and stoichiometry on temperature dependent electrical conductivity is discussed. The ability to produce high quality CaVO3 films without precise control of cation fluxes opens a robust synthesis route to explore the intrinsic physics of strongly correlated metals with reduced dimensionality.