Interface-Suppressed Nematicity and Enhanced Superconducting Pairing Strength of FeSe/NdFeO3 in the Low-Doping Regime.

The discovery of interfacial superconductivity in monolayer FeSe/oxides has spurred intensive research interest. Here we not only extend the FeSe/FeOx superconducting interface to FeSe/NdFeO3 but also establish robust interface-enhanced superconductivity at a very low doping level. Specifically, well-annealed FeSe/NdFeO3 exhibits a low doping level of 0.038-0.046 e-/Fe with a larger superconducting pairing gap without a nematic gap, indicating an enhancement of the enhanced superconducting pairing strength and suppression of nematicity by the FeSe/FeOx interface compared with those of thick FeSe films. These results improve our understanding of the roles of the oxide interface in the low-electron-doped regime.

Large Nonlinear Transverse Conductivity and Berry Curvature in KTaO3 Based Two-Dimensional Electron Gas.

Two-dimensional electron gas (2DEG) at oxide interfaces exhibits various exotic properties stemming from interfacial inversion and symmetry breaking. In this work, we report large nonlinear transverse conductivities in the LaAlO3/KTaO3 interface 2DEG under zero magnetic field. Skew scattering was identified as the dominant origin based on the cubic scaling of nonlinear transverse conductivity with linear longitudinal conductivity and 3-fold symmetry. Moreover, gate-tunable nonlinear transport with pronounced peak and dip was observed and reproduced by our theoretical calculation. These results indicate the presence of Berry curvature hotspots and thus a large Berry curvature triplet at the oxide interface. Our theoretical calculations confirm the existence of large Berry curvatures from the avoided crossing of multiple 5d-orbit bands, orders of magnitude larger than that in transition-metal dichalcogenides. Nonlinear transport offers a new pathway to probe the Berry curvature at oxide interfaces and facilitates new applications in oxide nonlinear electronics.

Enhanced Hot Electron Flow and Catalytic Synergy by Engineering Core-Shell Structures on Au-Pd Nanocatalysts.

The synergistic catalytic performances of bimetallic catalysts are often attributed to the reaction mechanism associated with the alloying process of the catalytic metals. Chemically induced hot electron flux is strongly correlated with catalytic activity, and the interference between two metals at the atomic level can have a huge impact on the hot electron generation on the bimetallic catalysts. In this study, we investigate the correlation between catalytic synergy and hot electron chemistry driven by the electron coupling effect using a model system of Au-Pd bimetallic nanoparticles. We show that the bimetallic nanocatalysts exhibit enhanced catalytic activity under the hydrogen oxidation reaction compared with that of monometallic Pd nanocatalysts. Analysis of the hot electron flux generated in each system revealed the formation of Au/PdOx interfaces, resulting in high reactivity on the bimetallic catalyst. In further experiments with engineering the Au@Pd core-shell structures, we reveal that the hot electron flux, when the topmost surface Pd atoms were less affected by inner Au, due to the concrete shell, was smaller than the alloyed one. The alloyed bimetallic catalyst forming the metal-oxide interfaces has a more direct effect on the hot electron chemistry, as well as on the catalytic reactivity. The great significance of this study is in the confirmation that the change in the hot electron formation rate with the metal-oxide interfaces can be observed by shell engineering of nanocatalysts.

Combined Theoretical and Experimental Study of the Moiré Dislocation Network at the SrTiO3-(La,Sr)(Al,Ta)O3 Interface.

Recently, a highly ordered Moiré dislocation lattice was identified at the interface between a SrTiO3 (STO) thin film and the (LaAlO3)0.3(Sr2TaAlO6)0.7 (LSAT) substrate. A fundamental understanding of the local ionic and electronic structures around the dislocation cores is crucial to further engineer the properties of these complex multifunctional heterostructures. Here, we combine experimental characterization via analytical scanning transmission electron microscopy with results of molecular dynamics and density functional theory calculations to gain insights into the structure and defect chemistry of these dislocation arrays. Our results show that these dislocations lead to undercoordinated Ta/Al cations at the dislocation core, where oxygen vacancies can easily be formed, further facilitated by the presence of cation vacancies. The reduced Ti3+ observed experimentally at the dislocations by electron energy-loss spectroscopy is a consequence of both the structure of the dislocation itself and of the electron doping due to oxygen vacancy formation. Finally, the experimentally observed Ti diffusion into the LSAT around the dislocation core occurs only together with cation vacancy formation in the LSAT or Ta diffusion into STO.

Highly Rectifying Water-Mediated Hydrogen Bond-Coupled Organic-Inorganic Interfaces.

Asymmetrically conducting interfaces are the building blocks of electronic devices. While p-n junction diodes made of seminal inorganic semiconductors with rectification ratios close to the theoretical limits are routinely fabricated, the analogous organic-inorganic and organic-organic interfaces are still too leaky to afford functional use. We report fabricating highly rectifying organic-inorganic interfaces by forming water-mediated hydrogen bonds between the hydrophilic surfaces of a hole-conducting polymer anode and a polycrystalline n-type metal oxide cathode. These hydrogen bonds simultaneously strengthen the anode-cathode electronic coupling, facilitate the matching between their incompatible surface structures, and passivate the detrimental surface imperfections. Compared to an analogous directly joined interface, our hydrogen-bonded Au-PEDOT:PSS-H2O-TiO2-Ti diodes demonstrate 105 times higher rectification ratios. These results illustrate the strong electronic coupling power of the hydrogen bonds on a macroscopic scale and underscore the hydrogen-bonded interfaces as the building blocks of fabricating organic electronic and optoelectronic devices. The presented interface model is anticipated to advance designing electronic devices based on the organic-organic and organic-inorganic hetero-interfaces. Described electronic implications of hydrogen bonding on the conductive polymer interfaces are anticipated to be impactful in the organic electronics and neuromorphic engineering.

MXene-Regulated Metal-Oxide Interfaces with Modified Intermediate Configurations Realizing Nearly 100% CO2 Electrocatalytic Conversion.

Electrocatalytic CO2 reduction via renewable electricity provides a sustainable way to produce valued chemicals, while it suffers from low activity and selectivity. Herein, we constructed a novel catalyst with unique Ti3 C2 Tx MXene-regulated Ag-ZnO interfaces, undercoordinated surface sites, as well as mesoporous nanostructures. The designed Ag-ZnO/Ti3 C2 Tx catalyst achieves an outstanding CO2 conversion performance of a nearly 100% CO Faraday efficiency with high partial current density of 22.59 mA cm-2 at -0.87 V versus reversible hydrogen electrode. The electronic donation of Ag and up-shifted d-band center relative to Fermi level within MXene-regulated Ag-ZnO interfaces contributes the high selectivity of CO. The CO2 conversion is highly correlated with the dominated linear-bonded CO intermediate confirmed by in situ infrared spectroscopy. This work enlightens the rational design of unique metal-oxide interfaces with the regulation of MXene for high-performance electrocatalysis beyond CO2 reduction.

Metal-Metal Oxide Catalytic Interface Formation and Structural Evolution: A Discovery of Strong Metal-Support Bonding, Ordered Intermetallics, and Single Atoms.

In-depth investigation of metal-metal oxide interactions and their corresponding evolution is of paramount importance to heterogeneous catalysis as it allows the understanding and maneuvering of the structure of catalytic motifs. Herein, using a series of core/shell metal/iron oxide (M/FeOx, M = Pd, Pt, Au) nanoparticles and through a combination of in situ and ex situ electron and X-ray investigations, we revealed anomalous and dissimilar M-FeOx interactions among different systems under reducing conditions. Pd interacts strongly with FeOx after high-temperature reductive treatment, featured by the formation of Pd single atoms in the FeOx matrix and increased Pd-Fe bonding, while Pt transforms into ordered PtFe intermetallics and Pt single atoms immediately upon the coating of FeOx. In contrast, Au does not manifest strong bonding with FeOx. As a proof of concept of tailoring metal-metal oxide interactions for catalysis, optimized Pd/FeOx demonstrates 100% conversion and 86.5% selectivity at 60 °C for acetylene semihydrogenation.

Sr2Fe1.575Mo0.5O6-δ Promotes the Conversion of Methane to Ethylene and Ethane.

Oxidative coupling of methane can produce various valuable products, such as ethane and ethylene, and solid oxide electrolysis cells (SOECs) can electrolyze CH4 to produce C2H4 and C2H6. In this work, Sr2Fe1.575Mo0.5O6-δ electrode materials were prepared by impregnation and in situ precipitation, and Sr2Fe1.5Mo0.5O6-δ was taken as a reference to study the role of metal-oxide interfaces in the catalytic process. When the Fe/Sr2Fe1.575Mo0.5O6-δ interface is well constructed, the selectivity for C2 can reach 78.18% at 850 °C with a potential of 1.2 V, and the conversion rate of CH4 is 11.61%. These results further prove that a well-constructed metal-oxide interface significantly improves the catalytic activity and facilitates the reaction.

Effects of growth temperature, oxygen pressure, laser fluence and postannealing on transport properties of superconducting LaAlO3/KTaO3(111) interfaces.

The recent discovery of superconductivity at EuO (or LaAlO3)/KTaO3interfaces has attracted considerable research interest. However, an extensive study on growth of these interfaces is still lacking. In this work, we have fabricated LaAlO3/KTaO3(111) interfaces by growing LaAlO3thin films on KTaO3(111) single-crystalline substrates by pulsed laser deposition. We investigated the effects of growth temperature, oxygen pressure, laser fluence, and postannealing on transport properties. We found that all these key growth parameters show important effects on transport properties, and discussed their possible mechanisms. Our present study provides useful knowledge to further optimize these interfaces.

In Situ Spectroscopic Characterization and Theoretical Calculations Identify Partially Reduced ZnO1-x /Cu Interfaces for Methanol Synthesis from CO2.

The active site of the industrial Cu/ZnO/Al2 O3 catalyst used in CO2 hydrogenation to methanol has been debated for decades. Grand challenges remain in the characterization of structure, composition, and chemical state, both microscopically and spectroscopically, and complete theoretical calculations are limited when it comes to describing the intrinsic activity of the catalyst over the diverse range of structures that emerge under realistic conditions. Here a series of inverse model catalysts of ZnO on copper hydroxide were prepared where the size of ZnO was precisely tuned from atomically dispersed species to nanoparticles using atomic layer deposition. ZnO decoration boosted methanol formation to a rate of 877 gMeOH kgcat -1 h-1 with ≈80 % selectivity at 493 K. High pressure in situ X-ray absorption spectroscopy demonstrated that the atomically dispersed ZnO species are prone to aggregate at oxygen-deficient ZnO ensembles instead of forming CuZn metal alloys. By modeling various potential active structures, density functional theory calculations and microkinetic simulations revealed that ZnO/Cu interfaces with oxygen vacancies, rather than stoichiometric interfaces, Cu and CuZn alloys were essential to catalytic activation.

Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations.

We report a computational study and analysis of the optical absorption processes of Ag20 and Au20 clusters deposited on the magnesium oxide (100) facet, both regular and including point defects. Ag20 and Au20 are taken as models of metal nanoparticles and their plasmonic response, MgO as a model of a simple oxide support. We consider oxide defects both on the oxygen anion framework (i.e., a neutral oxygen vacancy) and in the magnesium cation framework (i.e., replacing Mg++ with a transition metal: Cu++ or Co++). We relax the clusters' geometries via Density-Functional Theory (DFT) and calculate the photo-absorption spectra via Time-Dependent DFT (TDDFT) simulations on the relaxed geometries. We find that the substrate/cluster interaction induces a broadening and a red-shift of the excited states of the clusters, phenomena that are enhanced by the presence of an oxygen vacancy and its localized excitations. The presence of a transition-metal dopant does not qualitatively affect the spectral profile. However, when it lies next to an oxygen vacancy for Ag20, it can strongly enhance the component of the cluster excitations perpendicular to the surface, thus favoring charge injection.

Resistive Switching in HfO2-x/La0.67Sr0.33MnO3 Heterostructures: An Intriguing Case of Low H-Field Susceptibility of an E-Field Controlled Active Interface.

High-performance nonvolatile resistive random access memories (ReRAMs) and their small stimuli control are of immense interest for high-speed computation and big-data processing in the emerging Internet of Things (IoT) arena. Here, we examine the resistive switching (RS) behavior in growth-controlled HfO2/La0.67Sr0.33MnO3 (LSMO) heterostructures and their tunability in a low magnetic field. It is demonstrated that oxygen-deficient HfO2 films show bipolar switching with a high on/off ratio, stable retention, as well as good endurance owing to the orthorhombic-rich phase constitution and charge (de)trapping-enabled Schottky-type conduction. Most importantly, we have demonstrated that RS can be tuned by a very low externally applied magnetic field (∼0-30 mT). Remarkably, application of a magnetic field of 30 mT causes RS to be fully quenched and frozen in the high resistive state (HRS) even after the removal of the magnetic field. However, the quenched state could be resurrected by applying a higher bias voltage than the one for initial switching. This is argued to be a consequence of the electronically and ionically "active" nature of the HfO2-x/LSMO interface on both sides and its susceptibility to the electric and low magnetic field effects. This result could pave the way for new designs of interface-engineered high-performance oxitronic ReRAM devices.

Two-dimensional conducting states in infinite-layer oxide/perovskite oxide hetero-structures.

Heterointerfaces sandwiched by oxides of dissimilar crystal structures will show strong interface reconstruction, leading to distinct interfacial effect arising from unusual physics. Here, we present a theoretical investigation on the interfaces between infinite-layer oxide and perovskite oxide (SrCuO2/SrTiO3and SrCuO2/KTaO3). Surprisingly, we found well-defined two-dimensional electron gas (2DEG), stemming from atomic reconstruction and polar discontinuity at interface. Moreover, the 2DEG resides in both the TiO2and CuO2interfacial layers, unlike LaAlO3/SrTiO3for which 2DEG exists only in the TiO2interfacial layer. More than that, no metal-to-insulator transition is observed as the SrCuO2layer thickness decreases to one unit cell, i.e., the metallicity of the new interface is robust. Further investigations show more unique features of the 2DEG. Due to the absence of apical oxygen at the SrCuO2/SrTiO3(KTaO3) interface, the conducting states in the interface TiO2(TaO2) layer follows thedxy

Gate Alignment of Liquid Water Molecules in Electric Double Layer.

The behavior of liquid water molecules near an electrified interface is important to many disciplines of science and engineering. In this study, we applied an external gate potential to the silica/water interface via an electrolyte-insulator-semiconductor (EIS) junction to control the surface charging state. Without varying the ionic composition in water, the electrical gating allowed an efficient tuning of the interfacial charge density and field. Using the sum-frequency vibrational spectroscopy, we found a drastic enhancement of interfacial OH vibrational signals at high potential in weakly acidic water, which exceeded that from conventional bulk-silica/water interfaces even in strong basic solutions. Analysis of the spectra indicated that it was due to the alignment of liquid water molecules through the electric double layer, where the screening was weak because of the low ion density. Such a combination of strong field and weak screening demonstrates the unique tuning capability of the EIS scheme, and would allow us to investigate a wealth of phenomena at charged oxide/water interfaces.

Engineering intermetallic-metal oxide interface with low platinum loading for efficient methanol electrooxidation.

Constructing a distinctive electrochemical interface with low platinum content to boost the sluggish methanol electrooxidation kinetics is critical for commercializing the direct methanol fuel cells. Herein, we have synthesized highly active electrocatalysts with unique intermetallic-metal oxide interfaces through a facile pyrolysis method. Physical characterizations demonstrate that the obtained PtFe(1:2)@a-FeOx/NC-C catalyst with low platinum content of 7.2 wt% possesses an interfacial structure composed of face-centered tetragonal (L10) PtFe intermetallic nanoparticles accompanied with amorphous iron oxide. Electrochemical measurements show that the synthesized PtFe(1:2)@a-FeOx/NC-C catalyst not only exhibits excellent methanol electrooxidation activities with a mass activity of 1.48 A mg-1Pt and a specific activity of 2.34 mA cm-2Pt in acid medium, but also possesses better CO-tolerant performance and faster methanol oxidation kinetics compared with commercial Pt/C. The improved electrochemical performances may ascribe to the modified electronic structure by alloying platinum with iron and the special PtFe@a-FeOx interface, which render strong synergistic interactions between bimetallic PtFe nanoparticles and amorphous iron oxide. Consequently, the presented strategy offers new prospects into the construction of low-cost electrocatalysts with unique electrochemical interface for enhancing catalytic performances.

Heterogeneous Synergetic Effect of Metal-Oxide Interfaces for Efficient Hydrogen Evolution in Alkaline Solutions.

Water dissociation in alkaline solutions is one of the biggest challenges in hydrogen evolution reactions (HERs). The key is to obtain a catalyst with optimal and balanced OH adsorption energy and H adsorption/H2 desorption energy. Herein, we synthesized a Ni17W3/WO2 catalyst on the Ni foam that optimized the coverage and size of Ni17W3 alloys decorated on the NiWO4/WO2 substrate. Our experiments showed that Ni17W3-NiWO4 interfaces could accelerate water dissociation, and Ni17W3-WO2 interfaces facilitate adsorbed H atoms spillover and H2 desorption. In addition, we applied a suite of characterization techniques to analyze surface evolution processes in catalysts under various cathodic potentials so as to illustrate the competition between chemical oxidation and electrochemical reduction reactions. The results demonstrated that high coverage of large Ni17W3 nanoparticles resulted in a greater stable interface. The two efficient interfaces synergetically promote the Volmer-Tafel reaction. Ni17W3/WO2 catalysts exhibited extraordinary HER activity with a low overpotential of 48 mV at a 10 mA cm-2 current density and a Tafel slope of 33 mV dec-1. This work has shown that low-cost catalysts with proper hierarchical interfaces can be engineered and can be optimized into a tandem system, which will significantly promote HER activity in alkaline electrolytes.

Green Nanocoatings Based on the Deposition of Zirconium Oxide: The Role of the Substrate.

Herein, the influence of the substrate in the formation of zirconium oxide monolayer, from an aqueous hexafluorozirconic acid solution, by chemical conversion and by electro-assisted deposition, has been approached. The nanoscale dimensions of the ZrO2 film is affected by the substrate nature and roughness. This study evidenced that the mechanism of Zr-EAD is dependent on the potential applied and on the substrate composition, whereas conversion coating is uniquely dependent on the adsorption reaction time. The zirconium oxide based nanofilms were more homogenous in AA2024 substrates if compared to pure Al grade (AA1100). It was justified by the high content of Cu alloying element present in the grain boundaries of the latter. Such intermetallic active sites favor the obtaining of ZrO2 films, as demonstrated by XPS and AFM results. From a mechanistic point of view, the electrochemical reactions take place simultaneously with the conventional chemical conversion process driven by ions diffusion. Such findings will bring new perspectives for the generation of controlled oxide coatings in modified electrodes used, as for example, in the construction of battery cells; in automotive and in aerospace industries, to replace micrometric layers of zinc phosphate by light-weight zirconium oxide nanometric ones. This study is particularly addressed for the reduction of industrial waste by applying green bath solutions without the need of auxiliary compounds and using lightweight ceramic materials.

Two-Dimensional Electron Gas at the Spinel/Perovskite Interface: Suppression of Polar Catastrophe by an Ultrathin Layer of Interfacial Defects.

Two-dimensional electron gas (2DEG) at the interface between two insulating perovskite oxides has attracted much interest for both fundamental physics and potential applications. Here, we report the discovery of a new 2DEG formed at the interface between spinel MgAl2O4 and perovskite SrTiO3. Transport measurements, electron microscopy imaging, and first-principles calculations reveal that the interfacial 2DEG is closely related to the symmetry breaking at the MgAl2O4/SrTiO3 interface. The critical film thickness for the insulator-to-metal transition is approximately 32 Å, which is twice as thick as that reported on the widely studied LaAlO3/SrTiO3 system. Scanning transmission electron microscopy imaging indicates the formation of interfacial Ti-Al antisite defects with a thickness of ∼4 Å. First-principles density functional theory calculations indicate that the coexistence of the antisite defects and surface oxygen vacancies may explain the formation of interfacial 2DEG as well as the observed critical film thickness. The discovery of 2DEG at the spinel/perovskite interface introduces a new material platform for designing oxide interfaces with desired characteristics.

Atomic-Scale Insight into Exsolution of CoFe Alloy Nanoparticles in La0.4 Sr0.6 Co0.2 Fe0.7 Mo0.1 O3-δ with Efficient CO2 Electrolysis.

In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal-oxide interface for CO2 electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La0.4 Sr0.6 Co0.2 Fe0.7 Mo0.1 O3-δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal-oxide interface improves CO2 adsorption and activation, showing a higher CO2 electrolysis performance than the LSCFM counterparts.

Role of the Interface between Ag and ZnO in the Electric Conductivity of Ag Nanoparticle-Embedded ZnO.

The addition of Ag nanoparticles (Ag NPs) with an average size of 30 nm into ZnO increases the electric conductivity up to 1000 times. While a similar increase in the conductivity is observed in a mixture of Ag nanoparticles and Al-doped ZnO (AZO) films, a physical mechanism underlying the change in electric conductivity is not the same for Ag NP-added ZnO and Ag NP-added AZO. In Ag NP-added ZnO, an ohmic junction is formed at the ZnO-Ag interface, and electrons are accumulated in ZnO near the ZnO-Ag interface until electron-rich islands are connected. However, in Ag NP-added AZO, electrons in Ag NPs move to the AZO matrix via thermionic emission and travel through the AZO matrix. This change in electron transport at ZnO-Ag and AZO-Ag interfaces is due to the fact that the work function of ZnO (4.62 eV) is larger than those of Ag (4.24 eV) and AZO (4.15 eV). An increase in Ag NP content in the ZnO matrix leads to the overlap of the electron accumulation regions and forms a percolation path for the electron transport without deteriorating the electron mobility. Hence, the electron concentration increases to 2.4 × 1020/cm3 in the 1.4 vol % Ag NP-added ZnO film. In addition, Ag NPs have a negligible effect on the transmittance, and the best Haacke figure of merit (ΦH) values are 2.86 and 5.18 for ZnO:Ag NP and AZO:Ag NP, respectively.