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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

On the Nature of the Increase in the Electron Mobility in the Inversion Channel at the Silicon–Oxide Interface after the Field Effect

The conduction characteristics of the inversion channel of Si-transistor structures after the ionic polarization and depolarization of samples are measured in (0–5)-T transverse magnetic fields at temperatures from 100 to 200 K. After ionic polarization in a strong electric field at 420 K, no less than 6 × 10{sup 13} cm{sup –2} ions flowed through the oxide. The previously found tenfold increase in the conductivity in the source–drain circuit after the polarization of insulating layers is explained by the formation of a new electron transport path along the surface impurity band, related to delocalized D{sup –} states; these states are generated by neutralized ions located in the insulating layer at its interface with the semiconductor.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Polarity‐Driven Atomic Displacements at the 2D Mg 2 TiO 4 ‐MgO (001) Oxide Interface for Hosting Potential Interlayer Excitons

Abstract Interlayer excitons in solid‐state systems have emerged as candidates for realizing novel platforms ranging from excitonic transistors and optical qubits to exciton condensates. Interlayer excitons have been discovered in 2D transition metal dichalcogenides, with large exciton binding energies and the ability to form various van der Waals heterostructures. Here, an oxide system consisting of a single unit cell of Mg 2 TiO 4 on MgO (001) is proposed as a platform for hosting interlayer excitons. Using a combination of density functional theory (DFT) calculations, molecular beam epitaxy growth, and in situ crystal truncation rod measurements, it is shown that the Mg 2 TiO 4 ‐MgO interface can be precisely controlled to yield an internal electric field suitable for hosting interlayer excitons. The atoms in the polar Mg 2 TiO 4 layers are observed to be displaced to reduce polarity at the interface with the non‐polar MgO (001) surface. Such polarity‐driven atomic displacements strongly affect electrostatics of the film and the interface, resulting in localization of filled and empty band‐edge states in different layers of the Mg 2 TiO 4 film. The DFT calculations suggest that the electronic structure is favorable for localization of photoexcited electrons in the bottom layer and holes in the top layer, which may bind to form interlayer exciton states.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Simultaneous Activation of CH4 and CO2 for Concerted C-C Coupling at the Oxide-Oxide Interfaces

Catalytic conversion of CO2 and CH4 to value-added platform chemicals via the direct C-C coupling provides one of the most effective routes that not only address global climate change but also alleviate the dependency on traditional fossil fuels. Herein, three oxide-on-oxide catalysts that can realize direct C-C coupling on the basis of simultaneous activation of CH4 and CO2 were investigated using density functional theory (DFT) calculations. With the formation of oxide-on-oxide interfacial sites between the substrate (In2O3) and dispersed oxides ((ZnO)3, (ZrO2)3, or Ga2O3), it is found that CO2 can be activated at the defective site of In2O3 while the C-H bond of CH4 can be simultaneously activated at the M-O pair of the supported metal oxide. In contrast to the Eley-Rideal mechanism that C-C coupling of CO2 and CH3 stabilized on Zn-doped ceria follows, the formation of a Zn-C-C-O transition state at the active centers originates from a Langmuir-Hinshelwood mechanism where the activated CO2 also enhances the dissociative adsorption of CH4. There is a linear relationship between the C-C coupling reaction energy/activation barrier and CH4 dissociation energy. The results indicate that dissociative adsorption of CH4 plays a dominant role in the direct C-C coupling, whereas the adsorption/activation of CO2 is less significant. DFT calculation results of CH4 and CO2 to acetic acid on the (ZnO)3/In2O3 catalyst surface indicates that the C-C coupling step is the kinetically most relevant step. Compared with Ga2O3/In2O3 and (ZrO2)3/In2O3 catalyst surfaces, (ZnO)3/In2O3(110) is more active for the acetic acid formation. The present work provides new mechanistic insights into the direct C-C coupling of CH4 and CO2, which would be useful to design more efficient catalyst.

CH4 activation, C-C coupling, supported oxides, In↗
DOE OSTI2025

Alkali-induced catalytic tuning at metal and metal oxide interfaces

Alkali metals have been recognized as effective promoters in heterogeneous catalysis, capable of enhancing catalytic activity and tuning product distributions. Over the past few decades, significant efforts have been made aiming to reveal the mechanisms underlying the promoting effect of alkalis. However, the roles that alkali metals play in the catalytic process remain elusive due to challenges in capturing their catalytic behaviours upon exposure to reactive environments. This review summarizes recent surface science and theoretical studies of alkali (potassium, cesium)-decorated metal and metal oxide model catalysts, revealing the crucial tuning by alkalis of activity and selectivity for CO 2 hydrogenation. The analysis of electronic structures identifies the selective binding mechanism of the positively charged alkali ions on the surface, being able to reduce the surface work function and lead to strong electron polarization on the surfaces. Depending on the alkali–support interaction, the deposition of alkalis can selectively modify the bindings of reaction intermediates involved in CO 2 hydrogenation via the interplay among the ionic, covalent and electrostatic tunings. As a result, CO 2 can be effectively activated and converted into diverse products at the alkali–support interface, ranging from formic acid to methanol and ethanol. The identified selective bond-tuning advances the application of alkalis in promoting catalytic activity and controlling catalytic selectivity at alkali–support interfaces.

03 NATURAL GAS↗
DOE OSTI2019

Topological Hall effect and emergent skyrmion crystal at manganite-iridate oxide interfaces

Scalar spin chirality is expected to induce a finite contribution to the Hall response at low temperatures. We observe this spin-chirality-driven Hall effect, known as the topological Hall effect, at the manganite side of the interface between La 1- x Sr x MnO 3 and SrIrO 3 . The ferromagnetic double-exchange hopping at the manganite layer, in conjunction with the Dzyaloshinskii-Moriya (DM) interaction which arises at the interface due to broken inversion symmetry and strong spin-orbit coupling from the iridate layer, could produce a skyrmion-crystal (SkX) phase in the presence of an external magnetic field. Using the Monte Carlo technique and a two-orbital spin-fermion model for manganites, supplemented by an in-plane DM interaction, we obtain phase diagrams which reveal at low temperatures a clear SkX phase and also a low-field spin-spiral phase. Increasing temperature, a skyrmion-gas phase, precursor of the SkX phase upon cooling, was identified. The topological Hall effect primarily appears in the SkX phase, as observed before in oxide heterostructures. We determine that the manganite-iridate superlattices give another useful platform to discover a plethora of unconventional magnetic and transport properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Direct observation of a two-dimensional hole gas at oxide interfaces

The discovery of a two-dimensional electron gas (2DEG) at the LaAlO 3 /SrTiO 3 interface has resulted in the observation of many properties not present in conventional semiconductor heterostructures, and so become a focal point for device applications. Its counterpart, the two-dimensional hole gas (2DHG), is expected to complement the 2DEG. However, although the 2DEG has been widely observed, the 2DHG has proved elusive. Here in this paper we demonstrate a highly mobile 2DHG in epitaxially grown SrTiO 3 /LaAlO 3 /SrTiO 3 heterostructures. Using electrical transport measurements and in-line electron holography, we provide direct evidence of a 2DHG that coexists with a 2DEG at complementary heterointerfaces in the same structure. First-principles calculations, coherent Bragg rod analysis and depth-resolved cathodoluminescence spectroscopy consistently support our finding that to eliminate ionic point defects is key to realizing a 2DHG. Lastly, the coexistence of a 2DEG and a 2DHG in a single oxide heterostructure provides a platform for the exciting physics of confined electron-hole systems and for developing applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Cu deposited on CeOx-modified TiO 2 (110): Synergistic effects at the metal–oxide interface and the mechanism of the WGS reaction

Experimental techniques and DFT calculations have been combined to study and compare the effect of the metal–substrate interaction in Cu/TiO 2 (110) and Cu/CeO x /TiO 2 (110) catalysts for the water–gas shift (WGS) reaction. Experiments and theory show that CeOx nanoparticles affect the dispersion of copper on titania, and on the formed copper–ceria interface, there are synergistic effects which favor water dissociation and the WGS reaction. The minimum energy path for the WGS reaction on the new highly active catalytic system Cu/CeO x /TiO 2 (110) has been predicted by theoretical calculations. Main steps such as adsorption–dissociation of water and *OCOH carboxyl intermediate formation–deprotonation have been characterized. In this very particular system, water splitting is no longer the rate-limiting step because it can dissociate overcoming an energy barrier of only 0.92 kcal/mol. One important insight of the present work is to show that easy full hydration of the ceria particles strongly lowers the reaction barrier for the deprotonation of the *OCOH intermediate and facilitates the evolution of the WGS reaction. For the first time, a system has been found on which the WGS reaction is able to work with all the involved energy barriers below 12 kcal/mol. This remarkable behavior makes the metal/CeO x /TiO 2 family a potential candidate for industrial application as catalysts in the WGS reaction. In conclusion, the change in the metal–support interactions when going from Cu/TiO 2 to Cu/CeO x /TiO 2 illustrates the importance of optimizing the oxide phase when improving the performance of metal/oxide catalysts for the WGS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

High-Temperature 2D Optical Relaxation Visualizes Enhanced Oxygen Exchange Kinetics at Metal-Mixed Conducting Oxide Interfaces

Solid-state heterointerfaces are of interest for emergent local behavior that is distinct from either bulk parent compound. One technologically relevant example is the case of mixed ionic/electronic conductor (MIEC)–metal interfaces, which play an important role in electrochemistry. Metal–MIEC composite electrodes can demonstrate improved catalytic activity vs single-phase MIECs, improving fuel cell efficiency. Similarly, MIEC surface reaction kinetics are often evaluated using techniques that place metal current collectors in contact with the surface under evaluation, potentially altering the response vs the native surface. Here, techniques enabling direct and local in situ observation of the behavior at and around such heterointerfaces are needed. Here, we develop a spatially resolved optical transmission relaxation (2D-OTR) method providing continuous evaluation of local, high-temperature, controlled atmosphere defect kinetics across a ~1 cm2 sample area simultaneously in a contact-free manner. We apply it to observe the spatial variance of oxygen incorporation and evolution rates at ~525–620 °C, in response to step changes in oxygen partial pressure, on MIEC SrTi 0.65 Fe 0.35 O 3–x films as a function of distance from porous Pt and Au layers. Using this model geometry, we find significant enhancements in kinetics adjacent to the metals that decay over a few millimeter distance. To extract kinetic parameters, we fit the short-term optical data (initial portion of relaxations) with an exponential decay function appropriate for surface-exchange-limited kinetics, yielding apparent surface exchange coefficients (k chem ) with spatial resolution, decreasing with distance from the metal. To understand the kinetic processes governing the complete (long-term) optical relaxations, we performed COMSOL simulations, which demonstrated that a combination of laterally varying k chem and in-plane diffusion controls the observed kinetics over the full time range. Further support for spatially varying kchem comes from demonstrations of changing surface and bulk chemistry vs distance from the metal–MIEC interface, by X-ray photoelectron and optical absorption spectroscopies, respectively. Although microporous Pt and Au are not excellent electrodes in isolation, both metals exert a synergistic effect on the oxygen surface exchange rate in the presence of the mixed conducting film.

36 MATERIALS SCIENCE↗