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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Hidden Interface Driven Exchange Coupling in Oxide Heterostructures

A variety of emergent phenomena have been enabled by interface engineering in complex oxides. The existence of an intrinsic interfacial layer has often been found at oxide heterointerfaces. However, the role of such an interlayerin controlling functionalities is not fully explored. Here, we report the control of the exchange bias (EB) in single-phase manganite thin films with nominallyuniform chemical composition across the interfaces. The sign of EB depends on the magnitude of the cooling field. A pinned layer, confirmed by polarized neutron reflectometry, provides the source of unidirectional anisotropy. The origin of the exchange bias coupling is discussed in terms of magnetic interactions between the interfacial ferromagnetically reduced layer and the bulk ferromagnetic region. The sign of EB is related to the frustration of antiferromagnetic coupling between the ferromagnetic region and the pinned layer. Our results shed new light on using oxide interfaces to design functional spintronic devices.

epitaxial thin films↗
DOE OSTI2020

Lithium oxidation and electrolyte decomposition at Li-metal/liquid electrolyte interfaces

In this work, we examine the evolution of events occurring when a Li metal surface is in contact with a 2 M solution of a Li salt in a solvent or mixture of solvents, via classical molecular dynamics simulations with a reactive force field allowing bond breaking and bond forming. The main events include Li oxidation and electrolyte reduction along with expansion of the Li surface layers forming a porous phase that is the basis for the formation of the solid-electrolyte interphase (SEI) components. Nucleation of the main SEI components (LiF, Li oxides, and some organics) is characterized. The analysis clearly reveals the details of these physical–chemical events as a function of time, during 20 nanoseconds. The effects of the chemistry of the electrolyte on Li oxidation and dissolution in the liquid electrolyte, and SEI nucleation and structure are identified by testing two salts: LiPF 6 and LiCF 3 SO 3 , and various solvents including ethers and carbonates and mixtures of them. The kinetics and thermodynamics of Li 6 F, the core nuclei in the LiF crystal, are studied by analysis of the MD trajectories, and via density functional theory calculations respectively. The SEI formed in this computational experiment is the “native” film that would form upon contact of the Li foil with the liquid electrolyte. As such, this work is the first in a series of computational experiments that will help elucidate the intricate interphase layer formed during battery cycling using metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2015

Two-dimensional electron gas at the Ti-diffused BiFeO{sub 3}/SrTiO{sub 3} interface

Oxide heterostructures with the broken translational symmetry often trigger a two-dimensional quantum confinement and associated unique electronic properties that cannot be observed in bulk constituents. Particular interest is devoted to the formation of two-dimensional electron gas (2DEG) at heterointerfaces between two insulators, which offers a fertile ground for fabricating advanced electronic devices. Here, we combine atomic force microscopy, transmission electron microscopy, and atomistic first-principles calculations to demonstrate that the (100) BiFeO{sub 3}/SrTiO{sub 3} interface takes on a metallic nature and a 2DEG is generated at this interface. Our findings also reveal that the electronic reconstruction due to the polar discontinuity and the variation in valence state of Ti arising from diffusion of Ti cations in SrTiO{sub 3} to Fe sites of BiFeO{sub 3} are critical to the formation of 2DEG at the heterointerface.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Molecular-scale insights into the electrical double layer at oxide-electrolyte interfaces

The electrical double layer (EDL) at metal oxide-electrolyte interfaces critically affects fundamental processes in water splitting, batteries, and corrosion. However, limitations in the microscopic-level understanding of the EDL have been a major bottleneck in controlling these interfacial processes. Herein, we use ab initio-based machine learning potential simulations incorporating long-range electrostatics to unravel the molecular-scale picture of the EDL at the prototypical anatase TiO 2 -electrolyte interface under various pH conditions. Our large-scale simulations, capable of capturing interfacial water dissociation/recombination reactions and electrolytic proton transport, provide unprecedented insights into the detailed structure of the EDL. Moreover, the larger capacitance of the EDL under basic relative to acidic conditions, originating from the higher affinity of the cations for the oxide surface, is found to give rise to distinct charging mechanisms on negative and positive surfaces. Our results are validated by the agreement between the computed EDL capacitance and experimental data.

Chemical physics↗
DOE OSTI2012

Three-Dimensional Quantitative Chemical Roughness Of Buried ZrO2/In2O3 Interfaces Via Energy-Filtered Electron Tomography

The protocol to calculate the chemical roughness from three-dimensional (3-D) data cube acquired by energy-filtered electron tomography has been developed and applied to analyze the 3-D Zr distribution at the arbitrarily shaped interfaces in the ZrO2/In2O3 multilayer films. The calculated root-mean-square roughness quantitatively revealed the chemical roughness at the buried ZrO2/In2O3 interfaces, which is the deviation of Zr distribution from the ideal flat interface. Knowledge of the chemistry and structure of oxide interfaces in 3-D provides information useful for understanding changes in the behavior of a model ZrO2/In2O3 heterostructure that has potential to exhibit mixed conduction behavior. VC 2012 American Institute of Physics.

Zhong, X Y↗
DOE OSTI2016

Conducting interface in oxide homojunction: Understanding of superior properties in black TiO 2

Black TiO 2 nanoparticles with a crystalline core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO 2 . The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO 2 homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO 2 nanoparticles. Metallic conduction is achieved at the crystalline–amorphous homointerface via electronic interface reconstruction, which we show to be the main reason for the enhanced electron transport of black TiO 2 . As a result, this work not only achieves an unprecedented understanding of black TiO 2 but also provides a new perspective for investigating carrier generation and transport behavior at oxide interfaces, which are of tremendous fundamental and technological interest.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Theoretical Perspective of Promoting Direct Methane-to-Methanol Conversion at Complex Metal Oxide–Metal Interfaces

Direct methane conversion to methanol has been considered as an effective and economic way to release greenhouse effects and current high demand on methanol in industry. However, the process has long been challenging due to lack of viable catalysts to compromise the activation of methane that typically occurs high temperatures and retaining of produced methanol that requires mild conditions. Here, this perspective demonstrates an effective strategy to promote direct methane to methanol conversion by engineering the active sites and chemical environments at complex metal oxide - copper oxide - copper interfaces. Such effort strongly depends on the extensive theoretical studies by combining density functional theory (DFT) calculations and kinetic Monte Carlo (KMC) simulations to provide in-depth understanding of reaction mechanism and active sites, which built the strong basis to enable the identification of design principles and advance the catalyst optimization for selective CH 4 -to-CH 3 OH conversion.

03 NATURAL GAS↗
DOE OSTI2012

Reduction in interface state density of Al{sub 2}O{sub 3}/InGaAs metal-oxide-semiconductor interfaces by InGaAs surface nitridation

We report the decrease in interface trap density (D{sub it}) in Al{sub 2}O{sub 3}/InGaAs metal-oxide-semiconductor (MOS) capacitors by using electron cyclotron resonance plasma nitridation of the InGaAs surfaces. The impact of the nitridation process on the MOS interface properties is quantitatively examined. The plasma nitridation process is observed to form a nitrided layer at the InGaAs surface. The nitridation using microwave power (P{sub microwave}) of 250 W and nitridation time (t{sub nitridation}) of 420 s can form Al{sub 2}O{sub 3}/InGaAs MOS interfaces with a minimum D{sub it} value of 2.0 Multiplication-Sign 10{sup 11} cm{sup -2} eV{sup -1}. On the other hand, the nitridation process parameters such as P{sub microwave} and t{sub nitridation} are found to strongly alter D{sub it} (both decrease and increase are observed) and capacitance equivalent thickness (CET). It is found that the nitridation with higher P{sub microwave} and shorter t{sub nitridation} can reduce D{sub it} with less CET increase. Also, it is observed that as t{sub nitridation} increases, D{sub it} decreases first and increases later. It is revealed from XPS analyses that minimum D{sub it} can be determined by the balance between the saturation of nitridation and the progress of oxidation. As a result, it is found that the superior MOS interface formed by the nitridation is attributable to the existence of oxide-less InGaN/InGaAs interfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Synthesis of Interface-Driven Tunable Bandgap Metal Oxides

Mixed bandgap and bandgap tunability in semiconductors is critical in expanding their use. Composition altera-tions through single-crystal epitaxial growth and formation of multi-layer tandem structures are often employed to achieve mixed bandgaps albeit with limited tunability. In this study, self-assembled one-dimensional coordination polymers provide a fac-ile synthon and template for graphitic C-doped mesoporous oxides, gC-β-Ga 2 O 3 or gC-In 2 O 3 via controlled oxidative ligand ablation. These materials have mixed bandgaps, and colors, depending on amount of gC present. The carbon-oxide interface leads to induced gap states, hence, a stoichiometrically tunable band structure. Structurally, a multi-scale porous network percolating throughout the material is realized. The nature of heat-treatment and top-down process allows for facile tunabil-ity and formation of mixed bandgap metal oxides through controlled carbon deposition. As a proof of concept, gC-β-Ga 2 O 3 was utilized as a photocatalyst for CO 2 reduction, which demonstrated excellent selectivity and conversion rates into CH 4 and CO.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Asymmetric spin absorption across a low-resistance oxide barrier

An unconventional method of nonlocal spin detection is demonstrated in mesoscopic lateral spin valves at room temperature. Clear nonlocal spin signals are detected between the two ends of an extended ferromagnetic spin detector. This is different from the conventional method in which the nonlocal voltage is measured between the spin detector and the nonmagnetic channel. The results can be understood as spatially non-uniform absorption of a pure spin current into the spin detector across a low-resistance oxide interface.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2012

Interface dipole between two metallic oxides caused by localized oxygen vacancies

Oxygen vacancies are increasingly recognized to play a role in phenomena observed at transition-metal oxide interfaces. Here in this paper, we report a study of SrRuO 3 and La 0.7 Sr 0.3 MnO 3 interfaces using a combination of quantitative aberration-corrected scanning transmission electron microscopy, electron energy-loss spectroscopy, and density functional calculations. Cation displacements are observed at the interface, indicative of a dipolelike electric field even though both materials are nominally metallic. The observed displacements are reproduced by theory if O vacancies are present in the near-interface La 0.7 Sr 0.3 MnO 3 layers. The results suggest that atomic-scale structural mapping can serve as a quantitative indicator of the presence of O vacancies at interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Aqueous Titania Interfaces

Water–metal oxide interfaces are central to many phenomena and applications, ranging from material corrosion and dissolution to photoelectrochemistry and bioengineering. In particular, the discovery of photocatalytic water splitting on TiO 2 has motivated intensive studies of water-TiO 2 interfaces for decades. So far, a broad understanding of the interaction of water vapor with several TiO 2 surfaces has been obtained. However, much less is known about liquid water–TiO 2 interfaces, which are more relevant to many practical applications. Probing these complex systems at the molecular level is experimentally challenging and is sometimes possible only through computational studies. This review summarizes recent advances in the atomistic understanding, mostly through computational simulations, of the structure and dynamics of interfacial water on TiO 2 surfaces. The main focus is on the nature, molecular or dissociated, of water in direct contact with low-index defect-free crystalline surfaces. The hydroxyls resulting from water dissociation are essential in the photooxidation of water and critically affect the surface chemistry of TiO 2.

density functional theory↗
DOE OSTI2015

Irradiation-induced formation of a spinel phase at the FeCr/MgO interface

Oxide dispersion strengthened ferritic/martensitic alloys have attracted significant attention for their potential uses in future nuclear reactors and storage vessels, as the metal/oxide interfaces act as stable high-strength sinks for point defects while also dispersing helium. Here, in order to unravel the evolution and interplay of interface structure and chemistry upon irradiation in these types of materials, an atomically sharp FeCr/MgO interface was synthesized at 500 °C and separately annealed and irradiated with Ni 3+ ions at 500 °C. After annealing, a slight enrichment of Cr atoms was observed at the interface, but no other structural changes were found. However, under irradiation, sufficient Cr diffuses across the interface into the MgO to form a Cr-enriched transition layer that contains spinel precipitates. First-principles calculations indicate that it is energetically favorable to incorporate Cr, but not Fe, substitutionally into MgO. Furthermore, our results indicate that irradiation can be used to form new phases and complexions at interfaces, which may have different radiation tolerance than the pristine structures.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Understanding the Role of Overpotentials in Lithium Ion Conversion Reactions: Visualizing the Interface

Oxide conversion reactions are known to have substantially higher specific capacities than intercalation materials used in Li-ion batteries, but universally suffer from large overpotentials associated with the formation of interfaces between the resulting nanoscale metal and Li 2 O products. Here we use the interfacial sensitivity of operando X-ray reflectivity to visualize the structural evolution of ultrathin NiO electrodes and their interfaces during conversion. We observe two additional reactions prior to the well-known bulk, three-dimensional conversion occurring at 0.6 V: an accumulation of lithium at the buried metal/oxide interface (at 2.2 V) followed by interfacial lithiation of the buried NiO/Ni interface at the theoretical potential for conversion (at 1.9 V). To understand the mechanisms for bulk and interfacial lithiation, we calculate interfacial energies using density functional theory to build a potential-dependent nucleation model for conversion. These calculations show that the additional space charge layer of lithium is a crucial component for reducing energy barriers for conversion in NiO.

25 ENERGY STORAGE↗
DOE OSTI2012

STEM-EELS imaging of complex oxides and interfaces

The success of the correction of spherical aberration in the electron microscope has revolutionized our views of oxides. This is a very important class of materials that poses an exciting promise towards future applications of some of the most intriguing phenomena in condensed matter physics: colossal magnetoresistance, colossal ionic conductivity, high Tc superconductivity, ferroelectricity, etc. Understanding the physics underlying such phenomena, especially in low dimensional systems (thin films, interfaces, nanowires, nanoparticles, etc), relies on the availability of techniques capable of looking at these systems in real space and with atomic resolution and even beyond: in many cases the system properties depend on minuscule amounts of minuscule point defects that alter the materials properties dramatically. Atomic resolution spectroscopy in the aberration corrected electron microscope is one of the most powerful techniques available to materials scientists today. This article will briefly review some state-of-the-art applications of these techniques to oxide materials: from atomic resolution elemental mapping and single atom imaging to applications to real systems including oxide interfaces and mapping of physical properties such as the spin state of magnetic atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Impact of process temperature on GaSb metal-oxide-semiconductor interface properties fabricated by ex-situ process

We have studied the impact of process temperature on interface properties of GaSb metal-oxide-semiconductor (MOS) structures fabricated by an ex-situ atomic-layer-deposition (ALD) process. We have found that the ALD temperature strongly affects the Al{sub 2}O{sub 3}/GaSb MOS interface properties. The Al{sub 2}O{sub 3}/GaSb MOS interfaces fabricated at the low ALD temperature of 150 °C have the minimum interface-trap density (D{sub it}) of ∼4.5 × 10{sup 13 }cm{sup −2} eV{sup −1}. We have also found that the post-metalization annealing at temperature higher than 200 °C degrades the Al{sub 2}O{sub 3}/GaSb MOS interface properties. The low-temperature process is preferable in fabricating GaSb MOS interfaces in the ex-situ ALD process to avoid the high-temperature-induced degradations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

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/FeO x , 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–FeO x interactions among different systems under reducing conditions. Further, Pd interacts strongly with FeO x after high-temperature reductive treatment, featured by the formation of Pd single atoms in the FeO x matrix and increased Pd–Fe bonding, while Pt transforms into ordered PtFe intermetallics and Pt single atoms immediately upon the coating of FeO x . In contrast, Au does not manifest strong bonding with FeO x . As a proof of concept of tailoring metal–metal oxide interactions for catalysis, optimized Pd/FeO x demonstrates 100% conversion and 86.5% selectivity at 60 °C for acetylene semihydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗