Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “oxide interfaces”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 793 records · Page 44

Effect of nitrogen passivation on interface composition and physical stress in SiO 2 /SiC(4H) structures

Here, the electron density and physical stress at the thermally oxidized SiC/SiO 2 interface, and their change with nitrogen incorporation, were observed using x-ray reflectivity, Raman scattering, and a novel stress determination technique. There is no evidence for residual carbon species at the SiO 2 /SiC. Instead, a ~1 nm thick low electron density layer is formed at this interface, consistent with interfacial suboxides (SiO x , 0.3 < x < 2), along with high interfacial stress. Nitrogen passivation, a known process to improve the interface state density and electronic properties, eliminates the low density component and simultaneously releases the interface stress. On the basis of these findings, a new chemical interaction model is proposed to explain the effect of the nitrogen, and a guideline, stress managing together with elemental control of the dielectric/SiC interface, is suggested to achieve high quality gate stack on SiC.

36 MATERIALS SCIENCE↗

XPS study of interface formation of CVD SiO2 on InSb

The interfacial chemistry of CVD SiO2 films deposited on thin native oxides grown on InSb substrates is examined using X-ray photoemission spectroscopy (XPS) and a relatively benign chemical etching technique for depth profiling. An intensity analysis of XPS spectra is used to derive the compositional structure of the interfaces obtained in the SiO2/native oxide/InSb system. Peak positions in these spectra are used to follow the change in substrate surface potential during the etch sequence, and to establish the chemical nature of the species formed during deposition and subsequent processing. Reaction of the substrate with oxygen resulted in an In-rich native oxide and 1-2 monolayers of excess elemental Sb at the native-oxide/substrate interface, incompletely oxidized silane reduced the native oxide, leaving less than 1 monolayer of elemental In at the SiO2/native oxide interface. Etch removal of this thin In-rich layer leads to a change in the substrate surface potential of 0.06 eV, corresponding to a net increase in positive charge. The results are consistent with simple thermodynamic considerations; they are also compared to previously reported studies of deposited dielectrics on III-V compound semiconductors.

Vasquez, R. P.↗

Characterization of iron oxide nanoparticle films at the air–water interface in Arctic tundra waters

Here, massive amounts of organic carbon have accumulated in Arctic permafrost and soils due to anoxic and low temperature conditions that limit aerobic microbial respiration. Alternative electron acceptors are thus required for microbes to degrade organic carbon in these soils. Iron or iron oxides have been recognized to play an important role in carbon cycle processes in Arctic soils, although the exact form and role as an electron acceptor or donor remain poorly understood. Here, Arctic biofilms collected during the summers of 2016 and 2017 from tundra surface waters on the Seward Peninsula of western Alaska were characterized with a suite of microscopic and spectroscopic methods. We hypothesized that these films contain redox-active minerals bound to biological polymers. The major components of the films were found to be iron oxide nanoparticle aggregates associated with extracellular polymeric substances. The observed mineral phases varied between films collected in different years with magnetite (Fe 2+ Fe 2 3+ O 4 ) nanoparticles (<5 nm) predominantly identified in the 2016 films, while for films collected in 2017 ferrihydrite-like amorphous iron oxyhydroxides were found. While the exact formation mechanism of these Artic iron oxide films remains to be explored, the presence of magnetite and other iron oxide/oxyhydroxide nanoparticles at the air–water interface may represent a previously unknown source of electron acceptors for continual anaerobic microbial respiration of organic carbon within poorly drained Arctic tundra.

54 ENVIRONMENTAL SCIENCES↗

Traveling interface modulations and anisotropic front propagation in ammonia oxidation over Rh(110)

The bistable NH{sub 3} + O{sub 2} reaction over a Rh(110) surface was explored in the pressure range 10{sup −6}–10{sup −3} mbar and in the temperature range 300–900 K using photoemission electron microscopy and low energy electron microscopy as spatially resolving methods. We observed a history dependent anisotropy in front propagation, traveling interface modulations, transitions with secondary reaction fronts, and stationary island structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling Magnetization Vector Depth Profiles of La 0.7 Sr 0.3 CoO 3 /La 0.7 Sr 0.3 MnO 3 Exchange Spring Bilayers via Interface Reconstruction

The La 0.7 Sr 0.3 CoO 3–δ /La 0.7 Sr 0.3 MnO 3–δ (LSCO/LSMO) bilayer system is an ideal perovskite oxide platform for investigating interface reconstruction and its effect on their magnetic properties. Previous studies have shown that LSCO can separate into magnetic sublayers, which possess distinct trends as the total LSCO thickness increases. Here, we used polarized neutron reflectometry to quantify changes in the magnetic and chemical depth profiles, and it confirms the formation of ~12 Å-thick interfacial LSCO and LSMO layers, characterized by a decreased nuclear scattering length density compared to the bulk of the layers. This decrease is attributed to the combined effects of oxygen vacancy formation and interfacial charge transfer, which lead to magnetically active Co 2+ ions with ionic radii larger than the Co 3+ /Co 4+ ions typically found in bulk LSCO or single-layer films. The interfacial magnetization values, as well as Co 2+ ion and oxygen vacancy concentrations, depend strongly on the LSCO layer thickness. These results highlight the sensitive interplay of the cation valence states, oxygen vacancy concentration, and magnetization at interfaces in perovskite oxide multilayers, demonstrating the potential to tune their functional properties via careful design of their structure.

36 MATERIALS SCIENCE↗

Enhancing Acidic Oxygen Evolution Activity by Controlling Oxidation State of Iridium

Iridium oxides with high oxidation states have been reported to be effective in enhancing the acidic oxygen evolution reaction (OER) performance. Herein, we develop ultrasmall IrO x nanoparticles (NPs) over titanium nitride (TiN), which undergoes surface oxidation under oxidative conditions to form oxygen-modified TiN (oxi-TiN), enabling the formation of highly oxidized Ir δ+ (δ > 4). This IrO x /oxi-TiN catalyst delivers higher Ir mass activity than commercial IrO 2 , while comparable stability is maintained. The superior OER activity of IrO x /oxi-TiN is further demonstrated in a proton exchange membrane water electrolyzer (PEMWE), requiring only 1.88 V to reach 3 A cm −2 , achieving the U.S. Department of Energy 2025 target (1.90 V at 3 A cm −2 ). In situ X-ray absorption spectroscopy (XAS) confirms that the superior OER activity of IrO x /oxi-TiN originates from highly oxidized Ir δ+ under OER conditions. Further, density functional theory (DFT) calculations reveal a general correlation between the oxidation state of Ir and OER overpotential. Specifically, the introduction of interfacial oxygen at the Ir/TiN interface increases the oxidation state of deposited Ir δ+ from δ < 4 to δ > 4, decreasing the OER overpotential. This study highlights the critical role of high oxidation states of Ir δ+ in enhancing OER activity, providing guidance for the development of advanced acidic OER catalysts.

In situ measurements↗

Enhancing Acidic Oxygen Evolution Activity by Controlling Oxidation State of Iridium

Iridium oxides with high oxidation states have been reported to be effective in enhancing the acidic oxygen evolution reaction (OER) performance. In this work, we develop ultrasmall IrO x nanoparticles (NPs) over titanium nitride (TiN), which undergoes surface oxidation under oxidative conditions to form oxygen‐modified TiN (oxi‐TiN), enabling the formation of highly oxidized Ir δ+ (δ > 4). This IrO x /oxi‐TiN catalyst delivers higher Ir mass activity than commercial IrO 2 , while comparable stability is maintained. The superior OER activity of IrO x /oxi‐TiN is further demonstrated in a proton exchange membrane water electrolyzer (PEMWE), requiring only 1.88 V to reach 3 A cm −2 , achieving the U.S. Department of Energy 2025 target (1.90 V at 3 A cm −2 ). In situ X‐ray absorption spectroscopy (XAS) confirms that the superior OER activity of IrO x /oxi‐TiN originates from highly oxidized Ir δ+ under OER conditions. Density functional theory (DFT) calculations reveal a general correlation between the oxidation state of Ir and OER overpotential. Specifically, the introduction of interfacial oxygen at the Ir/TiN interface increases the oxidation state of deposited Ir δ+ from δ < 4 to δ > 4, decreasing the OER overpotential. This study highlights the critical role of high oxidation states of Ir δ+ in enhancing OER activity, providing guidance for the development of advanced acidic OER catalysts.

58 GEOSCIENCES↗

Experimental observations of the chemistry of the SiO2/Si interface

Changes in silicon surface preparation prior to thermal oxidation are shown to leave a signature by altering the final SiO2/Si interface structure. Surface analytical techniques, including XPS, static SIMS, ion milling, and newly developed wet-chemical profiling procedures are used to obtain detailed information on the chemical structure of the interface. The oxides are shown to be essentially SiO2 down to a narrow transitional interface layer (3-7 A). A number of discrete chemical species are observed in this interface layer, including different silicon bonds (e.g., C-, OH-, H-) and a range of oxidation states of silicon (0 to +4). The effect of surface preparation and the observed chemical species are correlated with oxide growth rate, surface-state density, and flatband shifts after irradiation.

Grunthaner, F. J.↗

Some TEM observations of Al2O3 scales formed on NiCrAl alloys

The microstructural development of Al2O3 scales on NiCrAl alloys has been examined by transmission electron microscopy. Voids were observed within grains in scales formed on a pure NiCrAl alloy. Both voids and oxide grains grew measurably with oxidation time at 1100 C. The size and amount of porosity decreased towards the oxide-metal growth interface. The voids resulted from an excess number of oxygen vacancies near the oxidemetal interface. Short-circuit diffusion paths were discussed in reference to current growth stress models for oxide scales. Transient oxidation of pure, Y-doped, and Zr-doped NiCrAl was also examined. Oriented alpha-(Al, Cr)2O3 and Ni(Al, Cr)2O4 scales often coexisted in layered structures on all three alloys. Close-packed oxygen planes and directions in the corundum and spinel layers were parallel. The close relationship between oxide layers provided a gradual transition from initial transient scales to steady state Al2O3 growth.

Smialek, J.↗

Spatiotemporal refraction of light in an epsilon-near-zero indium tin oxide layer: frequency shifting effects arising from interfaces

When light travels through a medium in which the refractive index is rapidly changing with time, the light will undergo a shift in its frequency. Significant frequency shifting effects have recently been reported for transparent conductive oxides. These observations have been interpreted as emerging from temporal changes to the propagation phase in a bulk medium resulting from temporal variations in the refractive index. It is an effect referred to as temporal refraction. Here, we show that the frequency shift in an epsilon-near-zero layer made of indium tin oxide originates not only from this bulk response but includes a significant effect resulting from temporal changes to the spatial boundary conditions. This boundary effect can lead to a dominant, opposing shift to the bulk effect for certain angles. Hence, this process gives rise to a frequency shift that can be tailored through the angle, decoupling the amplitude and phase modulation.

Bohn, Justus (ORCID:0000000214376450)↗

Controlling Interfacial Charge Separation Energetics and Kinetics

The overall goal is to probe electron transfer kinetics of the Marcus inverted region at interfaces. This project specifically uses a dye‐semiconductor interface with a reversible electron transfer reagent in solution where the semiconductor conduction band and electron transfer reagent ideally have a potential energy difference firmly within the Marcus inverted region. The goals of this project are: (Goal 1) Identify dye design elements that give dyes with low energy ground‐state oxidation potentials while retaining desirable electron transfer kinetics at the semiconductor interface. (Goal 2) Identify dye designs with excited‐state oxidation potentials set to fixed energies through molecular design while the dye ground‐state oxidation potentials are varied to allow for the evaluation of varied electron transfer reagents/redox shuttles (RS) with different free energies for electron transfer. (Goal 3) Within the context of the functionality identified in goals 1 and 2, goal 3 seeks to design dyes with features maximizing charge carrier lifetimes by minimizing recombination losses at metal oxide interfaces with high voltage systems. (Goal 4) Probe electron transfer kinetics in a high voltage‐dye sensitized solar cell with both the oxidized dye and RS firmly within the Marcus inverted region with regard to the TiO2 CB. (Goal 5) Identify tailored sensitizer/redox shuttle pairs with desirable electron transfer kinetics in defined spectral regions capable of “banding off” incident solar irradiation to give high voltage multijunction systems capable of exceeding the Shockley‐Queisser limit and powering catalytic processes.

14 SOLAR ENERGY↗

Migration of Cobalt Species within Mixed Platinum-Cobalt Oxide Bifunctional Electrocatalysts in Alkaline Electrolytes

Bifunctional oxygen electrocatalysts have significant potentials for energy storage and conversion applications. Here we report a facile strategy toward bifunctional electrocatalysts by supporting mixed platinum and cobalt oxide nanoparticles on carbon black. The composite electrocatalyst (denoted as Pt+CoO x /C) is found to exhibit higher oxygen evolution reaction (OER) activity than CoOx/C, but slightly lower oxygen reduction reaction (ORR) activity than Pt/C in alkaline electrolytes. The bifunctional catalytic performance is ascribed to the in situ formation of heterogenous platinum-cobalt (hydro)oxide (Pt-CoO x H y ) interfaces under the electrochemical reaction conditions. Calculated electrochemical phase (Pourbaix) diagrams suggest that the migration of Co species was driven by the relative stability of Pt-CoO x H y interfaces versus bulk (hydroxy)oxides or aqueous ions of cobalt.

25 ENERGY STORAGE↗

Formation of Secondary Organic Aerosols (SOA) via Nitrate Ion Photochemistry In and On Particles (Final Technical Report)

DOE has funded our work in three areas: (1) reactions of sea salt aerosols to form photochemically labile halogen gases that help to drive tropospheric chemistry; (2) oxidation of organics at interfaces and formation of SOA driven by oxides of nitrogen photochemistry; and (3) nucleation and growth of new particles in the troposphere from reactions of methanesulfonic acid with amines.

atmospheric chemistry↗

Properties of the SiO{sub 2}- and SiN{sub x}-capped GaAs(100) surfaces of GaInAsN/GaAs quantum-well heterostructures studied by photoelectron spectroscopy and photoluminescence

SiO{sub 2} and SiN{sub x} layers are routinely deposited onto III-V(100) surfaces at different device processing steps. We elucidate these insulator-interface properties with photoemission and photoluminescence (PL) of SiO{sub 2}- and SiN{sub x}-capped GaAs(100) surfaces of GaInAsN/GaAs quantum wells (QWs). Post-growth annealing led to an increase of the QW-PL intensity, of which origin can be clearly linked to the SiO{sub 2} and SiN{sub x} interfaces. Concomitantly, Ga{sub 2}O-related photoemission increased, indicating useful formation of Ga{sub 2}O at both insulator interfaces. Furthermore, higher Ga-oxidation-state emission, identified with Ga diffused into SiO{sub 2} and SiN{sub x}, correlates with the blue-shift of the QW-PL wavelength. Also, interfacial As-As related photoemission was identified.

36 MATERIALS SCIENCE↗

First-Principles study of interface capture of Ni during high-temperature oxidation of NiCr alloys

The formation of precipitated phases of less reactive metals within an oxide scale during alloy oxidation can disrupt its structural integrity, significantly compromising the protective function of the oxide. To better understand this phenomenon, it is crucial to investigate the atomic-level diffusion mechanisms that drive precipitate formation. In this study, we employ first-principles calculations to examine the diffusion and aggregation of Ni atoms across the NiCr/Cr 2 O 3 interface during the high-temperature oxidation of NiCr alloys. Our results reveal that, in the absence of Cr vacancies, Ni atoms predominantly remain within the NiCr substrate, with minimal migration toward the Cr 2 O 3 layer. However, when Cr vacancies are present at both the NiCr/Cr 2 O 3 interface and within the Cr 2 O 3 bulk, Ni atoms exhibit a strong propensity to migrate from the NiCr substrate into the Cr 2 O 3 bulk, where they aggregate into Ni-rich regions with a corundum structure. This study provides valuable atomic-level insights into the diffusion and aggregation of less-reactive metals at the alloy/oxide interface, enhancing our understanding of solute capture and its contribution to the degradation of oxidation resistance in alloys.

Chen, Jianmin [Xiangtan University (China)] (ORCID↗

Magnetic proximity effect at the interface between a cuprate superconductor and an oxide spin valve

A heterostructure that consists of the YBa{sub 2}Cu{sub 3}O{sub 7–δ} cuprate superconductor and the SrRuO{sub 3}/La{sub 0.7}Sr{sub 0.3}MnO{sub 3} ruthenate/manganite spin valve is investigated using SQUID magnetometry, ferromagnetic resonance, and neutron reflectometry. It is shown that a magnetic moment is induced due to the magnetic proximity effect in the superconducting part of the heterostructure, while the magnetic moment in the composite ferromagnetic interlayer is suppressed. The magnetization emerging in the superconductor coincides in order of magnitude with the results of calculations taking into account the induced magnetic moment of Cu atoms because of orbital reconstruction at the interface between the superconductor and the ferromagnet, as well as with the results of the model taking into account the variations in the density of states at a distance on the order of the coherence length in the superconductor. The experimentally obtained characteristic penetration depth of the magnetic moment in the superconductor considerably exceeds the coherence length of the cuprate superconductor, which indicates the predominance of the mechanism of induced magnetic moment of Cu atoms.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Influence of a Buffer Layer on the Formation of a Thin-Film Nickel Catalyst for Carbon Nanotube Synthesis

The formation of nanoparticles of a thin-film nickel catalyst applied on a buffer layer in the form of pure titanium, titanium oxide, or titanium nitride has been studied. It has been shown that if nanotubes are synthesized in three stages (oxidation, reduction, and growth of nanotubes), the situation may arise when the metallic catalyst becomes isolated from the surface, and hence, from the hydrocarbon flux, as a result of which the nanotube growth stops. Isolation takes place when the interface between titanium oxide and the gas phase in the reactor moves. In this case, titanium oxide goes round a nickel oxide nanoparticle and insulates it. The displacement rate of this interface and the coefficient of hydrogen diffusion in titanium dioxide have been determined.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electron escape depth variation in thin SiO2 films measured with variable photon energy

A double crystal monochromator at the Stanford Synchrotron Radiation Laboratory is used to study the Si/SiO2 interface, using photon energies of hv = 1950-3700 eV. This photon energy range allows interfaces to be observed through oxide layers 50 A thick or more. Variations in electron escape depth and/or oxide density as a function of distance from the interface are observed over the entire kinetic energy range (100-3600 eV). These differences are attributed to a strained oxide layer near the interface.

Hecht, M. H.↗