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At least 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Charge carrier motion and effect of fixed oxide charge in a microstructured silicon radiation detector

Signal formation in a microstructured semiconductor neutron detector is more complex than in planar diode geometry. Three-dimensional microstructures are laterally smaller than the ionization cloud length, and the electric fields may be weak enough to exhibit plasma time effects. This work is the first detailed treatment of charge carrier motion in these complex semiconductor devices to replicate the time profile and signal magnitude. Simulations were performed using COMSOL Multiphysics to investigate various parameters that affect the propagation of the charge cloud. It was observed that the size of the simulated three-dimensional structure had an impact on the induced current pulse, indicating the importance of simulation geometry optimization to accurately simulate charge cloud expansion. COMSOL Multiphysics was used to replicate accurate charge creation profiles using energy deposition information imported from radiation transport codes. A detailed simulation methodology is presented to benchmark preamplifier event pulses along with complexities in modeling the charge carrier motion along the etched microstructured trenches with Si–SiO 2 boundary conditions, including fixed oxide charge and interface trapping.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2026

Electrolyte-Dependent, “Microscopically Irreversible” H-Atom Transfer Kinetics of Ce-Based Metal–Organic Framework, Ce-MOF-808

Redox reactions at the interface of metal oxides and protic electrolytes almost always involve protons and electrons in equal amounts. Given the stoichiometry, these proton-coupled electron transfer (PCET) reactions are thermochemically equivalent to net H-atom transfer (HAT) reactions. The correlation between the chemical nature of solid catalysts and HAT kinetics has been employed for decades as the design principle for energy-relevant reactions (e.g., reactions of 2H + /H 2 ). More recently, chemists have experimentally determined that a change in liquid electrolytes that alters the microenvironment at the redox-active sites has an equally profound impact on electrocatalysis involving PCET/HAT. Yet, precise correlations between the chemical nature of electrolytes and the PCET kinetics are, to date, rare in the literature. Herein, we report our findings using the Ce-based metal−organic framework, Ce-MOF-808, as a model system. Each Ce 6 (μ 3 −O) 4 (μ 3 − OH) 4 (OH) 6 (H 2 O) 6 node of this MOF undergoes a 1H + /1e − redox reaction. Using chronoamperometry and the Cottrell analysis, we have determined that the PCET hopping kinetics within the pores of Ce-MOF-808 can change by orders of magnitude by altering the buffer species and the proton activity of the electrolyte. Furthermore, in all buffers, reductive reactions were ∼3−10 times faster in kinetics than the reverse oxidative reaction with the same electrochemical driving force, suggesting that the system, at first glance, violates the principle of microscopic reversibility. Isothermal titration calorimetry (ITC) and computational simulations corroborated that the buffer-node binding thermodynamics are quite distinct, depending on the chemical nature of the buffer and the oxidation state of the node. Together, these results suggest that the substrate and the product during the oxidative vs reductive reaction of Ce-MOF-808 are chemically different species, which explains the apparent ‘microscopic irreversibility.’ Thus, the rational modulation of electrolytes can dramatically enhance PCET kinetics, even though the solid electrodes remain identical. Implications of these findings are contrasted with the electrochemical/electrocatalytic behavior of other redox-active MOFs, heterogeneous catalysts, and enzymatic systems at the solid−liquid interface.

Ce-based MOF↗
NASA NTRS1991

Relative sliding durability of two candidate high temperature oxide fiber seal materials

A test program to determine the relative sliding durability of two candidate ceramic fibers for high temperature sliding seal applications is described. Pin on disk tests were used to evaluate potential seal materials. Friction during the tests and fiber wear, indicated by the extent of fibers broken in a test bundle or yarn, was measured at the end of a test. In general, friction and wear increase with test temperature. This may be due to a reduction in fiber strength, a change in the surface chemistry at the fiber/counterface interface due to oxidation, adsorption and/or desorption of surface species and, to a lesser extent, an increase in counterface surface roughness due to oxidation at elevated temperatures. The relative fiber durability correlates with tensile strength indicating that tensile data, which is more readily available than sliding durability data, may be useful in predicting fiber wear behavior under various conditions. A simple model developed using dimensional analysis shows that the fiber durability is related to a dimensionless parameter which represents the ratio of the fiber strength to the fiber stresses imposed by sliding.

Dellacorte, Christopher↗
NASA NTRS1992

Relative sliding durability of two candidate high temperature oxide fiber seal materials

A test program to determine the relative sliding durability of two candidate ceramic fibers for high temperature sliding seal applications is described. Pin on disk tests were used to evaluate potential seal materials. Friction during the tests and fiber wear, indicated by the extent of fibers broken in a test bundle or yarn, was measured at the end of a test. In general, friction and wear increase with test temperature. This may be due to a reduction in fiber strength, a change in the surface chemistry at the fiber/counterface interface due to oxidation, adsorption and/or desorption of surface species and, to a lesser extent, an increase in counterface surface roughness due to oxidation at elevated temperatures. The relative fiber durability correlates with tensile strength indicating that tensile data, which is more readily available than sliding durability data, may be useful in predicting fiber wear behavior under various conditions. A simple model developed using dimensional analysis shows that the fiber durability is related to a dimensionless parameter which represents the ratio of the fiber strength to the fiber stresses imposed by sliding.

Dellacorte, Christopher↗
DOE OSTI2018

Discovery of a magnetic conductive interface in PbZr 0.2 Ti 0.8 O 3 /SrTiO 3 heterostructures

Here, emergent physical properties often arise at interfaces of complex oxide heterostructures due to the interplay between various degrees of freedom, especially those with polar discontinuities. It is desirable to explore if these structures may generate pure and controllable spin currents, which are needed to attain unmatched performance and energy efficiency in the next-generation spintronic devices. Here we report the emergence of a spin-polarized two-dimensional electron gas (SP-2DEG) at the interface of two insulators, SrTiO 3 and PbZr 0.2 Ti 0.8 O 3 . This SP-2DEG is strongly localized at the interfacial Ti atoms, due to the interplay between Coulomb interaction and band bending, and can be tuned by the ferroelectric polarization. Our findings open a door for engineering ferroelectric/insulator interfaces to create tunable ferroic orders for magnetoelectric device applications and provide opportunities for designing multiferroic materials in heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2016

In Situ Spectroscopic Investigation into the Active Sites for Crotonaldehyde Hydrogenation at the Pt Nanoparticle–Co 3 O 4 Interface

The hydrogenation of crotonaldehyde by platinum nanoparticles supported on cobalt oxide was used as a reaction to probe the effect of the interface between the two materials on the activity and selectivity of the catalyst. Four potential products can be formed by this reaction: propylene, butyraldehyde, crotyl alcohol, and butanol. When Pt nanoparticles are supported on SiO 2 , an inert support, only propylene and butyraldehyde are formed. However, when Pt is supported on cobalt oxide, the alcohols make up roughly 40% of the total activity, indicating that cobalt oxide plays a pivotal role in the reaction, much like other active supports such as TiO 2 . To elucidate the mechanism of alcohol formation, in situ sum frequency generation vibrational spectroscopy (SFG) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) were utilized to probe the reactant adsorption and intermediate formation and the chemical state of the materials under working catalytic conditions. The SFG data indicate that crotonaldehyde adsorbs on the oxide surface, likely through the aldehyde oxygen as well as on the Pt surface through the alkene group. AP-XPS results show that the surface of the Co 3 O 4 support becomes partially reduced under the reaction conditions and Pt exists in its metallic state. Taking these results together, we propose in this paper that the crotonaldehyde adsorbs at reduced oxide surface sites and that this adsorption mode is responsible for the production of alcohol products. A platinum nanoparticle density dependence study was also undertaken to change the abundance of interface sites and study their effect on the reaction. The selectivity between the two alcohol products was altered as a function of the Pt nanoparticle density: higher selectivity toward butanol and lower selectivity toward crotyl alcohol was obtained with increasing density, while propylene and butyraldehyde selectivities were constant with respect to density. Finally, on the basis of the data presented, we propose that butanol is preferentially formed at the metal–oxide interface, while crotyl alcohol is formed at oxide surface sites by reaction with spillover hydrogen.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1979

Metal-dielectric interactions

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Buckley, D. H.↗
DOE OSTI2020

Colossal oxygen vacancy formation at a fluorite-bixbyite interface

Oxygen vacancies in complex oxides are indispensable for information and energy technologies. There are several means to create oxygen vacancies in bulk materials. However, the use of ionic interfaces to create oxygen vacancies has not been fully explored. As such, we report an oxide nanobrush architecture designed to create high-density interfacial oxygen vacancies. An atomically well-defined (111) heterointerface between the fluorite CeO 2 and the bixbyite Y 2 O 3 is found to induce a charge modulation between Y 3+ and Ce 4+ ions enabled by the chemical valence mismatch between the two elements. Local structure and chemical analyses, along with theoretical calculations, suggest that more than 10% of oxygen atoms are spontaneously removed without deteriorating the lattice structure. Our fluorite–bixbyite nanobrush provides an excellent platform for the rational design of interfacial oxide architectures to precisely create, control, and transport oxygen vacancies critical for developing ionotronic and memristive devices for advanced energy and neuromorphic computing technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Proposed framework for thermomechanical life modeling of metal matrix composites

The framework of a mechanics of materials model is proposed for thermomechanical fatigue (TMF) life prediction of unidirectional, continuous-fiber metal matrix composites (MMC's). Axially loaded MMC test samples are analyzed as structural components whose fatigue lives are governed by local stress-strain conditions resulting from combined interactions of the matrix, interfacial layer, and fiber constituents. The metallic matrix is identified as the vehicle for tracking fatigue crack initiation and propagation. The proposed framework has three major elements. First, TMF flow and failure characteristics of in situ matrix material are approximated from tests of unreinforced matrix material, and matrix TMF life prediction equations are numerically calibrated. The macrocrack initiation fatigue life of the matrix material is divided into microcrack initiation and microcrack propagation phases. Second, the influencing factors created by the presence of fibers and interfaces are analyzed, characterized, and documented in equation form. Some of the influences act on the microcrack initiation portion of the matrix fatigue life, others on the microcrack propagation life, while some affect both. Influencing factors include coefficient of thermal expansion mismatch strains, residual (mean) stresses, multiaxial stress states, off-axis fibers, internal stress concentrations, multiple initiation sites, nonuniform fiber spacing, fiber debonding, interfacial layers and cracking, fractured fibers, fiber deflections of crack fronts, fiber bridging of matrix cracks, and internal oxidation along internal interfaces. Equations exist for some, but not all, of the currently identified influencing factors. The third element is the inclusion of overriding influences such as maximum tensile strain limits of brittle fibers that could cause local fractures and ensuing catastrophic failure of surrounding matrix material. Some experimental data exist for assessing the plausibility of the proposed framework.

Halford, Gary R.↗
DOE OSTI2016

Structural and electrical properties of AlN layers grown on silicon by reactive RF magnetron sputtering

AlN films of different thicknesses were deposited on n-Si (100) substrates by reactive radio frequency (rf) magnetron sputtering. Dependences of structure and electrical properties on thickness of deposited films were researched. The structures of the films were analyzed with scanning electron microscopy (SEM) and with transmitting electron microscopy (TEM). Electrical properties of the films were investigated on Au-AlN-(n-Si) structures by means of current-voltage (I-V), capacitance-voltage (C-V) and deep level transient spectroscopy (DLTS) techniques. Electron microscopy investigations had shown that structure and chemical composition of the films were thickness stratified. Near silicon surface layer was amorphous aluminum oxide one contained traps of positive charges with concentration of about 4 × 10{sup 18} cm{sup −3}. Upper layers were nanocrystalline ones consisted of both wurzite AlN and cubic AlON nanocrystals. They contained traps both positive and negative charges which were situated within 30 nm distance from silicon surface. Surface densities of these traps were about 10{sup 12} cm{sup −2}. Electron traps with activation energies of (0.2 ÷ 0.4) eV and densities of about 10{sup 10} cm{sup −2} were revealed on interface between aluminum oxide layer and silicon substrate. Their densities varied weakly with the film thickness.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte

Surface degradation on cycled lithium-ion battery cathode particles is governed not only by intrinsic thermodynamic properties of the material but also, oftentimes more predominantly, by the side reactions with the electrolytic solution. A superior electrolyte inhibits these undesired side reactions on the cathode and at the electrolyte interface, which consequently minimizes the deterioration of the cathode surface. The present study investigates a new boron-based anion receptor, tris(2,2,2-trifluoroethyl)borate (TTFEB), as an electrolyte additive in cells containing a lithium- and manganese-rich layered oxide cathode, Li 1.16 Ni 0.2 Co 0.1 Mn 0.54 O 2 . Our electrochemical studies demonstrate that the cycling performance and Coulombic efficiency are significantly improved because of the additive, in particular, under elevated temperature conditions. Spectroscopic analyses revealed that the addition of 0.5 wt % TTFEB is capable of reducing the content of lithium-containing inorganic species within the cathode-electrolyte interphase layer and minimizing the reduction of tetravalent Mn4+ at the cathode surface. Furthermore, our work introduces a novel additive highly effective in improving lithium-ion battery performance, highlights the importance in preserving the surface properties of cathode materials, and provides new insights on the working mechanism of electrolyte additives.

25 ENERGY STORAGE↗
DOE OSTI2021

Spin and Charge Interconversion in Dirac-Semimetal Thin Films

We use spin torque ferromagnetic resonance and ferromagnetic-resonance-driven spin pumping to detect spin-charge interconversion at room temperature in heterostructure devices that interface an archetypal Dirac semimetal, Cd 3 As 2 , with a metallic ferromagnet, Ni 0.80 Fe 0.20 (permalloy). Angle-resolved photoemission directly reveals the Dirac-semimetal nature of the samples prior to device fabrication and high-resolution transmission electron microscopy is used to characterize the crystalline structure and the relevant heterointerfaces. We find that the spin-charge interconversion efficiency in Cd 3 As 2 /permalloy heterostructures is comparable to that in heavy metals and that it is enhanced by the presence of an interfacial oxide. Spin torque ferromagnetic resonance measurements reveal an in-plane spin polarization regardless of an oxidized or pristine interface. We discuss the underlying mechanisms for spin-charge interconversion by comparing our results with first principles calculations and conclude that extrinsic mechanisms dominate the observed phenomena. Our results indicate a need for caution in interpretations of spin-transport and spin-charge conversion experiments in Cd 3 As 2 devices that seek to invoke the role of topological Dirac and Fermi arc states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Ionic Strength-Controlled Mn (Hydr)oxide Nanoparticle Nucleation on Quartz: Effect of Aqueous Mn(OH) 2

The early formation of manganese (hydr)oxide nanoparticles at mineral–water interfaces is crucial in understanding how Mn oxides control the fate and transport of heavy metals and the cycling of nutrients. Using atomic force microscopy, we investigated the heterogeneous nucleation and growth of Mn (hydr)oxide under varied ionic strengths (IS; 1–100 mM NaNO 3 ). Experimental conditions (i.e., 0.1 mM Mn 2+ (aq) concentration and pH 10.1) were chosen to be relevant to Mn remediation sites. We found that IS controls Mn(OH) 2 (aq) formation, and that the controlled Mn(OH) 2 (aq) formation can affect the system’s saturation and subsequent Mn(OH) 2 (s) and further Mn 3 O 4 (s) nanoparticle formation. In 100 mM IS system, nucleated Mn (hydr)oxide particles had more coverage on the quartz substrate than those in 1 mM and 10 mM IS systems. This high IS also resulted in low supersaturation ratio and thus favor heterogeneous nucleation, having better structural matching between nucleating Mn (hydr)oxides and quartz. Here, the unique information obtained in this work improves our understanding of Mn (hydr)oxide formation in natural as well as engineered aqueous environments, such as groundwater contaminated by natural leachate and acid mine drainage remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Size dependence of inter- and intra-cluster interactions in core-shell iron-iron oxide nanoclusters

The room temperature magnetic properties of core-shell iron-iron oxide nanoclusters (NCs) synthesized by a cluster deposition system have been investigated, and their dependence on mean cluster size has been discussed. In this study, the surface/boundary spins of clusters were not frozen and were thermally activated during the measurements. The inter-cluster interactions between clusters and intra-cluster interactions between the iron core (ferromagnetic) and iron oxide shell (ferrimagnetic) have been investigated by field dependent isothermal remanent magnetization and dc demagnetization measurements at room temperature. The Henkel plot and delta M plot support the existence of dipolar inter-cluster interactions which become stronger with the growth of cluster size. The derivative of the initial magnetization curve implies that smaller clusters require less field and time than the bigger ones to overcome various energy barriers before aligning along the field direction. Coercive field and magnetization are also correlated with the interaction parameters. To compare the room temperature magnetic results, one system was studied at low temperature, where exchange coupling at the interface between the oxide and metallic phases was observed through bias effect and anisotropy enhancement.

core-shell structure↗
DOE OSTI2016

Strongly enhanced Rashba splittings in an oxide heterostructure: A tantalate monolayer on BaHfO 3

In the two-dimensional electron gas emerging at the transition metal oxide surface and interface, various exotic electronic ordering and topological phases can become experimentally more accessible with the stronger Rashba spin-orbit interaction. Here, we present a promising route to realize significant Rashba-type band splitting using a thin film heterostructure. Based on first-principles methods and analytic model analyses, a tantalate monolayer on BaHfO 3 is shown to host two-dimensional bands originating from Ta t 2g states with strong Rashba spin splittings, nearly 10% of the bandwidth, at both the band minima and saddle points. An important factor in this enhanced splitting is the significant t 2g –e g interband coupling, which can generically arise when the inversion symmetry is maximally broken due to the strong confinement of the 2DEG on a transition metal oxide surface. Here, our results could be useful in realizing topological superconductivity at oxide surfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Ferroelectric Self-Polarization Controlled Magnetic Stratification and Magnetic Coupling in Ultrathin La 0.67 Sr 0.33 MnO 3 Films

Multiferroic oxide heterostructures consisting of ferromagnetic and ferroelectric components hold the promise for nonvolatile magnetic control via ferroelectric polarization, advantageous for the low-dissipation spintronics. Modern understanding of the magnetoelectric coupling in these systems involves structural, orbital, and magnetic reconstructions at interfaces. Previous works have long proposed polarization-dependent interfacial magnetic structures; however, direct evidence is still missing, which requires advanced characterization tools with near-atomic-scale spatial resolutions. Here, extensive polarized neutron reflectometry (PNR) studies have determined the magnetic depth profiles of PbZr 0.2 Ti 0.8 O 3 /La 0.67 Sr 0.33 MnO 3 (PZT/LSMO) bilayers with opposite self-polarizations. When the LSMO is 2–3 nm thick, the bilayers show two magnetic transitions on cooling. However, temperature-dependent magnetization is different below the lower-temperature transition for opposite polarizations. PNR finds that the LSMO splits into two magnetic sublayers, but the inter-sublayer magnetic couplings are of opposite signs for the two polarizations. Near-edge X-ray absorption spectroscopy further shows contrasts in both the Mn valences and the Mn–O bond anisotropy between the two polarizations. Finally, this work completes the puzzle for the magnetoelectric coupling model at the PZT/LSMO interface, showing a synergic interplay among multiple degrees of freedom toward emergent functionalities at complex oxide interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

In situ surface and interface study of crystalline (3×1)-O on InAs

The oxidation behavior of de-capped InAs (100) exposed to O{sub 2} gas at different temperatures is investigated in situ with high resolution of monochromatic x-ray photoelectron spectroscopy and low energy electron diffraction. The oxide chemical states and structure change dramatically with the substrate temperature. A (3 × 1) crystalline oxide layer on InAs is generated in a temperature range of 290–330 °C with a coexistence of In{sub 2}O and As{sub 2}O{sub 3}. The stability of the crystalline oxide upon the atomic layer deposition (ALD) of HfO{sub 2} is studied as well. It is found that the generated (3 × 1) crystalline oxide is stable upon ALD HfO{sub 2} growth at 100 °C.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Modified Oxygen Defect Chemistry at Transition Metal Oxide Heterostructures Probed by Hard X-ray Photoelectron Spectroscopy and X-ray Diffraction

Transition metal oxide hetero-structures are interesting due to the distinctly different properties that can arise from their interfaces, such as superconductivity, high catalytic activity and magnetism. Oxygen point defects can play an important role at these interfaces in inducing potentially novel properties. The design of oxide hetero-structures in which the oxygen defects are manipulated to attain specific functionalities requires the ability to resolve the state and concentration of local oxygen defects across buried interfaces. In this work, we utilized a novel combination of hard x-ray photoelectron spectroscopy (HAXPES) and high resolution xray diffraction (HRXRD) to probe the local oxygen defect distribution across the buried interfaces of oxide heterolayers. This approach provides a non-destructive way to qualitatively probe locally the oxygen defects in transition metal oxide hetero-structures. We studied two trilayer structures as model systems - the La 0.8 Sr 0.2 CoO 3-δ /(La 0.5 Sr 0.5 ) 2 CoO 4 /La 0.8 Sr 0.2 CoO 3-δ (LSC 113 /LSC 214 ) and the La 0.8 Sr 0.2 CoO 3-δ /La 2 NiO 4+δ /La 0.8 Sr 0.2 CoO 3-δ (LSC 113 /LNO 214 ) on SrTiO 3 (001) single crystal substrates. We found that the oxygen defect chemistry of these transition metal oxides was strongly impacted by the presence of interfaces and the properties of the adjacent phases. Under reducing conditions, the LSC 113 in the LSC 113 /LNO 214 tri-layer had less oxygen vacancies than the LSC 113 in the LSC 113 /LSC 214 tri-layer and the LSC 113 single phase film. On the other hand, LSC 214 and LNO 214 were more reduced in the two tri-layer structures when in contact with the LSC 113 layer compared to their single phase counterparts. Furthermore, the results point out a potential way to modify the local oxygen defect states at oxide hetero-interfaces.

36 MATERIALS SCIENCE↗