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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Study of CO 2 Adsorption Properties on the SrTiO 3 (001) Surface with Ambient Pressure XPS

The adsorption properties of CO 2 on the SrTiO 3 (001) surface were investigated using ambient pressure X-ray photoelectron spectroscopy under elevated pressure and temperature conditions. On the Nb-doped TiO 2 -enriched (1 × 1) SrTiO 3 surface, CO 2 adsorption, i.e., the formation of CO 3 surface species, occurs first at the oxygen lattice site under 10 –6 mbar CO 2 at room temperature. The interaction of CO 2 molecules with oxygen vacancies begins when the CO 2 pressure increases to 0.25 mbar. The adsorbed CO 3 species on the Nb-doped SrTiO 3 surface increases continuously as the pressure increases but starts to leave the surface as the surface temperature increases, which occurs at approximately 373 K on the defect-free surface. On the undoped TiO 2 -enriched (1 × 1) SrTiO 3 surface, CO 2 adsorption also occurs first at the lattice oxygen sites. Both the doped and undoped SrTiO 3 surfaces exhibit an enhancement of the CO 3 species with the presence of oxygen vacancies, thus indicating the important role of oxygen vacancies in CO 2 dissociation. When OH species are removed from the undoped SrTiO 3 surface, the CO 3 species begin to form under 10 –6 mbar at 573 K, thus indicating the critical role of OH in preventing CO 2 adsorption. The observed CO 2 adsorption properties of the various SrTiO 3 surfaces provide valuable information for designing SrTiO 3 -based CO 2 catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Cluster dynamics simulation of xenon diffusion during irradiation in UO 2

Diffusion of fission gas in UO 2 nuclear fuel impacts several important performance metrics, such as fission gas release, swelling, and thermal conductivity. Current empirical models of fission gas release have significant uncertainty, some of which derives from the bulk diffusion rate and its dependence on, for example, fuel chemistry and irradiation. In this work, we have applied the previously-developed Free Energy Cluster Dynamics (FECD) methodology in the code Centipede to calculate xenon cluster concentrations in UO 2 under intrinsic (high temperature) and irradiation-enhanced (intermediate temperature) conditions in order to develop a model of the xenon diffusion coefficient based on the atomic scale mechanisms responsible for transport. While the diffusion mechanism for xenon in UO 2 is adequately described by the Xe + U 2 O vacancy cluster for intrinsic conditions, a similar process is not capable of capturing measured in-pile fission gas diffusivity at intermediate temperatures. Therefore, a different diffusion mechanism must dominate under this regime. Using calculated atomistic data, we have shown that irradiation-enhanced diffusion at intermediate temperatures occurs via the larger Xe + U 4 O y vacancy clusters, which have lower migration barriers and increase in concentration by several orders of magnitude compared to intrinsic conditions. This mechanism is enabled by the increased uranium vacancy concentration under irradiation due to Frenkel pair production. In addition, the fast migration of uranium interstitials with two attached oxygen interstitials lowers the total uranium interstitial concentration through reactions with sinks. This allows the extended defects, such as Xe + U 4 O y vacancy clusters, to maintain high concentrations by limiting annihilation with attached vacancies. Furthermore, predictions using the Xe + U 4 O y diffusion mechanism are in good agreement with experiment, albeit with some differences in the Arrhenius slope, which we believe may be related to either experimental or model parameter uncertainty. Lastly, an analytical expression suitable for application in fuel performance simulations was derived to capture the predictions of the Centipede simulations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

On Proton Defects and the Phase Transformation of NiO 2

One approach to high-capacity Li-ion battery cathodes is to increase the Ni content. Unfortunately, Ni-rich materials undergo a phase transition and volume collapse at a high state of charge (SOC), which degrades battery performance. At a high SOC, NiO 2 undergoes a phase transition from the O 3 to the O 1 phase. The O 1 phase appears to be more thermodynamically stable than the O 3 phase. However, density functional theory (DFT) often predicts higher stability for O 3 , depending on the DFT approximation. The energy difference between the O 1 and O 3 phases is on the order of 10 meV/atom. Furthermore, we find that proton defects are more stable in the O 1 phase than in the O 3 phase by about 90 meV per proton. Defects in NiO 2 energetically favor the O 3 -O 1 phase transition observed in a high SOC in Li $x$ NiO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electronic surface reconstruction of TiO 2 nanocrystals revealed by resonant inelastic x-ray scattering

The identification of lattice multiphases in TiO 2 nanocrystals is studied by high resolution transmission electron microscope and electron diffraction patterns. Based on the spectroscopic analysis using soft x-ray absorption and resonant inelastic soft x-ray scattering, it is believed that the oxygen vacancies at the interface exhibit structural distortion of the TiO$^{8-}_6$ cluster around the defect site as for the multiphase lattice. We elucidate that the extra 3d electrons nearby induce the inelastic scattering features with the excitation energy dependence owing to different energy relaxation processes, a characteristic of the electron-phonon coupling or the nature of the electron-hole pair at the intermediate state. The manifold dd excitations driven by the strong interaction between Ti-3d and O-2p electrons are noticeably rich, coexisting on both Ti and O sites. Finally, this sophisticated experiment can advance the perspective of nanocomposite TiO 2 for various interactions of surface Ti 3+ in applications of future devices.

36 MATERIALS SCIENCE↗
NASA NTRS1969

Complex defects in CoO.

CoO complex defects indicated by negative enthalpy of formation, considering isobaric electrical conductivity measurements at various temperatures and oxygen pressures

Hed, A. Z.↗
NASA NTRS1991

Ground and space based optical analysis of materials degradation in low-Earth-orbit

There is strong interest in being able to accurately and sensitively monitor materials degradation in both ground-based and space-based environments. Two optical techniques for sensitive degradation monitoring are reviewed: spectroscopic ellipsometry and photothermal spectroscopy. These techniques complement each other in that ellipsometry is sensitive to atomically thin surface and subsurface changes, and photothermal spectroscopy is sensitive to local defects, pin-holes, subsurface defects, and delamination. Progress in applying these spectroscopies (both ex situ and in situ) to atomic oxygen degradation of space materials is reviewed.

Woollam, John A.↗
DOE OSTI2023

Excited State Properties of Point Defects in Semiconductors and Insulators Investigated with Time-Dependent Density Functional Theory

Here, we present a formulation of spin-conserving and spin-flip hybrid time-dependent density functional theory (TDDFT), including the calculation of analytical forces, which allows for efficient calculations of excited state properties of solid-state systems with hundreds to thousands of atoms. We discuss an implementation on both GPU- and CPU-based architectures along with several acceleration techniques. We then apply our formulation to the study of several point defects in semiconductors and insulators, specifically the negatively charged nitrogen-vacancy and neutral silicon-vacancy centers in diamond, the neutral divacancy center in 4H silicon carbide, and the neutral oxygen-vacancy center in magnesium oxide. Our results highlight the importance of taking into account structural relaxations in excited states in order to interpret and predict optical absorption and emission mechanisms in spin defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Tracking oxygen vacancy migration in memristor devices using operando hard X-ray photoelectron spectroscopy

Fabrication of ultrathin (sub-2 nm) oxide semiconductor memristors poses the fundamental challenge of achieving oxide growth with atomic precision in terms of electronic structure and defect formation. Recently, ultrathin memristors consisting of bilayers of mixed Al 2 O 3 and MgO atomic layers were fabricated using an in vacuo atomic layer deposition process. This approach offers a unique platform for precise atomic control of oxygen vacancies in the device in which the vacancies are introduced by placing MgO atomic layers between pristine Al 2 O 3 layers. In this work, we present a systematic operando Hard X-ray PhotoElectron Spectroscopy (HAXPES) study of the switching of such memristors, combined with complementary current-voltage and capacitance-voltage (C-V) measurements. We used a memristor stack of Al 2 O 3 /MgO atomic layers, with the MgO-containing oxide deposited on the bottom Al metal electrode and a pure Al 2 O 3 layer below the top Pd electrode. HAXPES analysis shows a substantial change in the chemical shift of the Aluminum oxide when switching between the ”OFF” and ”ON” states indicative of a redistribution of oxygen vacancies in the device active layer. Interestingly, subsequent switching to the OFF state shows hysteretic behavior indicating the retention of some oxygen vacancies in the top Al 2 O 3 layer. This vacancy retention can be correlated with the stochastic behavior of the switching voltage observed in these devices. C–V measurements show a clear frequency-dependent response in the OFF state, consistent with enhanced polarization and vacancy trapping at low frequencies.

47 OTHER INSTRUMENTATION↗
NASA NTRS1996

Prediction of In-Space Durability of Protected Polymers Based on Ground Laboratory Thermal Energy Atomic Oxygen

The probability of atomic oxygen reacting with polymeric materials is orders of magnitude lower at thermal energies (greater than O.1 eV) than at orbital impact energies (4.5 eV). As a result, absolute atomic oxygen fluxes at thermal energies must be orders of magnitude higher than orbital energy fluxes, to produce the same effective fluxes (or same oxidation rates) for polymers. These differences can cause highly pessimistic durability predictions for protected polymers and polymers which develop protective metal oxide surfaces as a result of oxidation if one does not make suitable calibrations. A comparison was conducted of undercut cavities below defect sites in protected polyimide Kapton samples flown on the Long Duration Exposure Facility (LDEF) with similar samples exposed in thermal energy oxygen plasma. The results of this comparison were used to quantify predicted material loss in space based on material loss in ground laboratory thermal energy plasma testing. A microindent hardness comparison of surface oxidation of a silicone flown on the Environmental Oxygen Interaction with Materials-III (EOIM-III) experiment with samples exposed in thermal energy plasmas was similarly used to calibrate the rate of oxidation of silicone in space relative to samples in thermal energy plasmas exposed to polyimide Kapton effective fluences.

Banks, Bruce A.↗
DOE OSTI2024

Stabilization of Catalytically Active Surface Defects on Ga-doped La–Sr–Mn Perovskites for Improved Solar Thermochemical Generation of Hydrogen

Solar thermochemical hydrogen (STCH) production from water splitting typically requires performing redox cycles at temperatures above 1200 °C to reduce and re-oxidize the bulk of a reversible material. Bulk processes such as oxygen vacancy formation and oxygen diffusion energies dictate the viability of a material for STCH. The surface plays an important role in the formation and destruction of vacancies and interacts with gas phase water and surface adsorbed species. These surface processes can lead to surface reconfigurations and even the formation of surface phases with stoichiometry and oxygen content very different from the bulk composition. Understanding in-situ the surface chemical state and its evolution under water splitting is important to design nonstoichiometric oxides capable of longer-lasting STCH generation at lower temperatures. In this work, we describe the water splitting active defect sites in LSM ((La 0.65 Sr 0.35 ) 0.95 MnO 3–δ ) and Ga-doped LSM ((La 0.6 Sr 0.4 ) 0.95 (Mn 0.8 Ga 0.2 )O 3–δ ) perovskites during Operando thermochemical water splitting conditions using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) experiments at 800 °C under steam. We show that sub-stoichiometric La +3 in the oxygen-vacancy rich surface at operating conditions can be used to correlate surface water splitting activity and the creation of surface hydroxide intermediates. The addition of Ga in LSM is shown to drastically stabilize the surface chemical composition by preventing Sr segregation and stabilizing catalytically active surface defects that promote the binding of adsorbed hydroxides. Here, we use Operando AP-XPS quantification of metastable surface hydroxide intermediates (La(OH) 3 ) to determine the amount of catalytically active surface sites in LSM (2.9%) and in LSMG (7.8–8.1%, depending on the bulk oxidation state).

08 HYDROGEN↗
DOE OSTI2022

2D Oxides Realized via Confinement Heteroepitaxy

Novel confinement techniques facilitate the formation of non-layered 2D materials. Here it is demonstrated that the formation and properties of 2D oxides (GaO x , InO x , SnO x ) at the epitaxial graphene (EG)/silicon carbide (SiC) interface is dependent on the EG buffer layer properties prior to element intercalation. Using 2D Ga, it is demonstrated that defects in the EG buffer layer lead to Ga transforming to GaO x with non-periodic oxygen in a crystalline Ga matrix via air oxidation at room temperature. However, crystalline monolayer GaO 2 and bilayer Ga 2 O 3 with ferroelectric wurtzite structure(FE-WZ') can then be formed via subsequent high-temperature O 2 annealing. Furthermore, the graphene/X/SiC (X = 2D Ga or Ga 2 O 3 ) junction is tunable from Ohmic to a Schottky or tunnel barrier depending on the interface species. Finally, using vertical transport measurements and electron energy loss spectroscopy analysis, the bandgap of 2D gallium oxide is identified as 6.6 ± 0.6 eV, significantly larger than that of bulk β-Ga 2 O 3 (≈4.8 eV), suggesting strong quantum confinement effects at the 2D limit. Furthermore, the study presented here is foundational for development of atomic-scale, vertical 2D/3D heterostructure for applications requiring short transit times, such as GHz and THz devices.

2D gallium oxides↗
DOE OSTI2025

Atomically Revealing Bulk Point Defect Dynamics in Hydrogen‐Driven γ‐Fe 2 O 3 → Fe 3 O 4 → FeO Transformation

Understanding how point defects in the bulk govern redox transformations is essential for advancing hydrogen-based metal production and designing high-performance oxide materials. This study reveals the atomic-scale mechanisms driving hydrogen-induced reduction of γ-Fe 2 O 3 to Fe 3 O 4 , focusing on how bulk vacancy dynamics dictate structural evolution and reaction kinetics. A key finding is the pronounced contrast in defect behavior between the two oxides: in γ-Fe 2 O 3 , intrinsic Fe vacancies promote oxygen vacancy clustering, destabilizing the local lattice and driving nanopore formation. In contrast, Fe 3 O 4 exhibits a higher oxygen vacancy formation energy and lacks intrinsic Fe vacancies, suppressing vacancy aggregation and maintaining a dense, pore-free structure. This divergence governs distinct reduction pathways—γ-Fe 2 O 3 undergoes an interface-reaction-limited transformation confined to the γ-Fe 2 O 3 /Fe 3 O 4 boundary, while Fe 3 O 4 supports a uniform increase in oxygen vacancy concentration, enabling bulk-phase reduction to lower-oxide FeO. Integrated in situ electron microscopy and density functional theory modeling uncover a vacancy-mediated mechanism, where synergistic cation-anion vacancy dynamics steer microstructure evolution and phase progression. These insights highlight the critical role of vacancy dynamics in controlling oxide reactivity and offer a pathway toward vacancy engineering to enhance reduction kinetics in hydrogen metallurgy and to tailor porosity, reactivity, and structural resilience in oxide-based catalysts and energy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Defective Sn-Zn perovskites through bio-directed routes for modulating CO 2 RR

Sn and Zn oxides can catalyze electrochemical CO 2 reduction reactions (CO 2 RR) to produce useful chemicals. Herein, we report on perovskite-type tin-zinc oxides (TZO) synthesized by a biomineralization approach under benign aqueous conditions. The resulting TZO catalysts are disordered and possess a high quantity of defects, which serve as highly reactive active sites in CO 2 RR. Selectively toward formate or CO is tunable toward the relative amounts of Sn and Zn and their associated O defects. In-situ X-ray absorption spectroscopy measurements reveal electronic and structural transformations consistent with oxygen vacancy formation at Sn-O-Zn bridges as a function of cathodic potential that strongly correlates to CO2RR selectivity. Further, Density functional theory (DFT) calculations demonstrate that introducing an oxygen vacancy in TZO influences drastically influences formate/CO selectivity, consistent with our in-situ XAS findings and catalytic performance. Overall, these findings demonstrate the potential of biomineralization to fabricate perovskite-type metal oxides for energy conversion reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Selenomethionine protects oxidative-stress-damaged bone-marrow-derived mesenchymal stem cells via an antioxidant effect and the PTEN/PI3K/AKT pathway

Highlights: • Oxidative stress stimuli by H{sub 2}O{sub 2} suppressed osteogenic differentiation of BMSCs. • Selenomethionine could alleviate osteogenic dysfunction of oxidative-stress-damaged BMSCs. • Selenomethionine rescued osteogenic ability partly through the modulation of the PTEN/PI3K/AKT pathway. Dental implant surgery is currently a routine therapy for the repair of missing dentition or dentition defects. Both clinical and basic research have elucidated that oxidative stress caused by the accumulation of reactive oxygen species (ROS) for various reasons impairs the process of osteointegration after dental implantation. Therefore, the osteogenic micro-environment must be ameliorated to decrease the damage caused by oxidative stress. Selenomethionine (SEMET) has been reported to play an important role in alleviating oxidative stress and accelerating cell viability and growth. However, it remains unclear whether it exerts protective effects on bone-marrow-derived mesenchymal stem cells (BMSCs) under oxidative stress. In this study, we explored the influence of selenomethionine on the viability and osteogenic differentiation of BMSCs under oxidative stress and the underlying mechanisms. Results showed that 1 μM selenomethionine was the optimum concentration for BMSCs under H{sub 2}O{sub 2} stimulation. H{sub 2}O{sub 2}-induced oxidative stress suppressed the viability and osteogenic differentiation of BMSCs, manifested by the increases in ROS production and cell apoptosis rates, and by the decrease of osteogenic differentiation-related markers. Notably, the aforementioned oxidative damage and osteogenic dysfunction induced by H{sub 2}O{sub 2} were rescued by selenomethionine. Furthermore, we found that the PTEN expression level was suppressed and its downstream PI3K/AKT pathway was activated by selenomethionine. However, when PTEN was stimulated, the PI3K/AKT pathway was down-regulated, and the protective effects of selenomethionine on BMSC osteogenic differentiation diminished, while the inhibition of PTEN up-regulated the protective effects of selenomethionine. Together, these results revealed that selenomethionine could attenuate H{sub 2}O{sub 2}-induced BMSC dysfunction through an antioxidant effect, modulated via the PTEN/PI3K/AKT pathway, suggesting that selenomethionine is a promising antioxidant candidate for reducing oxidative stress during the process of dental implant osteointegration.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Multi-scale investigation of heterogeneous swift heavy ion tracks in stannate pyrochlore

Er 2 Sn 2 O 7 pyrochlore was irradiated with swift heavy Au ions (2.2 GeV), and the induced structural modifications were systematically examined using complementary characterization techniques including transmission electron microscopy (TEM), X-ray diffraction (XRD), and neutron total scattering with pair distribution function (PDF) analysis. Each technique probes different aspects and length scales of the transformed material regions. TEM revealed a core–shell ion track structure—an amorphous core surrounded by a disordered, anion-deficient fluorite shell—which was confirmed by XRD. Neutron total scattering, with sensitivity to the oxygen sublattice, provided relative fractions of amorphous and disordered fluorite phases and confirmed the presence of a defective pyrochlore phase, which largely maintains its structural ordering but is clearly distinct from the pristine pyrochlore matrix. This defect-rich pyrochlore phase forms a halo extending radially beyond the well-characterized core–shell track morphology observed in electron micrographs. Despite their differing long-range periodicity, the short-range structures of the amorphous, disordered, and defective pyrochlore phases are all modeled well with a weberite-type configuration. Evolution of the phase fractions with increasing ion fluence was examined to ascertain the phase-to-phase pathways that occur during primary and secondary ion impact. Furthermore, this approach extends knowledge about the multi-scale response of stannate pyrochlores to swift heavy ion irradiation in the electronic energy loss regime and improves existing track-overlap models.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Metallene-related materials for electrocatalysis and energy conversion

As a member of graphene analogs, metallenes are a class of two-dimensional materials with atomic thickness and well-controlled surface atomic arrangement made of metals or alloys. When utilized as catalysts, metallenes exhibit distinctive physicochemical properties endowed from the under-coordinated metal atoms on the surface, making them highly competitive candidates for energy-related electrocatalysis and energy conversion systems. Significantly, their catalytic activity can be precisely tuned through the chemical modification of their surface and subsurface atoms for efficient catalyst engineering. Here, this minireview summarizes the recent progress in the synthesis and characterization of metallenes, together with their use as electrocatalysts toward reactions for energy conversion. In the Synthesis section, we pay particular attention to the strategies designed to tune their exposed facets, composition, and surface strain, as well as the porosity/cavity, defects, and crystallinity on the surface. We then discuss the electrocatalytic properties of metallenes in terms of oxygen reduction, hydrogen evolution, alcohol and acid oxidation, carbon dioxide reduction, and nitrogen reduction reaction, with a small extension regarding photocatalysis. At the end, we offer perspectives on the challenges and opportunities with respect to the synthesis, characterization, modeling, and application of metallenes.

36 MATERIALS SCIENCE↗
NASA NTRS1984

The effects of lithium counterdoping on radiation damage and annealing in n(+)p silicon solar cells

Boron-doped silicon n(+)p solar cells were counterdoped with lithium by ion implantation and the resultant n(+)p cells irradiated by 1 MeV electrons. Performance parameters were determined as a function of fluence and a deep level transient spectroscopy (DLTS) study was conducted. The lithium counterdoped cells exhibited significantly increased radiation resistance when compared to boron doped control cells. Isochronal annealing studies of cell performance indicate that significant annealing occurs at 100 C. Isochronal annealing of the deep level defects showed a correlation between a single defect at E sub v + 0.43 eV and the annealing behavior of short circuit current in the counterdoped cells. The annealing behavior was controlled by dissociation and recombination of this defect. The DLTS studies showed that counterdoping with lithium eliminated three deep level defects and resulted in three new defects. The increased radiation resistance of the counterdoped cells is due to the interaction of lithium with oxygen, single vacancies and divacancies. The lithium-oxygen interaction is the most effective in contributing to the increased radiation resistance.

Weinberg, I.↗