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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

High-Field One-Dimensional and Two-Dimensional 27Al Magic-Angle Spinning Nuclear Magnetic Resonance Study of ?-, d-, and ?-Al2O3 Dominated Aluminum Oxides: Toward Understanding the Al Sites in ?-Al2O3

Herein, a detailed analysis was carried out using high-field (19.9 T) 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) on three specially prepared aluminum oxide samples where the ?-, d-, and ?-Al2O3 phases are dominantly expressed through careful control of the synthesis conditions. Specifically, two-dimensional (2D) multiquantum (MQ) MAS 27Al was used to obtain high spectral resolution, which provided a guide for analyzing quantitative 1D 27Al NMR spectra. Six aluminum sites were resolved in the 2D MQ MAS NMR spectra, and seven aluminum sites were required to fit the 1D spectra. A set of octahedral and tetrahedral peaks with well-defined quadrupolar line shapes was observed in the ?-phase dominant sample and was unambiguously assigned to the ?-Al2O3 phase. The distinct line shapes related to the ?-Al2O3 phase provided an opportunity for effectively deconvoluting the more complex spectrum obtained from the d-Al2O3 dominant sample, allowing the peaks/quadrupolar parameters related to the d-Al2O3 phase to be extracted. The results show that the d-Al2O3 phase contains three distinct AlO sites and three distinct AlT sites. This detailed Al site structural information offers a powerful way of analyzing the most complex ?-Al2O3 spectrum. It is found that the ?-Al2O3 phase consists of Al sites with local structures similar to those found in the d-Al2O3 and ?-Al2O3 phases albeit with less ordering. Spin–lattice relaxation time measurement further confirms the disordering of the lattice. Collectively, this study uniquely assigns 27Al features in transition aluminas, offering a simplified method to quantify complex mixtures of aluminum sites in transition alumina samples.

Xu, Suochang↗
DOE OSTI2020

Reversible Oxidation Quantified by Optical Properties in Epitaxial Fe2CrO4+d Films on (001) MgAl2O4

We report on the structural and optical properties of Fe2CrO4+d epitaxial films grown by molecular beam epitaxy on MgAl2O4 (001) as a function of ?. The average Fe valence can be correlated with the out-of-plane lattice parameter and the extent of light absorption in the infrared spectral region. Over-oxidized films (0 < d < 0.5) exhibit reduced lattice parameters and suppressed infrared absorption. We discuss the behavior of a novel infrared transition at ~0.6 eV in stoichiometric Fe2CrO4 films deposited on MgAl2O4 (MAO) at or above 400 °C. This research provides new insight into the atomic structure, optical processes, oxidation states, electronic structure, and application potentials of Fe2CrO4+d.

ellipsometry, Epitaxy, thin film, oxidation, reduc↗
DOE OSTI2019

Dynamic Interplay between Copper Tetramers and Iron Oxide Boosting CO2 Conversion to Methanol and Hydrocarbons under Mild Conditions.

Atomically precise subnanometer catalysts are of significant interest because of their remarkable efficiency in a variety of catalytic reactions. However, the dynamic changes of active sites under reaction conditions, in particular, the transition of cluster-oxide interface structure have not yet been well-elucidated, lacking in situ measurements. By using multiple state-of-the-art in situ characterizations, here we show a dynamic interplay between copper tetramers and iron oxides in a single-size Cu-4/Fe2O3 catalyst, yielding an enrichment of surface Cu-4-Fe2+ species under reaction conditions that boosts CO2 hydrogenation at near-atmospheric pressures. During reaction, Cu-4 clusters facilitate the reduction of Fe2O3 producing surface-rich Fe2+ species in the proximate sites. The as-formed Fe2+ species in return promotes CO2 activation and transformation over Cu4 cluster, resulting in strikingly high methanol synthesis at low temperatures and C-1/C-3 hydrocarbon production in a high-temperature regime. The discovery of highly active Cu-4-Fe2+ sites thus provides new insights for the atomic-level design of copper catalyst toward high-efficiency CO2 conversion under mild conditions.

CO2 conversion↗
DOE OSTI2017

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework

The catalyzed conversion of shale gas-derived light hydrocarbons, e.g. methane to methanol, for further application as automotive fuels and/or bulk chemicals is especially attractive in light of improved methods of hydrocarbon extraction. MOF based catalysts have previously been demonstrated to be active for a range of catalytic reactions. In this work we used Cu-NU1000 as a methane-to-methanol oxidation catalyst. In addition to product studies, in-situ X-ray Absorption Spectroscopic (XAS) experiments are performed under catalytic conditions in order to follow the modification of the Cu-species and directly probe the structure/activity properties of the Cu-NU1000 system. The insights reported herein serve as a first look at metal-organic framework materials as catalysts for methane oxidation and be the basis for development of the subsequent generations of materials.

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

Optimizing conditions for utilization of an H 2 oxidation catalyst with outer coordination sphere functionalities

[Ni(PCy2NArginine2)2]2+ ( CyArg ) or [Ni(PCy2NBenzyl2)2]2+ ( CyBn ) were evaluated for H 2 oxidation as a function of temperature, pressure, and solvent. 70 °C and 100 atm H 2 result in a TOF of 1.1 × 106 s -1 and an overpotential of 240 mV for CyArg in water. In methanol the rates were 280 s -1 for CyArg and 80 s -1 for CyBn , demonstrating the importance of water and the outer coordination sphere ( OCS ).

bio-inspired↗
DOE OSTI2019

Atomic Layer Deposition of Vanadium Oxide to Reduce Parasitic Absorption and Improve Stability in n-i-p Perovskite Solar Cells for Tandems

Two critical issues associated with semi-transparent, n-i-p perovskite solar cells for 2-terminal tandem devices are parasitic absorption and long-term instability associated with the widely used spiro-OMeTAD and MoOx hole transport and buffer layers, respectively. In this work, we present an alternative hole contact bilayer that consists of a 30 nm undoped layer of spiro-TTB in conjunction with 9 nm of air-stable vanadium oxide (VOx) deposited via atomic layer deposition. The low absorption of UV and visible light in this bilayer results in the fabrication of a semi-transparent perovskite cell with 18.9 mA cm-2 of photocurrent, a 14% increase compared to the 16.6 mA cm-2 generated in a control device with 150 nm of doped spiro-OMeTAD. The ALD VOx buffer layer shows promise as a stable alternative to MoOx; an unencapsulated Cs0.17FA0.83Pb(Br0.17I0.83)3 device with ALD VOx and ITO as the top contact maintains its efficiency following 1000 hours at 85 degrees C in a N2 environment. Lastly, we use transfer matrix modeling of the optimized perovskite stack to predict its optical performance in a monolithic tandem cell with heterojunction silicon.

14 SOLAR ENERGY↗
DOE OSTI2014

Effect of nitrogen doping on wetting and photoactive properties of laser processed zinc oxide-graphene oxide nanocomposite layers

Zinc oxide-graphene oxide nanocomposite layers were submitted to laser irradiation in air or controlled nitrogen atmosphere using a frequency quadrupled Nd:YAG (λ = 266 nm, τ{sub FWHM} ≅ 3 ns, ν = 10 Hz) laser source. The experiments were performed in air at atmospheric pressure or in nitrogen at a pressure of 2 × 10{sup 4} Pa. The effect of the irradiation conditions, incident laser fluence value, and number of subsequent laser pulses on the surface morphology of the composite material was systematically investigated. The obtained results reveal that nitrogen incorporation improves significantly the wetting and photoactive properties of the laser processed layers. The kinetics of water contact angle variation when the samples are submitted to laser irradiation in nitrogen are faster than that of the samples irradiated in air, the surfaces becoming super-hydrophilic under UV light irradiation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Self-formed copper oxide contact interlayer for high-performance oxide thin film transistors

Oxide thin film transistor employing copper source/drain electrodes shows a small turn on voltage and reduced hysteresis. Cross-sectional high-resolution transmission electron microscopy image confirmed the formation of ∼4 nm CuO{sub x} related interlayer. The lower bond-dissociation energy of Cu-O compared to Si-O and In-O suggests that the interlayer was formed by adsorbing oxygen molecules from surrounding environment instead of getting oxygen atoms from the semiconductor film. The formation of CuO{sub x} interlayer acting as an acceptor could suppress the carrier concentration in the transistor channel, which would be utilized to control the turn on voltage shifts in oxide thin film transistors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105)

We report dispersion-corrected density functional theoretical calculations of the unreacted equation of state (EOS) of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105) under hydrostatic compression of up to 45 GPa. Convergence tests for k-points sampling in the Brillouin zone show that a 3 × 1 × 2 mesh is required to reproduce the X-ray crystal structure at ambient conditions, and we confirm our finding with a separate supercell calculation. Our high-pressure EOS yields a bulk modulus of 19.2 GPa, and indicates a tendency towards anisotropic compression along the b lattice vector due to molecular orientations within the lattice. We find that the electronic energy band gap decreases from a semiconductor type of 1.3 eV at 0 GPa to quasi-metallic type of 0.6 eV at 45 GPa. The extensive intermolecular hydrogen bonds involving the oxide (–NO) and dioxide (–NO{sub 2}) interactions with the amine (–NH{sub 2}) group showed enhanced interactions with increasing pressure that should be discernible in the mid IR spectral region. We do not find evidence for structural phase transitions or chemically induced transformations within the pressure range of our study. The gas phase heat of formation is calculated at the G4 level of theory to be 22.48 kcal/mol, while we obtain 25.92 kcal/mol using the ccCA-PS3 method. Density functional theory calculations of the crystal and the gas phases provided an estimate for the heat of sublimation of 32.4 kcal/mol. We thus determine the room-temperature solid heat of formation of LLM-105 to be −9.9 or −6.5 kcal/mol based on the G4 or ccCA-PS3 methods, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

High quality HfO{sub 2}/p-GaSb(001) metal-oxide-semiconductor capacitors with 0.8 nm equivalent oxide thickness

We investigate in-situ cleaning of GaSb surfaces and its effect on the electrical performance of p-type GaSb metal-oxide-semiconductor capacitor (MOSCAP) using a remote hydrogen plasma. Ultrathin HfO{sub 2} films grown by atomic layer deposition were used as a high permittivity gate dielectric. Compared to conventional ex-situ chemical cleaning methods, the in-situ GaSb surface treatment resulted in a drastic improvement in the impedance characteristics of the MOSCAPs, directly evidencing a much lower interface trap density and enhanced Fermi level movement efficiency. We demonstrate that by using a combination of ex-situ and in-situ surface cleaning steps, aggressively scaled HfO{sub 2}/p-GaSb MOSCAP structures with a low equivalent oxide thickness of 0.8 nm and efficient gate modulation of the surface potential are achieved, allowing to push the Fermi level far away from the valence band edge high up into the band gap of GaSb.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides

Hydrophobic surfaces that are robust can have widespread applications in drop-wise condensation, anti-corrosion, and anti-icing. Recently, it was shown that the class of ceramics comprising the lanthanide series rare-earth oxides (REOs) is intrinsically hydrophobic. The unique electronic structure of the rare-earth metal atom inhibits hydrogen bonding with interfacial water molecules resulting in a hydrophobic hydration structure where the surface oxygen atoms are the only hydrogen bonding sites. Hence, the presence of excess surface oxygen can lead to increased hydrogen bonding and thereby reduce hydrophobicity of REOs. Herein, we demonstrate how surface stoichiometry and surface relaxations can impact wetting properties of REOs. Using X-ray Photoelectron Spectroscopy and wetting measurements, we show that freshly sputtered ceria is hydrophilic due to excess surface oxygen (shown to have an O/Ce ratio of ∼3 and a water contact angle of ∼15°), which when relaxed in a clean, ultra-high vacuum environment isolated from airborne contaminants reaches close to stoichiometric O/Ce ratio (∼2.2) and becomes hydrophobic (contact angle of ∼104°). Further, we show that airborne hydrocarbon contaminants do not exclusively impact the wetting properties of REOs, and that relaxed REOs are intrinsically hydrophobic. This study provides insight into the role of surface relaxation on the wettability of REOs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Analyzing the kinetic response of tin oxide-carbon and tin oxide-CNT composites gas sensors for alcohols detection

Tin oxide nanoparticles are synthesized using solution combustion technique and tin oxide – carbon composite thick films are fabricated with amorphous carbon as well as carbon nanotubes (CNTs). The x-ray diffraction, Raman spectroscopy and porosity measurements show that the as-synthesized nanoparticles are having rutile phase with average crystallite size ∼7 nm and ∼95 m{sup 2}/g surface area. The difference between morphologies of the carbon doped and CNT doped SnO{sub 2} thick films, are characterized using scanning electron microscopy and transmission electron microscopy. The adsorption-desorption kinetics and transient response curves are analyzed using Langmuir isotherm curve fittings and modeled using power law of semiconductor gas sensors.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Novel comparison of microscopy and diffraction techniques on the structure of iron oxide nanoparticle monolayers transferred by Langmuir-Schaefer method

Iron oxide nanoparticles undergo self-assembly into well-ordered monolayer films of macroscopic size at the air-water interface. This self-assembly process is the result of the van der Waals forces between the constituent particles. For roughly spherical particles, this monolayer is a 2D hexagonal close packed lattice. With Grazing Incidence X-Ray Diffraction (GID), one can obtain global statistical information about the film’s spacing and correlation length. Herein, we demonstrate that comparable structural information can be obtained by a novel Fourier transform analysis method applied to Scanning Electron Microscopy (SEM) images taken of the film after it has been transferred to a silicon substrate. This consists of using numerical methods to isolate the lattice structure of the monolayer in the SEM image to which a 2D discrete Fourier Transform is applied and the result integrated. This results in Bragg peak information akin to that obtained from GID, whose structure shows the same hexagonal close packed lattice with similar spacing and of greater peak contrast. Furthermore, this analysis technique may prove to be a suitable alternative or compliment to GID for many applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Research Update: Towards designed functionalities in oxide-based electronic materials

One of the grand challenges facing materials-by-design approaches for complex oxide deployment in electronic devices is how to balance transformative first-principles based predictions with experimental feasibility. Here, we briefly review the functionality-driven approach (inverse design) for materials discovery, encapsulated in three modalities for materials discovery (m{sup 3}D) that integrate experimental feedback. We compare it to both traditional theoretical and high-throughput database-directed approaches aimed at advancing oxide-based materials into technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The high pressure structure and equation of state of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) up to 20 GPa: X-ray diffraction measurements and first principles molecular dynamics simulations

Recent theoretical studies of 2,6-diamino-3,5-dinitropyrazine-1-oxide (C{sub 4}H{sub 4}N{sub 6}O{sub 5} Lawrence Livermore Molecule No. 105, LLM-105) report unreacted high pressure equations of state that include several structural phase transitions, between 8 and 50 GPa, while one published experimental study reports equation of state (EOS) data up to a pressure of 6 GPa with no observed transition. Here we report the results of a synchrotron-based X-ray diffraction study and also ambient temperature isobaric-isothermal atomistic molecular dynamics simulations of LLM-105 up to 20 GPa. We find that the ambient pressure phase remains stable up to 20 GPa; there is no indication of a pressure induced phase transition. We do find a prominent decrease in b-axis compressibility starting at approximately 13 GPa and attribute the stiffening to a critical length where inter-sheet distance becomes similar to the intermolecular distance within individual sheets. The ambient temperature isothermal equation of state was determined through refinements of measured X-ray diffraction patterns. The pressure-volume data were fit using various EOS models to yield bulk moduli with corresponding pressure derivatives. We find very good agreement between the experimental and theoretically derived EOS.

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

Gd-doped BaSnO{sub 3}: A transparent conducting oxide with localized magnetic moments

We have synthesized transparent, conducting, paramagnetic stannate thin films via rare-earth doping of BaSnO{sub 3}. Gd{sup 3+} (4f{sup 7}) substitution on the Ba{sup 2+} site results in optical transparency in the visible regime, low resistivities, and high electron mobilities, along with a significant magnetic moment. Pulsed laser deposition was used to stabilize epitaxial Ba{sub 0.96}Gd{sub 0.04}SnO{sub 3} thin films on (001) SrTiO{sub 3} substrates, and compared with Ba{sub 0.96}La{sub 0.04}SnO{sub 3} and undoped BaSnO{sub 3} thin films. Gd as well as La doping schemes result in electron mobilities at room temperature that exceed those of conventional complex oxides, with values as high as 60 cm{sup 2}/V·s (n = 2.5 × 10{sup 20 }cm{sup −3}) and 30 cm{sup 2}/V·s (n = 1 × 10{sup 20 }cm{sup −3}) for La and Gd doping, respectively. The resistivity shows little temperature dependence across a broad temperature range, indicating that in both types of films the transport is not dominated by phonon scattering. Gd-doped BaSnO{sub 3} films have a strong magnetic moment of ∼7 μ{sub B}/Gd ion. Such an optically transparent conductor with localized magnetic moments may unlock opportunities for multifunctional devices in the design of next-generation displays and photovoltaics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗