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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 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Epitaxial growth of oriented CoO films by radio-frequency sputtering deposition

Rock-salt CoO is a p-type semiconductor and its Neel temperature is close to room temperature. CoO-based compounds are known as promising systems for renewable energy harvest with high efficiency. CoO with catalytic and exchange bias properties can be widely used for industrial applications. In this paper, we report high-quality stable CoO(111) and (100) films epitaxially grown on c-cut (0001) and r-cut ($10\bar1$2) alpha-Al 2 O 3 substrates, respectively, using radio-frequency sputtering deposition. X-ray diffraction (XRD) measurements revealed that the CoO films had a rock-salt structure (Fm3m) with lattice constants of 4.2477 Å and 4.2617 Å for film grown on (0001) and ($10\bar1$2) α-Al 2 O 3 substrates, respectively. CoO films with the best crystal quality were grown at a substrate temperature of similar to ~700°C. XRD measurements of CoO(111) films indicated a lack of structural residual strain, whereas CoO(100) films had substantial amounts of structural strain. X-ray reflectivity (XRR) and transmission electron microscopy measurements showed neither oxygen vacancy nor defects in both CoO(111) and (100) films. Further, XRR revealed that the mean electron density of the CoO films was nearly identical to a pure CoO and that the films were considerably stable under the atmosphere.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structure and Function of BorB, the Type II Thioesterase from the Borrelidin Biosynthetic Gene Cluster

α/β hydrolases make up a large and diverse protein superfamily. In natural product biosynthesis, cis-acting thioesterase α/β hydrolases can terminate biosynthetic assembly lines and release products by hydrolyzing or cyclizing the biosynthetic intermediate. Thioesterases can also act in trans, removing aberrant intermediates and restarting stalled biosynthesis. Knockout of this "editing" function leads to reduced product titers. The borrelidin biosynthetic gene cluster from Streptomyces parvulus Tü4055 contains a hitherto uncharacterized stand-alone thioesterase, borB. In this work, we demonstrate that purified BorB cleaves acyl substrates with a preference for propionate, which supports the hypothesis that it is also an editing thioesterase. The crystal structure of BorB shows a wedgelike hydrophobic substrate binding crevice that limits substrate length. To investigate the structure-function relationship, we made chimeric BorB variants using loop regions from characterized homologues with different specificities. BorB chimeras slightly reduced activity, arguing that the modified region is a not major determinant of substrate preference. Overall, the structure-function relationships described here contribute to the process of elimination for understanding thioesterase specificity and, ultimately, engineering and applying trans-acting thioesterases in biosynthetic assembly lines.

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

Altering Linear Scaling Relationships on Metal Catalysts via Ligand–Adsorbate Hydrogen Bonding

Linear scaling relationships for adsorption energies of related molecules provide a simple tool for the prediction of catalytic properties and also reveal inherent constraints in heterogeneous catalyst design. In an effort to predict materials that preferentially stabilize intermediates capable of forming hydrogen bonds (H-bonds) and thus reduce these constraints, scaling relations for thiolate-coated fcc (111) surfaces were developed. Here, we demonstrate how ligand–adsorbate H-bonds lead to the stabilization of certain adsorbates and how this affects the linear scaling of adsorption energies for similarly bound intermediates. For H-bonds that occur remote from the surface, ligand–adsorbate H-bond strength is independent of metal composition and instead depends only on the acidities of the H-bond-forming functional groups. As the distance of H-bond-accepting groups from the surface decreases and interactions with the metal strengthen, the effect of surface composition on H-bond strength increases while additional factors, such as conformational changes and steric hinderance, can offset the stabilizing effect of the ligands. In this work, these competing factors may influence both the slope and y-intercept of adsorption strength scaling. These findings aid the rational design of enhanced catalytic materials by enabling the screening of ligand- or spectator-modified materials that do not conform to the linear scaling relations of bare metal surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Relationships between Water’s Structure and Solute Affinity at Polypeptoid Brush Surfaces

Excellent antifouling surfaces are generally thought to create a tightly bound layer of water that resists solute adsorption, and highly hydrophilic surfaces such as those with zwitterionic functionalities are of significant current interest as antifoulant strategies. Furthermore, despite significant proofs-of-concept, we still lack a fundamental understanding of how the nanoscopic structure of this hydration layer translates to reduced fouling, how surface chemistry can be tuned to achieve antifouling through hydration water, and why, in particular, zwitterionic surfaces seem so promising. Here, we use molecular dynamics simulations and free energy calculations to investigate the molecular relationships among surface chemistry, hydration water structure, and surface–solute affinity across a variety of surface-decorated chemistries. Specifically, we consider polypeptoid-decorated surfaces that display well-known experimental antifouling capabilities and that can be synthesized sequence specifically, with precise backbone positioning of, e.g., charged groups. Through simulations, we calculate the affinities of a range of small solutes to polypeptoid brush surfaces of varied side-chain chemistries. We then demonstrate that measures of the structure of surface hydration water in response to a particular surface chemistry signal solute–surface affinity; specifically, we find that zwitterionic chemistries produce solute–surface repulsion through highly coordinated hydration water while suppressing tetrahedral structuring around the solute, in contrast to uncharged surfaces that show solute–surface affinity. Based on the relationship of this structural perturbation to the affinity of small-molecule solutes, we propose a molecular mechanism by which zwitterionic surface chemistries enhance solute repulsion, with broader implications for the design of antifouling surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Exploring Sources of Surface Bias in HRRR Using New York State Mesonet

In recent years, there has been increasing demand for applications of short-term forecasting of renewable energy potential and assessments of the likelihood of extreme weather events using the High-Resolution Rapid Refresh (HRRR) model. Examining the biases in the newest version of HRRR is necessary to promote further model development. Using data from one of the most comprehensive and dense monitoring networks, New York State Mesonet (NYSM), we evaluate the HRRR version 3 meteorological fields for an entire year. In this work, the land-atmosphere-cloud coupling system is evaluated as an integrated whole. We investigate the physical processes influencing the soil hydrological balance and the thermodynamic interactions, from surface fluxes up to the level of boundary layer convection from both temporal (seasonal and diurnal) and spatial perspectives. Results show that the model 2 m temperature and humidity biases are seasonally dependent, with warm and dry bias present during the warm season, and an extreme nocturnal cold bias in winter. The summer warm bias includes both a land-surface-induced bias and a cloud-induced bias. Inaccurate representation of energy partition and soil hydrological process across different land use types as well as a hydrological bias in describing spring snowmelt are identified as the main source of the land-surface-induced bias. A feedback loop linking cloud presence, flux changes, and temperature contributes to the cloud-induced bias. The positive solar radiation bias increases from clear sky to overcast sky conditions. The most significant bias occurs during overcast and thick cloud conditions associated with frontal passage and thunderstorms.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Long‐Term Observations of Turbulence Vertical Velocity Spectra in a Convective Mixed Layer: Dependence on Land‐Surface Forcing in the U.S. Southern Great Plains

Doppler lidar vertical velocity retrievals were analyzed for the scale and structure of mixed-layer turbulence over a 7-year period, on fair-weather warm season days (442 cases) in the U.S. Southern Great Plains. Based on the hypothesized influence of land-surface forcing and updraft size on convective boundary layer clouds, a spectral analysis was performed to quantify effects of surface forcing (surface buoyancy flux, friction velocity, and evaporative fraction) on turbulence scale. Significant (order-of-magnitude) variations in spectral density were found in the energy-production subrange and mesoscale regimes. Integral scale decreased with increasing buoyancy flux (and Monin-Obukhov stability parameter), while spectral density in the energy-production subrange increased, implying a transition to buoyancy-driven cellular structures with narrower updrafts. The influence of stability parameter was limited to the neutral to convective transition, and could not explain the wide variation in spectral density in the mesoscale regime. However, high friction velocity (u* > 0.5 m s –1 ) was associated with larger integral scale (updraft width), and a greater portion of spectral density in the mesoscale regime. Lidar profiles and radar reflectivity for individual cases revealed evidence of roll and wave-like structures contributing to mesoscale variability on high friction velocity days, suggesting shear instabilities on days with wetter land surface conditions and smaller buoyancy flux. The role of friction velocity emphasizes the multivariate nature of surface influences on turbulence, and implies that variance-based turbulence closures may not be adequate for capturing effects of surface forcing on updraft size.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Emergent electric field control of phase transformation in oxide superlattices

Electric fields can transform materials with respect to their structure and properties, enabling various applications ranging from batteries to spintronics. Recently electrolytic gating, which can generate large electric fields and voltage-driven ion transfer, has been identified as a powerful means to achieve electric-field-controlled phase transformations. The class of transition metal oxides provide many potential candidates that present a strong response under electrolytic gating. However, very few show a reversible structural transformation at room-temperature. Here, we report the realization of a digitally synthesized transition metal oxide that shows a reversible, electric-field-controlled transformation between distinct crystalline phases at room-temperature. In superlattices comprised of alternating one-unit-cell of SrIrO 3 and La 0.2 Sr 0.8 MnO 3 , we find a reversible phase transformation with a 7% lattice change and dramatic modulation in chemical, electronic, magnetic and optical properties, mediated by the reversible transfer of oxygen and hydrogen ions. Strikingly, this phase transformation is absent in the constituent oxides, solid solutions and larger period superlattices. Our findings open up this class of materials for voltage-controlled functionality.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evolution of spin excitations from bulk to monolayer FeSe

Abstract In ultrathin films of FeSe grown on SrTiO 3 (FeSe/STO), the superconducting transition temperature T c is increased by almost an order of magnitude, raising questions on the pairing mechanism. As in other superconductors, antiferromagnetic spin fluctuations have been proposed to mediate SC making it essential to study the evolution of the spin dynamics of FeSe from the bulk to the ultrathin limit. Here, we investigate the spin excitations in bulk and monolayer FeSe/STO using resonant inelastic x-ray scattering (RIXS) and quantum Monte Carlo (QMC) calculations. Despite the absence of long-range magnetic order, bulk FeSe displays dispersive magnetic excitations reminiscent of other Fe-pnictides. Conversely, the spin excitations in FeSe/STO are gapped, dispersionless, and significantly hardened relative to its bulk counterpart. By comparing our RIXS results with simulations of a bilayer Hubbard model, we connect the evolution of the spin excitations to the Fermiology of the two systems revealing a remarkable reconfiguration of spin excitations in FeSe/STO, essential to understand the role of spin fluctuations in the pairing mechanism.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Ultra-thin lithium aluminate spinel ferrite films with perpendicular magnetic anisotropy and low damping

Ultra-thin films of low damping ferromagnetic insulators with perpendicular magnetic anisotropy have been identified as critical to advancing spin-based electronics by significantly reducing the threshold for current-induced magnetization switching while enabling new types of hybrid structures or devices. Here, we have developed a new class of ultra-thin spinel structure Li 0.5 Al 1.0 Fe 1.5 O 4 (LAFO) films on MgGa 2 O 4 (MGO) substrates with: 1) perpendicular magnetic anisotropy; 2) low magnetic damping and 3) the absence of degraded or magnetic dead layers. These films have been integrated with epitaxial Pt spin source layers to demonstrate record low magnetization switching currents and high spin-orbit torque efficiencies. These LAFO films on MGO thus combine all of the desirable properties of ferromagnetic insulators with perpendicular magnetic anisotropy, opening new possibilities for spin based electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Magnetic excitations in strained infinite-layer nickelate PrNiO 2 films

Strongly correlated materials respond sensitively to external perturbations such as strain, pressure, and doping. In the recently discovered superconducting infinite-layer nickelates, the superconducting transition temperature can be enhanced via only ~ 1% compressive strain-tuning with the root of such enhancement still being elusive. Using resonant inelastic x-ray scattering (RIXS), we investigate the magnetic excitations in infinite-layer PrNiO 2 thin films grown on two different substrates, namely SrTiO 3 (STO) and (LaAlO 3 ) 0.3 (Sr 2 TaAlO 6 ) 0.7 (LSAT) enforcing different strain on the nickelates films. The magnon bandwidth of PrNiO 2 shows only marginal response to strain-tuning, in sharp contrast to the enhancement of the superconducting transition temperature T c in the doped superconducting samples. These results suggest the bandwidth of spin excitations of the parent compounds is similar under strain while T c in the doped ones is not, and thus provide important empirics for the understanding of superconductivity in infinite-layer nickelates.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Grand canonically optimized grain boundary phases in hexagonal close-packed titanium

Grain boundaries (GBs) profoundly influence the properties and performance of materials, emphasizing the importance of understanding the GB structure and phase behavior. As recent computational studies have demonstrated the existence of multiple GB phases associated with varying the atomic density at the interface, we introduce a validated, open-source GRand canonical Interface Predictor (GRIP) tool that automates high-throughput, grand canonical optimization of GB structures. While previous studies of GB phases have almost exclusively focused on cubic systems, we demonstrate the utility of GRIP in an application to hexagonal close-packed titanium. We perform a systematic high-throughput exploration of tilt GBs in titanium and discover previously unreported structures and phase transitions. In low-angle boundaries, we demonstrate a coupling between point defect absorption and the change in the GB dislocation network topology due to GB phase transformations, which has important implications for the accommodation of radiation-induced defects.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Switchable planar chirality and spin texture in highly ordered ferroelectric hybrid perovskite domains

Chiral organic-inorganic hybrid perovskites offer a promising platform for developing non-linear chiro-optical applications and chiral-induced spin selectivity. Here, we show that achiral hybrid perovskites that have highly ordered ferroelectric domains with orthogonal polarization exhibit planar chirality, as manifested by second harmonic generation with strong circular dichroism. Interestingly, the handedness of the second harmonic generation circular dichroism response can be alternatingly switched between orthogonally polarized domains and domain walls. To correlate the origin of planar chirality in these domains, atom-resolved atomic force microscopy is used to reveal distinct arrangements of atomic rows in these ferroelectric crystals that indicate planar symmetry breaking. Remarkably, a large SHG anisotropy factor of 0.41 is measured at the domain wall. Additionally, spatially resolved two-photon photoluminescence excitation measurement provide evidence of larger Rashba spin-splitting in these chiral ferroelectric domains compared to domain-free areas. Our discoveries of domain-dependent planar chirality and spin texture hold great promise for advancement of domain-specific chiro-optical applications.

36 MATERIALS SCIENCE↗