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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Flexible transparent conducting electrodes unexpectedly influence MAPbI 3 film morphology and perovskite solar cell performance

Fabricating perovskite solar cells (PSCs) on plastic substrates will enable cost-effective manufacturing of lightweight and portable energy systems. Here, we study the influence of flexible transparent conductive electrodes (TCEs) on the methylammonium lead iodide (MAPbI3) film morphology and PSC performance. Three types of TCEs on polyethylene terephthalate (PET) are compared: a custom-made AgNWs/indium zinc oxide hybrid TCE and two commercial substrates with indium tin oxide (ITO) or metal/insulator/metal (MIM) as the TCE. Using the same p-i-n architecture and hole transport layer (HTL), we find that PSCs fabricated on the hybrid TCE show better performance and stability compared to those made on commercial TCEs. The PSC performance enhancement is attributed to the superior structural and optical properties of MAPbI3 film deposited on the hybrid TCE, which is explained by the surface energy difference of the HTL. While it is anticipated that solar cell performance can be affected by TCEs’ transmittance and sheet resistance as they determine light absorption and carrier transport, respectively, our finding of TCE influencing the morphology and crystallinity of MAPbI3 film, and hence PSC performance, is unexpected.

14 SOLAR ENERGY↗
DOE OSTI2023

Solution epitaxy of polarization-gradient ferroelectric oxide films with colossal photovoltaic current

Solution growth of single-crystal ferroelectric oxide films has long been pursued for the low-cost development of high-performance electronic and optoelectronic devices. However, the established principles of vapor-phase epitaxy cannot be directly applied to solution epitaxy, as the interactions between the substrates and the grown materials in solution are quite different. Here, we report the successful epitaxy of single-domain ferroelectric oxide films on Nb-doped SrTiO 3 single-crystal substrates by solution reaction at a low temperature of ~200 o C. The epitaxy is mainly driven by an electronic polarization screening effect at the interface between the substrates and the as-grown ferroelectric oxide films, which is realized by the electrons from the doped substrates. Atomic-level characterization reveals a nontrivial polarization gradient throughout the films in a long range up to ~500 nm because of a possible structural transition from the monoclinic phase to the tetragonal phase. This polarization gradient generates an extremely high photovoltaic short-circuit current density of ~2.153 mA/cm 2 and open-circuit voltage of ~1.15 V under 375 nm light illumination with power intensity of 500 mW/cm 2 , corresponding to the highest photoresponsivity of ~4.306×10 -3 A/W among all known ferroelectrics. Our results establish a general low-temperature solution route to produce single-crystal gradient films of ferroelectric oxides and thus open the avenue for their broad applications in self-powered photo-detectors, photovoltaic and optoelectronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Domain nucleation across the metal-insulator transition of self-strained V 2 O 3 films

Bulk V 2 O 3 features concomitant metal-insulator (MIT) and structural (SPT) phase transitions at T C ~ 160 K. In thin films, where the substrate clamping can impose geometrical restrictions on the SPT, the epitaxial relation between the V 2 O 3 film and substrate can have a profound effect on the MIT. Here we present a detailed characterization of domain nucleation and growth across the MIT in (001)-oriented V 2 O 3 films grown on sapphire. By combining scanning electron transmission microscopy (STEM) and photoelectron emission microscopy (PEEM), we imaged the MIT with planar and vertical resolution. We observed that upon cooling, insulating domains nucleate at the top of the film, where strain is lowest, and expand downwards and laterally. This growth is arrested at a critical thickness of 50 nm from the substrate interface, leaving a persistent bottom metallic layer. As a result, the MIT cannot take place in the interior of films below this critical thickness. However, PEEM measurements revealed that insulating domains can still form on a very thin superficial layer at the top interface. Our results demonstrate the intricate spatial complexity of the MIT in clamped V 2 O 3 , especially the strain-induced large variations along the c axis. Finally, engineering the thickness-dependent MIT can provide an unconventional way to build out-of-plane geometry devices by using the persistent bottom metal layer as a native electrode.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Insights from designing an artificial cascade catalysis system using principles from substrate channeling in enzymes

Generalizing the key requirements of highly-selective, multi-step chemical conversions involving spatially separated reaction centers remains one of the grand challenges of chemistry. Much work towards this effort has focused on decomposing multi-step conversions into their constituent reactions, whose intermediates are successively upgraded in a chemical cascade via diffusion from center to center. This approach for synthesizing more complex molecules takes its cues from biochemical networks, where near-unit conversion of even complex carbohydrates is achieved by upgrading chemical precursors via enzymatic cascades. In this computational study we examine a simple cascade involving coupled Ag and Cu catalysts that sequentially converts CO2 to CO and then CO2 and CO to reduced products, generically named CO2Product and COProduct. The system architecture is inspired by the phenomenon of biological substrate channeling, and components are examined to evaluate their effects on conversion efficiency in the cascade. Aside from a substrate channel linking two reaction centers, we find efficient cascades must also incorporate directional substrate diffusion, compartmentalization of the reaction centers, and proper timing of substrate arrival at the active center. We make explicit linkages between these requirements and chemical conversion in known biological systems, revealing additional control elements that could be incorporated.

CO 2 reduction↗
DOE OSTI2024

Co-deposition of bismuth-nitrogen films on MgO (001) by molecular beam epitaxy

Here, we attempted to grow a thin film of BiN by co-deposition of bismuth and nitrogen on rock-salt structure MgO (001) substrates. Furthermore, we studied the effect of variation of the growth temperature and the nitrogen to bismuth flux ratios on sample growth. For the samples grown and conditions used, we do not find strong evidence for the formation of a bulk Bi-N alloy. Even for very high nitrogen to bismuth flux ratio, we observed only bismuth and no nitrogen using bulk Rutherford back-scattering spectroscopy measurements, and only 1%–2% nitrogen was seen through surface Auger electron spectroscopy measurements. The in-plane lattice measurements show that the resulting Bi (110) samples are strained, which is presumably caused by lattice mismatch between the sample and the substrate when grown without any buffer layer. The use of a high-temperature buffer layer helps to release strain in the sample but only along one axis. Measurements of the atomic layer spacing using x-ray diffraction and also scanning tunneling microscopy confirm the Bi (110) thin film sample structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Polyphenol rewiring of the microbiome reduces methane emissions

Methane mitigation is regarded as a critical strategy to combat the scale of global warming. Currently, ~40% of methane emissions originate from microbial sources, which is causing strategies to suppress methanogens—either through direct toxic effects or by diverting their substrates and energy—to gain traction. Problematically, current microbial methane mitigation knowledge lacks detailed microbiome-centered insights, limiting translation across conditions and ecosystems. Here we utilize genome-resolved metatranscriptomes and metabolomes to assess the impact of a proposed methane inhibitor, catechin, on greenhouse gas emissions for high-methane-emitting peatlands. In microcosms, catechin drastically reduced methane emissions by 72%–84% compared to controls. Longitudinal sampling allowed for reconstruction of a catechin degradation pathway involving Actinomycetota and Clostridium, which break down catechin into smaller phenolic compounds within the first 21 days, followed by degradation of phenolic compounds by Pseudomonas_E from Days 21 to 35. These genomes co-expressed hydrogen-uptake genes, suggesting hydrogenases may act as a hydrogen sink during catechin degradation and consequently reduce hydrogen availability to methanogens. In support of this idea, there was decreased gene expression by hydrogenotrophic and hydrogen-dependent methylotrophic methanogens under catechin treatment. There was also reduced gene expression from genomes inferred to be functioning syntrophically with hydrogen-utilizing methanogens. We propose that catechin metabolic redirection effectively starves hydrogen-utilizing methanogens, offering a potent avenue for curbing methane emissions across diverse environments including ruminants, landfills, and constructed or managed wetlands.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

O · , H · , and · OH radical etching probability of polystyrene obtained for a radio frequency driven atmospheric pressure plasma jet

Atmospheric pressure plasma jets have great potential for the surface modification of polymers. In this work, the authors report on polystyrene etching by a radio frequency driven atmospheric pressure plasma jet with a focus on the role of H · , O · , and · OH radicals in this process. The absolute flux of H · , O · , and · OH radicals reaching the surface of the polymer was determined by a COMSOL MULTIPHYSICS reacting fluid dynamics model incorporating detailed transport phenomena in the boundary layer near the substrate. The simulated results of H · and · OH densities in the jet effluent were experimentally verified by two-photon absorption laser induced fluorescence and laser induced fluorescence, respectively. The carbon atom removal flux from the polystyrene surface was taken from previously reported measurements using the same plasma source. The authors show that the boundary layer effects in the interfacial region above the substrate can have a significant impact on the calculated etching probabilities. The reaction probability (β) has a significant uncertainty although a variation of 2 orders of magnitude in β leads to uncertainties of approximately 1 order of magnitude variation in the determined etching probability. The etching probability of polystyrene by · OH radicals was confirmed to be at least an order of magnitude larger than the polystyrene etching probability by O · radicals. The authors also confirmed the weak polystyrene etching probability by H · radicals. The model suggests that the presence of a 30 ppm O 2 impurity can lead to the production of · OH radicals in the far effluent of the Ar + 1% H 2 plasma jet close to the substrate at sufficient densities to enable effective etching.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Formation of antireflective surfaces

Technologies are described for methods and systems effective for etching nanostructures in a substrate. The methods may comprise depositing a patterned block copolymer on the substrate. The patterned block copolymer may include first and second polymer block domains. The methods may comprise applying a precursor to the patterned block copolymer to generate an infiltrated block copolymer. The precursor may infiltrate into the first polymer block domain and generate a material in the first polymer block domain. The methods may comprise applying a removal agent to the infiltrated block copolymer to generate a patterned material. The removal agent may be effective to remove the first and second polymer block domains from the substrate. The methods may comprise etching the substrate. The patterned material on the substrate may mask the substrate to pattern the etching. The etching may be performed under conditions to produce nanostructures in the substrate.

Black, Charles T.↗
DOE OSTI2022

Formation of antireflective surfaces

Technologies are described for methods and systems effective for etching nanostructures in a substrate. The methods may comprise depositing a patterned block copolymer on the substrate. The patterned block copolymer may include first and second polymer block domains. The methods may comprise applying a precursor to the patterned block copolymer to generate an infiltrated block copolymer. The precursor may infiltrate into the first polymer block domain and generate a material in the first polymer block domain. The methods may comprise applying a removal agent to the infiltrated block copolymer to generate a patterned material. The removal agent may be effective to remove the first and second polymer block domains from the substrate. The methods may comprise etching the substrate. The patterned material on the substrate may mask the substrate to pattern the etching. The etching may be performed under conditions to produce nanostructures in the substrate.

Black, Charles T.↗
DOE OSTI2025

Host Cavities Enhance the Photocatalytic Conversion of α‐Terpinene to Ascaridole Under Visible‐Light Irradiation

BODIPY-functionalized host molecules have been used as effective visible-light photosensitizers in the conversion of α-terpinene to ascaridole in the presence of molecular oxygen. Host-guest interactions enhance the effective local concentration of the substrate and singlet oxygen generated by the photosensitizing host. This results in up to a 28-fold increase in the rate of conversion depending on the host employed. A tetramethyl BODIPY analogue, in which guest access to the host cavity is blocked, was also employed to confirm that the cavities do indeed enhance substrate turnover. Whilst the latter photocatalyst is more efficient due to the suppression of nonradiative relaxation pathways associated with rotation of the meso-phenyl substituent, the rate enhancement induced by host-guest binding is not present. Combined, this provides insight for the future design of enhanced systems.

Main, Mawgan U↗
DOE OSTI2023

Deposition-controlled phase separation in CuNb metallic alloys

Vapor co-deposited metal nanocomposites with immiscible components have shown to have several superior properties including mechanical performance, radiation tolerance, and enhanced functionalities. The morphology and structural design of these nanocomposites are important in determining the expression of these properties. The conditions used to deposit thin film nanocomposites are the governing factors in determining the final nanostructure. In this work, we link the effects of process gas pressure, substrate temperature, and sputtering target power on resultant Cu/Nb thin film nanostructures. Here, we find that for films with equiatomic phase fractions of Cu and Nb, inhomogeneous precipitate segregation dominated the structure at lower substrate temperature depositions while higher temperatures distributed the Cu and Nb phases more uniformly. Increasing process gas pressure during deposition lead to a spatially homogeneous, nanocrystalline structure of Cu/Nb. In situ annealing of this sample shows that the phase separated morphology of the two immiscible materials depends on the initial composition. Finally, compositions of Cu and Nb that were highly disparate lead to interface segregation of the minority phase. The morphological evolution observed in the Cu/Nb system is compatible with modified structural zone models for immiscible thin film systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tunable Semiconducting Behavior and Linear-Nonlinear Optical Properties of Ag–Sn Dual-Doped Nanocrystalline CdO Thin Films for Optoelectronics

Semiconductor-based thin films have a great impact on determining the anticipated optoelectronic device construction and the advancement of cutting-edge applications. Herein, Ag and Sn dual-doped nanocrystalline transparent conducting CdO thin films were prepared on glass substrates using a cost-effective spray coating method, and their structural, morphological, optical, and semiconducting behaviors were investigated. The successful incorporation of Ag and Sn resulted in the polycrystalline nature of the deposited films without the additional peaks, as verified by X-ray diffraction (XRD) analysis. The XRD report also revealed the enhanced crystallinity (65%) at the higher doping level (3 wt % Ag and Sn-doped CdO film). All the deposited CdO films exhibited homogeneous, spherical, or round-shaped grains, with agglomeration revealed by scanning electron microscopy analysis. UV–visible spectroscopy was utilized to determine the linear and nonlinear optical properties of the deposited CdO thin films, and a reduction in the band gap from 3.891 to 3.772 eV was observed. A significant enhancement in the first- and third-order nonlinear susceptibility and nonlinear refractive index of the doped CdO films was also observed with increasing doping concentration. Hall effect data were collected at room temperature to investigate the electrical properties of all of the CdO films. The charge carrier concentration of CdO thin films was increased from 142.08 × 10 18 to 169.10 × 10 18 cm –3 , and the highest conductivity was found to be 192 s/cm on doping 3 wt % Ag–Sn. All the CdO thin films exhibited n-type conductivity, while an incredible n-type to p-type charge carrier transition was noticed at a higher doping level (3 wt % Ag–Sn). The findings of the current work are expected to advance the synthesis of semiconductor thin films through cost-effective spray coating methods for optoelectronic device applications.

deposition↗
DOE OSTI2021

Controlled Single-Electron Transfer via Metal–Ligand Cooperativity Drives Divergent Nickel-Electrocatalyzed Radical Pathways

Electrocatalysis enables the construction of C-C bonds under mild conditions via controlled formation of carbon-centered radicals. For sequences initiated by alkyl halide reduction, coordinatively unsaturated Ni complexes commonly serve as single-electron transfer agents, giving rise to the foundational question of whether outer- or inner-sphere electron transfer oxidative addition prevails in redox mediation. Indeed, rational design of electrochemical processes requires the discrimination of these two electron transfer pathways, as they can have outsized effects on the rate of substrate bond activation and thus impact radical generation rates and downstream product selectivities. We present results from combined synthetic, electroanalytical, and computational studies that examine the mechanistic differences of single electron transfer to alkyl halides imparted by Ni metal-ligand cooperativity. Electrogenerated reduced Ni species, stabilized by delocalized spin density onto a redox-active tpyPY2Me polypyridyl ligand, activates alkyl iodides via outer-sphere electron transfer, allowing for the selective activation of alkyl iodide substrates over halogen atom donors and the controlled generation and sequestration of electrogenerated radicals. In contrast, the Ni complex possessing a redox-innocent pentapyridine congener activates the substrates in an inner-sphere fashion owning to a purely metal-localized spin, thereby activating both substrates and halogen atom donors in an indiscriminate fashion, generating a high concentration of radicals and leading to unproductive dimerization. Overall, our data establish that controlled electron transfer via Ni-ligand cooperativity can be used to limit undesired radical recombination products and promote selective radical processes in electrochemical environments, providing a generalizable framework for designing redox mediators with distinct rate and potential requirements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Multilevel Computational Studies Reveal the Importance of Axial Ligand for Oxygen Reduction Reaction on Fe–N–C Materials

The systematic improvement of Fe–N–C materials for fuel cell applications has proven challenging, due in part to an incomplete atomistic understanding of the oxygen reduction reaction (ORR) under electrochemical conditions. Herein, a multilevel computational approach, which combines ab initio molecular dynamics simulations and constant potential density functional theory calculations, is used to assess proton-coupled electron transfer (PCET) processes and adsorption thermodynamics of key ORR intermediates. These calculations indicate that the potential-limiting step for ORR on Fe–N–C materials is the formation of the Fe III –OOH intermediate. They also show that an active site model with a water molecule axially ligated to the iron center throughout the catalytic cycle produces results that are consistent with the experimental measurements. In particular, reliable prediction of the ORR onset potential and the Fe(III/II) redox potential associated with the conversion of Fe III –OH to Fe II and desorbed H 2 O requires an axial H 2 O co-adsorbed to the iron center. The observation of a five-coordinate rather than four-coordinate active site has significant implications for the thermodynamics and mechanism of ORR. Importantly, these findings highlight the importance of solvent–substrate interactions and surface charge effects for understanding the PCET reaction mechanisms and transition-metal redox couples under realistic electrochemical conditions.

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

Selective inhibition of cullin 3 neddylation through covalent targeting DCN1 protects mice from acetaminophen-induced liver toxicity

Cullin-RING E3 ligases (CRLs) regulate the turnover of approximately 20% of mammalian cellular proteins. Neddylation of individual cullin proteins is essential for the activation of each CRL. We report herein the discovery of DI-1548 and DI-1859 as two potent, selective and covalent DCN1 inhibitors. These inhibitors selectively inhibit neddylation of cullin 3 in cells at low nanomolar concentrations and are 2–3 orders of magnitude more potent than our previously reported reversible DCN1 inhibitor. Mass spectrometric analysis and co-crystal structures reveal that these compounds employ a unique mechanism of covalent bond formation with DCN1. DI-1859 induces a robust increase of NRF2 protein, a CRL3 substrate, in mouse liver and effectively protects mice from acetaminophen-induced liver damage. Taken together, this study demonstrates the therapeutic potential of selective inhibition of cullin neddylation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Evidence for quantum spin liquid behaviour in single-layer 1T-TaSe 2 from scanning tunnelling microscopy

Two-dimensional triangular-lattice antiferromagnets are predicted under some conditions to exhibit a quantum spin liquid ground state with no energy barrier to create emergent, fractionalized spinon excitations that carry spin but no charge. Materials that realize this kind of spin liquid are expected to have a low-energy behaviour described by a spinon Fermi surface. Directly imaging the resulting spinons, however, is difficult due to their chargeless nature. In this work, we use scanning tunnelling spectroscopy to image density waves consistent with the predictions of spinon density modulation arising from a spinon Fermi surface instability in single-layer 1T-TaSe 2 . We confirm the existence of a triangular lattice of localized spins in this material by contacting it with a metallic 1H-TaSe 2 substrate and measuring the Kondo effect. Spectroscopic imaging of isolated single-layer 1T-TaSe 2 reveals long-wavelength super-modulations at Hubbard band energies, consistent with the predicted behaviour of itinerant spinons. These super-modulations allow the direct experimental measurement of the spinon Fermi wavevector, in good agreement with theoretical predictions for a two-dimensional quantum spin liquid.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Experimental and modeling studies of the plasma chemistry in a humid Ar radiofrequency atmospheric pressure plasma jet

Abstract While humid atmospheric pressure plasmas are extensively modeled, reaction set validation for these conditions remains limited. We present a detailed comparison of a modelling and experimental study with a goal to elucidate the plasma chemistry in a humid Ar radiofrequency-driven atmospheric pressure plasma jet. A large group of species including radicals (H, OH, O, HO 2 ) and long-lived species (H 2 , O 2 and H 2 O 2 ) in the jet effluent was experimentally quantified by molecular beam mass spectroscopy (MBMS). MBMS measurements of H 2 O 2 , OH and H were validated by direct comparison with a liquid phase colorimetric measurement, laser-induced fluorescence (LIF) and two-photon absorption LIF respectively. While an excellent agreement was found for OH and H 2 O 2 by both techniques, a significant difference was found for H and shown to be due to boundary layer effects at the MBMS sampling substrate. The measured O, OH, HO 2 and H 2 are in good agreement with the plug model while H and O 2 were underestimated and H 2 O 2 was overestimated by the model. The accuracy of both the used reaction set and the diagnostics, as well as the observed discrepancies between the modeling and experimental results, are critically assessed. The results presented in this work enable us to identify further data needs for describing H 2 O vapor chemistry in low-temperature plasmas.

Physics↗
DOE OSTI2020

In-plane Néel wall chirality and orientation of interfacial Dzyaloshinskii-Moriya vector in magnetic films

The interfacial Dzyaloshinskii-Moriya interaction (DMI) is of great interest as it can stabilize chiral spin structures in thin films. Experiments verifying the orientation of the interfacial DMI vector remain rare, in part due to the difficulty of separating vector components of DMI. In this study, Fe/Ni bilayers and Co/Ni multilayers were deposited epitaxially onto Cu(001) and Pt(111) substrates, respectively. By tailoring the effective anisotropy, spin reorientation transitions (SRTs) are employed to probe the orientation of the DMI vector by measuring the spin structure of domain walls on both sides of the SRTs. In our results, the interfacial DMI is found to be sufficiently strong to stabilize chiral Néel walls in the out-of-plane magnetized regimes, while achiral Néel walls are observed in the in-plane magnetized regimes. Furthermore, these findings experimentally confirm that the out-of-plane component of the DMI vector is insignificant in these fcc(001) and fcc(111) oriented interfaces, even in the presence of atomic steps.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗