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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Nanostructured $\mathrm{GaAs/(Al,Ga)As}$ Waveguide for Low-Density Polariton Condensation from a Bound State in the Continuum

Exciton-polaritons are hybrid light-matter states that arise from strong coupling between an exciton resonance and a photonic cavity mode. As bosonic excitations, they can undergo a phase transition to a condensed state that can emit coherent light without a population inversion. This aspect makes them good candidates for thresholdless lasers, yet short exciton-polariton lifetime has made it difficult to achieve condensation at very low power densities. In this sense, long-lived symmetry-protected states are excellent candidates to overcome the limitations that arise from the finite mirror reflectivity of monolithic microcavities. In this work we use a photonic symmetry-protected bound state in the continuum coupled to an excitonic resonance to achieve state-of-the-art polariton condensation threshold in a GaAs/(Al,Ga)As waveguide. Most important, we show the influence of fabrication control and how surface passivation via atomic layer deposition provides a way to reduce exciton quenching at the grating sidewalls.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Growth and characterization of homoepitaxial β-Ga 2 O 3 layers

ß-Ga 2 O 3 is a next-generation ultra-wide bandgap semiconductor (E g = 4.8 eV to 4.9 eV) that can be homoepitaxially grown on commercial substrates, enabling next-generation power electronic devices among other important applications. Analyzing the quality of deposited homoepitaxial layers used in such devices is challenging, in part due to the large probing depth in traditional x-ray diffraction (XRD) and also due to the surface-sensitive nature of atomic force microscopy (AFM). Here, a combination of evanescent grazing-incidence skew asymmetric XRD and AFM are investigated as an approach to effectively characterize the quality of homoepitaxial ß-Ga 2 O 3 layers grown by molecular beam epitaxy at a variety of Ga/O flux ratios. Accounting for both structure and morphology, optimal films are achieved at a Ga/O ratio of ~1.15, a conclusion that would not be possible to achieve by either XRD or AFM methods alone. Finally, fabricated Schottky barrier diodes with thicker homoepitaxial layers are characterized by J-V and C-V measurements, revealing an unintentional doping density of 4.3×10 16 cm -3 - 2×10 17 cm -3 in the epilayer. These results demonstrate the importance of complementary measurement methods for improving the quality of the ß-Ga 2 O 3 homoepitaxial layers used in power electronic and other devices.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mass spectral molecular mapping shows benefits of thermal evaporation in prelithiated silicon-based electrodes

Silicon based composites have become increasingly popular as potential anodes for lithium-ion batteries due to their large storage capacity and potential ability to generate batteries with energy densities greater than 350 Wh kg −1 . These anodes often see reduced initial columbic efficiency (ICE) due to disruptive volume expansionup to 300% and continuous solid electrolyte interphase (SEI) layer formation. Prelithiation, where an excess reservoir of Li is added to the electrode to compensate for irreversible SEI formation losses during their sample preparation, has proven to solve the issue of immediate capacity loss. Thermal evaporation is a prelithiation technique with limited studies on its effectiveness. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to highlight the benefits of prelithiation via thermal evaporation. ToF-SIMS provides chemical mapping and spatial information in 2D and 3D visualizing the deposition of lithium, identifying Li x Si y alloy and Li x Si y O z silicate formation, and the distribution of lithium passivation into the electrodes. Passivation under different atmospheric conditions, such as inert Argon (Ar) and Ar/ carbon dioxide (CO 2 ), highlights the impact of the environment on the passivation effectiveness and formation of Li x Si y alloy and Li x Si y O z silicate. The ToF-SIMS molecular imaging and depth profiling results indicate that prelithiation via thermal evaporation effectively distributes lithium throughout the depth profile thickness of several hundred nanometers. It induces a greater degree of Li x Si y O z silicate formation over Li x Si y alloy. Our ToF-SIMS characterization results show the effectiveness of thermal evaporation in producing a more stable electrode and an electrode with an effective lithium reserve that can preserve its capacity.

Parker, Gabriel D. [Oak Ridge National Laboratory ↗
DOE OSTI2025

Bypassing sulfides: comparing the morphology and performance of solution processed Cu(In,Ga)Se 2 films prepared via two selenide molecular precursor routes

Solution-processing of thin-film photovoltaics offers an alternative to vacuum-deposition based approaches. The amine–thiol reactive solvent system has become a focal point for the solution-processing of chalcogenide species, owing to the convenience of precursor preparation and comparatively high performance of prepared devices. Selenide species prepared via the amine–thiol route typically progress through a sulfide intermediate phase, and as such are commonly afflicted with sulfur and carbon impurities along- side the presence of a carbonaceous fine-grained layer. Here, two routes of preparing films directly to a selenide phase are examined; first by the co-dissolution of selenium in an amine–thiol solution and second via the novel use of reactive alkylammonium polyselenides. Lamella are cut from these selenide precursor films and final devices, and STEM-EDX and TEM are used to characterize film morphology and secondary phases. A champion device efficiency of 11.2% is reported for the novel polyselenide route, and clear paths of improvement are identified.

36 MATERIALS SCIENCE↗
DOE OSTI2021

On the Development of Order and Interfaces during the Growth of Ultrathin La 2 CuO 4 Films by Molecular Beam Epitaxy

While the atomic structure of interfaces in complex oxide heterostructures created by epitaxial growth has been investigated extensively, few studies have been conducted on how interfaces form and restructure at the initial stage of film growth. The dynamic aspects of the growth behavior can strongly influence the final interfacial atomic structure, which may lead to the emergence of interface-specific properties, such as the rise of interfacial superconductivity between certain Ruddlesden-Popper oxide materials. In this report, the structural development of La2CuO 4 thin films grown by molecular beam epitaxy on a LaSrAlO 4 substrate is investigated by X-ray diffraction measurements with rapid scans over a volume of reciprocal space. This method provides far more detailed information on interface formation than traditional fixed-point measurements. The results show that the atomic structure of the interface becomes fully established after just a single unit cell of growth. Interestingly, restructuring continues to occur within the topmost half to one unit cell of the film during the deposition process. However, diffraction intensity oscillations from both reflection high-energy electron and X-ray measurements stabilize only after the growth of two unit cells, indicating that the growth front morphology continues to evolve until the start of the third unit cell. This multimodal investigation provides insights into the atomic processes taking place during layered oxide interface formation, including the dynamical rearrangement of LaO and CuO 2 layers. Such information is not only relevant to the engineering and optimization of functional layer structures but can also be critical for ultrathin films.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Adsorption Processes during Electrochemical Atomic Layer Deposition of Gold

Electrochemical atomic layer deposition (e-ALD) technique offers a simple and effective "wet chemistry" approach enabling high-precision monolayer-by-monolayer deposition of metal films. The process of e-ALD of Au involves lead underpotential deposition (PbUPD) followed by its redox replacement by a Au monolayer. The time evolution of the deposit mass during "one-pot" Au e-ALD is known to exhibit a unique three-stage response that is presently not well understood. In this work, we probe this response using voltammetry, electrochemical quartz crystal microgravimetry (e-QCM), and chronoamperometry to unravel the underlying mechanistic events during Au e-ALD. Furthermore, the presence of adsorbed Au +3 -ligand complex(es) (Au-L) on the Au surface is established. In stage I of e-ALD, this Au-L adsorbed layer is reduced to Au while a Pb UPD adlayer is formed. In stage II, the Pb UPD adlayer undergoes spontaneous surface-limited redox replacement by nobler Au under open-circuit conditions. Finally, in stage III, re-adsorption of the Au-L occurs on the newly deposited Au. Quantitative analysis of the deposit mass transients obtained under a variety of conditions provides an estimate of the Au-L mass and its molecular weight.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Epitaxially Grown Single-Crystalline SrTiO 3 Membranes Using a Solution-Processed, Amorphous SrCa 2 Al 2 O 6 Sacrificial Layer

Water-soluble sacrificial layers based on epitaxially-grown, single crystalline (Ca, Sr, Ba) 3 Al 2 O 6 layer are widely used for creating free-standing perovskite oxide membranes. However, obtaining these sacrificial layers with intricate stoichiometry remains a challenge, especially for molecular beam epitaxy (MBE). In this study, we demonstrate the hybrid MBE growth of epitaxial, single crystalline SrTiO 3 films using a solution processed, amorphous SrCa 2 Al 2 O 6 sacrificial layer onto SrTiO 3 (001) substrates. Prior to the growth, the oxygen plasma exposure was used to first create the crystalline SrCa 2 Al 2 O 6 layer with well-defined surface crystallinity. Utilizing reflection high energy electron diffraction, x-ray diffraction, and atomic force microscopy, we observe an atomic layer-by-layer growth of epitaxial, single crystalline SrTiO 3 film on the SrCa 2 Al 2 O 6 layer with atomically smooth surfaces. The SrCa 2 Al 2 O6 layer was subsequently dissolved in de-ionized water to create free-standing SrTiO3 membranes that were transferred onto a metal-coated Si wafer. Membranes created with Sr-deficiency revealed ferroelectric-like behavior measured using piezo force microscopy whereas stoichiometric films remained paraelectric-like. Furthermore, these findings underscore the viability of using ex-situ deposited amorphous SrCa2Al2O6 for epitaxial, single crystalline growth, as well as the importance of point defects in determining the ferroic properties in membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Structural and electronic switching of a single crystal 2D metal-organic framework prepared by chemical vapor deposition

The incorporation of metal-organic frameworks into advanced devices remains a desirable goal, but progress is hindered by difficulties in preparing large crystalline metal-organic framework films with suitable electronic performance. We demonstrate the direct growth of large-area, high quality, and phase pure single metal-organic framework crystals through chemical vapor deposition of a dimolybdenum paddlewheel precursor, Mo 2 (INA) 4 . These exceptionally uniform, high quality crystals cover areas up to 8600 µm 2 and can be grown down to thicknesses of 30 nm. Moreover, scanning tunneling microscopy indicates that the Mo 2 (INA) 4 clusters assemble into a two-dimensional, single-layer framework. Devices are readily fabricated from single vapor-phase grown crystals and exhibit reversible 8-fold changes in conductivity upon illumination at modest powers. Moreover, we identify vapor-induced single crystal transitions that are reversible and responsible for 30-fold changes in conductivity of the metal-organic framework as monitored by in situ device measurements. Gas-phase methods, including chemical vapor deposition, show broader promise for the preparation of high-quality molecular frameworks, and may enable their integration into devices, including detectors and actuators.

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

Role of Polysulfide Anions in Solid-Electrolyte Interphase Formation at the Lithium Metal Surface in Li–S Batteries

Delineating intricate interactions between highly reactive Li-metal electrodes and the diverse constituents of battery electrolytes has been a long-standing scientific challenge in materials design for advanced energy storage devices. Here, we isolated lithium polysulfide anions (LiS 4 - ) from an electrolyte solution based on their mass-to-charge ratio and deposited them on Li-metal electrodes under clean vacuum conditions using ion soft landing (ISL), a highly controlled interface preparation technique. The molecular level precision in the construction of these model interfaces with ISL, coupled with in situ x-ray photoelectron spectroscopy and ab initio theoretical calculations, allowed us to obtain unprecedented insight into the parasitic reactions of well-defined polysulfides on Li-metal electrodes. Our study reveals that the oxide-rich surface layer, which is amenable to direct electron exchange, drives multielectron sulfur oxidation (S o → S 6+ ) processes. Furthermore, our results have substantial implications for the rational design of future Li-S batteries with improved efficiency and durability.

25 ENERGY STORAGE↗
DOE OSTI2026

Protein Adhesion on Semi-Fluorinated Polystyrene Surfaces in Static and Dynamic Measurements

Reducing protein adhesion is a critical strategy in fouling-resistant material innovation, with broad applications spanning biomedical and healthcare devices, biosensors, industrial and environmental systems, and other important technological domains. Here, in this study, we elucidated protein adhesion behavior on polystyrene-based thin films by neutron reflectometry (NR) and quartz crystal microbalance with dissipation (QCM-D), using both lysozyme and bovine serum albumin (BSA) as model proteins. To this end, semifluorinated polystyrene thin films with gradient wettability and surface energy were fabricated through dry processing using plasma oxidation and gas-phase deposition. Although it is believed that a fully fluorinated alkyl chain offers extremely low surface energy, thus rejecting foulants, and has been used in many fouling-resistant surface designs, enhanced protein–surface interactions were observed consistently in NR and QCM-D results, due to the combined effects of surface morphology and chemistry. On the contrary, depositing shorter fluorinated silane onto a hydrophilic PS surface contributed to a more homogeneous nanoscale fluorine coating, resulting in less initial protein adsorption and improved surface recovery. Comparative analysis of proteins with different sizes on the nanopatterned semifluorinated surface revealed the influence of molecular characteristics on surface interactions. Lysozyme, being smaller and more compact, showed faster adsorption kinetics and higher surface coverage but largely reversible binding, whereas BSA, with its larger and more flexible structure, formed broader and more stable interfacial layers. This study fills the gap in understanding protein adhesion within the range of hydrophobicity (water contact angle ∼90°), as current strategies often associate with extreme hydrophilic and superhydrophobic surfaces due to hydration or low-surface-energy rejection mechanisms, respectively. It also provides in-depth insights into current combinatorial fouling-resistant surface design.

Yuan, Yue [Oak Ridge National Laboratory (ORNL), O↗
DOE OSTI2026

Polymer-Derived Amorphous Aluminosilicate Nanomembranes for H 2 Purification

Aluminosilicate zeolite membranes with robust microporous crystalline structures are attractive for the molecular separation of H 2 from light gases, but their large-scale fabrication is complicated and costly, hindering their practical applications. Herein, we present polymer-derived amorphous aluminosilicate nanomembranes that combine the exceptional processability of polymers with the superior gas separation properties of aluminosilicates. Specifically, thin-film composite membranes comprising 150 nm polydimethylsiloxane were first treated with oxygen plasma to generate 10 nm polyorganosilica (POSi) on the surface, which were then subjected to few-cycle atomic layer deposition (ALD) using trimethylaluminum as a metal precursor and water vapor as a coreactant. This scalable two-step process yields few-nanometer amorphous aluminosilicates with strong size-sieving ability. For example, three-cycle ALD treatment of POSi increases H 2 /CO 2 selectivity from 39 to 200 and H 2 /CH 4 selectivity from 190 to 500, while decreasing H 2 permeance from 990 to 210 GPU at 150 °C, superior to the state-of-the-art membranes. In conclusion, rapid and scalable manufacturing of amorphous aluminosilicate nanolayers can also be of interest for catalysis and adsorption applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Resistive Coatings for High-performance, Low-background MCPs Operating Across Broad Temperature Ranges and at Cryogenic Temperatures

Microchannel plate with improved thermo-electric properties are a high risk, high payoff development undertaken by a consortium of effort that links the Argonne National Lab, the Space-Science Lab at UC Berkeley and the small businesses (Incom Inc.) that will commercialize the advanced technology in open MCPs and LAPPDs. This development will satisfy the needs for new instrumentation for homeland security (non-proliferation) sensors to screen vehicles and cargo for Special Nuclear Materials (SNMs) and scientific detectors for astrophysics, electron microscopy, time-of-flight mass spectrometry, molecular and atomic collision studies, and fluorescence imaging applications in biotechnology and medical imaging products including positron emission tomography (PET scanning).

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2022

Molecular-level understanding of metal ion retention in clay-rich materials

Clay minerals retain or adsorb metal ions in the Earth’s critical zone. Rocks, sediments and soils rich in clay minerals can concentrate rare earth elements (REEs) in ion adsorption-type deposits (IADs) and are similarly effective at metallic contaminant remediation. However, the molecular-scale chemical and physical mechanisms of metal ion retention remain only partly understood. Here, we describe the nature, location and energy requirements of metal retention at clay mineral surfaces. Retention originates mainly from electrostatic interactions during cation exchange at low pH and chemical bonding in surface complexation and precipitation at neutral and high pH. Surface complexation can induce surface redox reactions and precipitation mechanisms including neoformation of clay mineral layered structures. In IADs, outer-sphere adsorption is the major retention mechanism of REE ions. By contrast, the use of clay minerals in pollution control relies on various mechanisms that can coexist, including cation exchange, surface complexation and nucleation growth. To more effectively leverage clay mineral–metal interactions in resource recovery and contaminant remediation, complex mechanisms such as surface precipitation and redox reactions must be better understood; for instance, by utilizing advances in quantum mechanical calculations, close combination between synchrotron and simulation techniques, and upscaling of molecular-level information in macroscopic thermokinetic predictive models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Understanding Solid-Electrolyte Interphase Formation at the Lithium Metal Anode of Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are one of the most promising chemistries for the next generation of energy storage devices. In a standard Li-S cell, the metallic lithium anode is an essential component of the battery due to its low density, extremely high theoretical specific capacity, and very low negative electrochemical potential. However, several challenges related to the use of Li metal have prevented this battery technology from becoming commercially available. For instance, Li-anodes are highly reactive, which results in the continuous decomposition of the electrolyte and the formation of the solid-electrolyte interphase (SEI) layer. This, combined with the non-uniform deposition of Liions during plating at the anode surface, can seriously affect the performance, cycling, and safety of the battery. In addition, it has been suggested that a controlled SEI formation at the metallic Li anode can yield enhanced battery performance. Hence, a comprehensive understanding of how the SEI layer is formed can help elucidate improvements in this battery technology. In this work, the formation of the SEI layer in Li-S batteries is investigated using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The stability of liquid organic-based electrolyte components, salt concentration, electron-rich environments, and the use of inorganic solid-state electrolyte (SSE) materials are explored in order to provide molecular-level fundamental insights into how the nature and composition of the electrolyte can alter the initial stages of the SEI formation. The products of electrolyte decomposition and electro-/chemical reaction pathways of liquid electrolyte component such as solvent and salts are predicted from AIMD simulations of electrolyte-anode interfaces. Energetics of reactions from DFT ground-state optimizations are also presented to confirm the decomposition mechanisms. Some significant differences are then drawn regarding the use of low and high salt concentrations. Simulations under electron-rich environments show additional multielectron electrochemical reactions of solvent and salt decomposition taking place due to the excess of electrons and the presence of radical anions in the solution. Finally, the initial stages of formation, stability, and main constituents of interfaces between Li-metal and Sbased electrodes with sulfide-based SSEs are characterized in detail.

25 ENERGY STORAGE↗
DOE OSTI2025

Tuning of electronic properties in highly lattice-mismatched epitaxial SmN

Here, we establish the relationship between native N vacancies, introduced through varying growth parameters, and the structural and transport properties in SmN thin films grown via molecular beam epitaxy grown on MgO(001). The varying levels of N vacancies introduced by varying the ratio of Sm to N atoms during deposition creates excess carriers that radically transform the electrical behavior of the film, over a range of five orders of magnitude, from highly resistive to highly conductive, and unlocking a phase transition evidenced by the presence of a ferromagnetic feature in resistivity. X-ray photoelectron spectroscopy results show that this effect is much less pronounced when varying the available nitrogen species. These samples retain a highly crystal quality despite being grown on a substrate with a lattice mismatch of 20%, alleviating the strain by forming a highly strained SmO oxide layer. The integration between SmN and several transition metal nitride compounds has the potential to unlock new architectures for Josephson junction devices.

36 - MATERIALS SCIENCE↗
DOE OSTI2022

Molecular Alignment of a Meta-Aramid on Carbon Nanotubes by In Situ Interfacial Polymerization

Molecularly organized nanocomposites of polymers and carbon nanotubes (CNTs) have great promise as high-performance materials; in particular, conformal deposition of polymers can control interfacial properties for mechanical load transfer, electrical or thermal transport, or electro/chemical transduction. However, controllability of polymer-CNT interaction remains a challenge with common processing methods that combine CNTs and polymers in melt or in solution, often leading to nonuniform polymer distribution and CNT aggregation. In this work, we demonstrate CNTs within net-shape sheets can be controllably coated with a conformal coating of meta-aramid by simultaneous capillary infiltration and interfacial polymerization. We determine that π-interaction between the polymer and CNTs results in chain alignment parallel to the CNT outer wall. Subsequent nucleation and growth of the precipitated aramid forms a smooth continuous layered sheath around the CNTs. These findings motivate future investigation of mechanical properties of the resulting composites, and adaptation of the in situ polymerization method to other substrates.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Unveiling the Interfacial Reconstruction Mechanism Enabling Stable Growth of the Delafossite PdCoO 2 on Al 2 O 3 and LaAlO 3

Delafossites, composed of noble metal (A + ) and strongly correlated sublayers (BO 2 – ), form natural superlattices with highly anisotropic properties. These properties hold significant promise for various applications, but their exploitation hinges on the successful growth of high-quality thin films on suitable substrates. Unfortunately, the unique lattice geometry of delafossites presents a significant challenge to thin-film fabrication. Different delafossites grow differently, even when deposited on the same substrate, ranging from successful epitaxy to complete growth suppression. These variations often lack a clear correlation to obvious causes like lattice mismatch. Unidentified stabilization mechanisms appear to enable growth in certain cases, allowing these materials to form stable thin films or act as buffer layers for subsequent delafossite growth. This study employs advanced scanning transmission electron microscopy techniques to investigate the nucleation mechanism underlying the stable growth of PdCoO 2 films on Al 2 O 3 and LaAlO 3 substrates grown via molecular-beam epitaxy. Our findings reveal the presence of a secondary phase within the substrate surface that stabilizes the films. This mechanism deviates from the conventional understanding of strain relief mechanisms at oxide heterostructure interfaces and differs significantly from those observed for Cu-based delafossites.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Probability Density Function for the spatial and intensity distribution of neutron-induced defects in Silicon

The ability to model semiconductor device degradation under neutron irradiation depends upon having a robust modeling capability for the neutron-induced collision cascades as well as a means to analytically fit the resulting probability distributions of defect production and ionizing energy deposition for purposes of extrapolation to low-probability, high-consequence scenarios. In this paper, the widely-utilized binary collision approximation codes MARLOWE and SRIM are deployed in conjunction with a critical examination of their parameterizations as benchmarked against higher-fidelity molecular dynamics simulations. A simple 3-parameter form described by the Generalized Logistic Distribution is shown to be a good fit to Frenkel pair and ionization intensity distributions in bulk silicon. The BCA codes are then applied to simulate cascades in 5 nm layers of a representative gate-all-around nanosheet transistor, where joint probability distributions of threshold levels of damage to multiple layers are evaluated.

36 MATERIALS SCIENCE↗