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DOE OSTI2024

Thermal Conversion of Ultrathin Nickel Hydroxide for Wide Band Gap 2D Nickel Oxides

Wide band gap (WBG) semiconductors (E g > 2.0 eV) are integral to the advancement of next-generation electronics, optoelectronics, and power industries owing to their capability for high-temperature operation, high breakdown voltage, and efficient light emission. Enhanced power efficiency and functional performance can be attained through miniaturization, specifically via the integration of device fabrication into a two-dimensional (2D) structure enabled by WBG 2D semiconductors. However, as an essential subgroup of WBG semiconductors, 2D transition metal oxides (TMOs) remain largely underexplored in terms of physical properties and applications in 2D optoelectronic devices, primarily due to the scarcity of sufficiently large 2D crystals. Thus, our goal is to develop synthesis pathways for 2D TMOs possessing large crystal domains (e.g., >10 μm), expanding the 2D TMO family and providing insights for future engineering of 2D TMOs. Here, we demonstrate the synthesis of WBG 2D nickel oxide (NiO) (E g > 2.7 eV) thermally converted from 2D nickel hydroxide (Ni(OH) 2 ) with a lateral domain size larger than 10 μm. Moreover, the conversion process is investigated using various microscopic techniques, such as atomic force microscopy, Raman spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy, providing significant insights into morphology and structural variations under different oxidative conditions. The electronic structure of the converted Ni x O y is further investigated using multiple soft X-ray spectroscopies, such as X-ray absorption and emission spectroscopies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1992

Microgravity accelerometer characterization on Columbia STS-32 mission

The Honeywell In-Space Accelerometer (HISA) is a three-axis microgravity accelerometer instrument package recently developed by Honeywell Systems and Research Center (SRC) to monitor oscillatory and transient accelerations onboard spacecraft and spaceborne structures. The HISA was designed to be co-located with materials and life sciences experiments to record real-time accelerometer event data, sampling time, and temperature. The HISA was originally developed to monitor the microgravity disturbances associated with a polymer morphology experiment developed by 3M Company in Minneapolis, Minnesota. The HISA was first flight tested with the 3M experiment on the Space Shuttle Atlantis STS-34 in October 1989. The HISA was successfully flown on a second shuttle mission (Columbia STS-32 in January 1990) in support of the NASA JSC-sponsored Microgravity Disturbances Experiment (MDE), which focused on the effects of microgravity disturbances on the growth of high-quality Indium crystals. The primary objective of the STS-32 MDE experiment was to investigate the effects of crew-induced gravity disturbances on the microstructure (crystal defects and uniformity of impurity distribution) of float-zone-grown crystals. The float-zone technique involves establishing a suspended molten zone between two cylindrical samples a pure, single-crystal sample and an impure, polycrystalline sample. Microgravity disturbances due to crew treadmill activity and orbiter maneuvering system thruster firings were sensed and recorded by the HISA to understand their effects on the stability of the float zone. The principle of operation of the HISA, the flight configuration of the HISA supporting the MDE experiment, and the characterization of STS-32 treadmill disturbance data are summarized.

Schoess, Jeff↗

DOE OSTI2025

Structural Transformation and Degradation of Cu Oxide Nanocatalysts during Electrochemical CO 2 Reduction

The electrochemical CO 2 reduction reaction (CO 2 RR) holds enormous potential as a carbon-neutral route to the sustainable production of fuels and platform chemicals. The durability for long-term operation is currently inadequate for commercialization, however, and the underlying deactivation process remains elusive. A fundamental understanding of the degradation mechanism of electrocatalysts, which can dictate the overall device performance, is needed. In this work, we report the structural dynamics and degradation pathway of Cu oxide nanoparticles (CuO x NPs) during the CO 2 RR by using in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). The in situ SAXS reveals a reduction in the size of NPs when subjected to a potential at which no reaction products are detected. At potentials where the CO 2 RR starts to occur, CuO x NPs are agglomerated through a particle migration and coalescence process in the early stage of the reaction, followed by Ostwald ripening (OR) as the dominant degradation mechanism for the remainder of the reaction. As the applied potential becomes more negative, the OR process becomes more dominant, and for the most negative applied potential, OR dominates for the entire reaction time. The morphological changes are linked to a gradual decrease in the formation rate for multicarbon products (C 2 H 4 and ethanol). Other reaction parameters, including reaction intermediates and local high pH, induce changes in the agglomeration process and final morphology of the CuO x NPs electrode, supported by post-mortem ex situ microscopic analysis. The in situ XAS analysis suggests that the CuO x NPs reduced into the metallic state before the structural transformation was observed. The introduction of high surface area carbon supports with ionomer coating mitigates the degree of structural transformation and detachment of the CuO x NPs electrode. These findings show the dynamic nature of Cu nanocatalysts during the CO 2 RR and can serve as a rational guideline toward a stable catalyst system under electrochemical conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Interactions between nonfullerene acceptors lead to unstable ternary organic photovoltaic cells

For organic photovoltaic (OPV) devices to achieve consistent performance and long operational lifetimes, organic semiconductors must be processed with precise control over their purity, composition, and structure. This is particularly important for high volume solar cell manufacturing where control of materials quality has a direct impact on yield and cost. Ternary-blend OPVs containing two acceptor–donor–acceptor (A–D–A)-type nonfullerene acceptors (NFAs) and a donor have proven to be an effective strategy to improve solar spectral coverage and reduce energy losses beyond that of binary-blend OPVs. Here, we show that the purity of such a ternary is compromised during blending to form a homogeneously mixed bulk heterojunction thin film. We find that the impurities originate from end-capping C=C/C=C exchange reactions of A–D–A-type NFAs, and that their presence influences both device reproducibility and long-term reliability. The end-capping exchange results in generation of up to four impurity constituents with strong dipolar character that interfere with the photoinduced charge transfer process, leading to reduced charge generation efficiency, morphological instabilities, and an increased vulnerability to photodegradation. As a consequence, the OPV efficiency falls to less than 65% of its initial value within 265 h when exposed to up to 10 suns intensity illumination. We propose potential molecular design strategies critical to enhancing the reproducibility as well as reliability of ternary OPVs by avoiding end-capping reactions.

14 SOLAR ENERGY↗

DOE OSTI2021

Mechanisms of Water-Stimulated Mg 2+ Intercalation in Vanadium Oxide: Toward the Development of Hydrated Vanadium Oxide Cathodes for Mg Batteries

As lithium-ion batteries approach their theoretical limits for energy density, magnesium-ion batteries are emerging as a promising next-generation energy storage technology. However, progress in magnesium-ion battery research has been stymied by a lack of available high capacity cathode materials that can reversibly insert magnesium ions. Vanadium Oxide (V 2 O 5 ) has emerged as one of the more promising candidate cathode materials, owing to its high theoretical capacity, facile synthesis methods, and relatively high operating voltage. This review focuses on the outlook of hydrated V 2 O 5 structures as a high capacity cathode material for magnesium-ion batteries. In general, V 2 O 5 structures exhibit poor experimental capacity for magnesium-ion insertion due to sluggish magnesium-ion insertion kinetics and poor electronic conductivity. However, several decades ago, it was discovered that the addition of water to organic electrolytes significantly improves magnesium-ion insertion into V 2 O 5 . This review clarifies the various mechanisms that have been used to explain this observation, from charge shielding to proton insertion, and offers an alternative explanation that examines the possible role of structural hydroxyl groups on the V 2 O 5 surface. While the mechanism still needs to be further studied, this discovery fueled new research into V 2 O 5 electrodes that incorporate water directly as a structural element. The most promising of these hydrated V 2 O 5 materials, many of which incorporate conductive additives, nanostructured architectures, and thin film morphologies, are discussed. Ultimately, however, these hydrated V 2 O 5 structures still face a significant barrier to potential applications in magnesium-ion batteries. During full cell electrochemical cycling, these hydrated structures tend to leach water into the electrolyte and passivate the surface of the magnesium anode, leading to poor cycle life and low capacity retention. Recently, some promising strides have been made to remedy this problem, including the use of artificial solid electrolyte interphase layers as an anode protection scheme, but a call to action for more anode protection strategies that are compatible with trace water and magnesium metal is required.

25 ENERGY STORAGE↗

NASA NTRS2016

Megafans of the Northern Kalahari Basin

We identify eleven megafans (partial cones of fluvial sediment, >80 km radius) in the northern Kalahari Basin, using several criteria based on VIS and IR remotely sensed data and SRTM-based surface morphology reconstructions. Two other features meet fewer criteria of the form which we class as possible megafans. The northern Kalahari megafans are located in a 1700 km arc around the southern and eastern flanks of the Angola's Bié Plateau, from northern Namibia through northwest Botswana to western Zambia. Three lie in the Owambo subbasin centered on the Etosha Pan, three in the relatively small Okavango rift depression, and five in the Upper Zambezi basin. The population includes the well-known Okavango megafan (150 km), Namibia's Cubango megafan, the largest megafan in the region (350 km long), and the largest nested group (the five major contiguous megafans on the west slopes of the upper Zambezi Valley). We use new, SRTM-based topographic roughness data to discriminate various depositional surfaces within the flat N. Kalahari landscapes. We introduce the concepts of divide megafans, derived megafans, and fan-margin rivers. Conclusions. (i) Eleven megafan cones total an area of ~190,000 sq km. (ii) Different controls on megafan size operate in the three component basins: in the Okavango rift structural controls become the prime constraint on megafan length by controlling basin dimensions. Megafans in the other les constricted basins appear to conform to classic relationships fan area, slope, and feeder-basin area. (iii) Active fans occupy the Okavango rift depression with one in the Owambo basin. The rest of the population are relict but recently active fans (surfaces are relict with respect to activity by the feeder river). (iv) Avulsive behavior of the formative river-axiomatic for the evolution of megafans-has resulted in repeated rearrangements of regional drainage, with likely effects in the study area well back into the Neogene. Divide megafans comprise the majority of the identified features, some of which have delivered water and sediment alternately to neighboring basins in the course of normal avulsion activity, likely resulting in significant changes in the hydrologies of two of the study-area subbasins. (v) Paleoclimatic inferences extracted from fluvial and lacustrine sediments therefore need to take account of avulsion-driven drainage configurations, especially where these are autogenically controlled.

Wilkinson, M. J.↗

DOE OSTI2025

Towards automated and real-time multi-object detection of anguilliform fishes from sonar data using YOLOv8 deep learning algorithm

Eels (Anguilla spp.), including American eels (Anguilla rostrata), European eels (Anguilla anguilla), and Japanese eels (Anguilla japonica), are species of critical management and regulatory concern due to their vulnerability to various stressors during downstream migrations. Accurate and efficient detection of migrating eels can improve our understanding of fish behaviors and fish-hydraulic structure interactions, thereby facilitating the design, operation, and optimization of more effective downstream passage facilities from both biological and economic perspectives. However, a real-time, automated framework for detecting migrating eels in real-world applications is currently lacking. Leveraging imaging sonar as a reliable technology for fish passage monitoring, field data are acquired using imaging sonar and then converted to single sonar frames/images for subsequent analysis. In this study, a framework based on the You Only Look Once Version 8 (YOLOv8)-based convolutional neural network is proposed for multi-object detection of eels and non-eel fish using the sonar images after image subtraction and additional wavelet denoising. The results from both training and testing phases demonstrate that the framework's ability can successfully detect both eels and non-eel fish in preprocessed sonar images, achieving F1-scores and mAP@0.50 exceeding 0.84. Additionally, the incorporation of wavelet denoising during preprocessing slightly improve detection performance. Furthermore, the transferability of this framework from eel to lamprey detection is demonstrated to be feasible given the similar morphological characteristics of these two species. Overall, the proposed framework achieves accurate and efficient detection of migrating eels, providing reliable and real-time information that can help conserve vulnerable eel and eel-like populations.

Deep learning↗

NASA NTRS2002

Emission Line Galaxies in the STIS Parallel Survey: Observations and Data Analysis - 1

In the first three years of operation STIS obtained slitless spectra of approximately 2500 fields in parallel to prime HST observations as part of the STIS Parallel Survey (SPS). The archive contains approximately 300 fields at high galactic latitude (|b| greater than 30) with spectroscopic exposure times greater than 3000 seconds. This sample contains 220 fields (excluding special regions and requiring a consistent grating angle) observed between 6 June 1997 and 21 September 2000, with a total survey area of approximately 160 square arcminutes. At this depth, the SPS detects an average of one emission line galaxy per three fields. We present the analysis of these data, and the identification of 131 low to intermediate redshift galaxies detected by optical emission lines. The sample contains 78 objects with emission lines that we infer to be redshifted [OII]3727 emission at 0.43 < z < 1.7. The comoving number density of these objects is comparable to that of Halpha-emitting galaxies in the NICMOS parallel observations. One quasar and three probable Seyfert galaxies are detected. Many of the emission-line objects show morphologies suggestive of mergers or interactions. The reduced data are available upon request from the authors.

Teplitz, Harry I.↗

NASA NTRS2010

Novel Thermotolerant Siderophilic Filamentous Cyanobacterium that Produces Intracellular Iron-Rich Phases

Cyanobacteria are the main producers of organic compounds in iron-depositing hot springs despite photosynthetically generated-oxygen and the abundance of reduced iron (Fe2+) that likely leads to enormous oxidative stress within cyanobacterial cells. Therefore, the study of cyanobacterial diversity, phylogeny, and biogeochemical activity in iron-depositing hot springs will not only provide insights into the contribution of CB to iron redox cycling in these environments, but it could also provide insights into CB evolution. This study characterizes the phylogeny, morphology, and physiology of isolate JSC-1, a novel filamentous CB isolated from an iron-depositing hot spring. While isolate JSC-1 is morphologically similar to the CB genus Leptolyngbya, 16S rDNA sequence data indicated that it shares 95 percent sequence similarity to the type strain L. boryanum. Strain JSC-1 fixes N2 and exhibited an unusually high ratio between photosystem (PS) I and PS II and was capable of complementary chromatic adaptation. Further, it synthesized only chlorophyll a and a unique set of carotenoids. Strain JSC-1 not only required high levels of Fe for growth (greater than or equal to 40 microM), but it also accumulated large amounts of extracellular ferrihydrite and generated intracellular ferric phosphates. Strain JSC-1 was found to secrete 2-oxoglutaric acid and possesses one ortholog and one paralog of bacterioferritin. Surprisingly, the latter has 70.13 % identity with a bacterioferritin in marine-proteobacterium HTCC 2080 and has joint node with bacterioferritins found in enterobacteria. Collectively, these observations provide insights into the physiological strategies that might have allowed CB to develop and proliferate in Fe-rich environments. Based on its genotypic and phenotypic characterization of strain, JSC-1 represents a new operational taxonomical unit (OTU) JSC-1.

Broun, Igor I.↗

NASA NTRS2002

Plasmaspheric Density Troughs: Global IMAGE EUV Observations and Analysis via Global Core Plasma Modeling

To date, the IMAGE EUV camera has observed several plasmaspheric density trough features inside the plasmapause under a wide range of geomagnetic activity. From the perspective of EUV, a density trough feature appears as a channel of diminished pixel counts which spans a width of L-shell (DELTA L) and magnetic local time (MLT) inside the plasmapause. Plasmaspheric density troughs are found to be morphologically complex possessing considerable spatial and temporal variability. We present an analysis of the evolution of trough DELTA L and MLT extent as functions of associated D (sub ST) and K (sub p) history. Trough features range in size from 0.16 less than or equal to DELTA L less than or equal to 1.2 with azimuthal extent from 1500 less than or equal to MLT less than or equal to 1200. All cases of plasmaspheric density troughs studied to date appear to have evolved as a result of the inner edge of the afternoon/evening plasma drainage plume being wrapped around through the nightside plasmasphere. The structure of plasmaspheric density trough features is further probed by analyzing simulated EUV images produced by forward modeling artificially introduced regions of depleted density into both static and dynamic global core plasmaspheric models. Forward modeling suggests that (1) L-shell refilling of density troughs during storm recovery can be modeled as filling from the ionosphere toward the equator (i.e., bottom-up refilling), and (2) that an erosion process is operating within flux tubes beyond the outer L-shell wall of the observed density troughs.

Adrian, M. L.↗

NASA NTRSDate not supplied

Physics and Modeling of Quasi-Steady and Forced Shock Trains

The dual-mode scramjet is a propulsive concept for contemporary hypersonic vehicles promising flight cruise speeds upwards of Mach 5. Despite decades of development and a recent resurgence in interest, such engines are not routinely deployed for commercial or military purposes. Instead, they have been confined to the realm of ground-test research and limited one-off flight test missions. One of the key stumbling blocks on the critical path to deployment of a dual-mode scramjet is the optimal design and stable operation of the isolator, a typically constant area duct that separates the scramjet inlet from the combustor. During ramjet mode at Mach numbers from 3 to 5 and during the transition to scramjet mode at higher Mach numbers, the isolator contains the pseudo-shock. Necessary to meet the back-pressure in the combustor, the pseudo-shock is typically divided into a shock dominated shock train region followed by a turbulence driven mixing region. Fluctuations in combustor pressure due to vehicle maneuvering, throttling, or combustion instabilities drive the shock train to shift streamwise within the isolator. In response to sharp pressure fluctuations, the shock train is unable to stabilize within the isolator, and the scramjet unstarts by ejecting the shock train out the inlet. This work addresses three key gaps in understanding of the isolator pseudo-shock. The phenomenon is studied in three experimental facilities to investigate the quasi-steady and unsteady fluid dynamics of the shock train in fueled and un-fueled test conditions. The strong link between boundary layer morphology and shock train structure is studied in detail and used as a tool to evaluate the state-of-the-art definitions and models of the pseudo-shock. Identifying the limitations of these models, a new process driven flux-conserved pseudo-shock model is proposed. This provides a computationally efficient model grounded in the fluid dynamic mechanisms of the pseudo-shock with better predictive capability than the current state-of-the-art across all facilities tested. The unsteady behavior of the shock train is further investigated to identify and understand two distinct forced dynamic modes: mechanically induced, low-rate forcing and high-rate combustion driven unsteadiness that sheds upstream propagating shocks. The proposed process driven model is found to be effective in the the limiting case of high-rate combustion driven unsteadiness by evaluating the model in a shock stationary reference frame. Further analysis identifies the approximately rigid chain motion of the shock train structure to mechanically induced forcing. The time delay between the onset of forced dynamics is found to saturate to a constant value and maximum shock train speed along the isolator with respect to the perturbation rate of change. The result of this work provides dual-mode scramjet designers with improved tools and physical understanding to develop more efficient, robust, and capable propulsion systems for hypersonic vehicles.

JAXA↗

NASA NTRS2017

Field Exploration and Life Detection Sampling Through Planetary Analogue Sampling (FELDSPAR).

Exploration missions to Mars rely on rovers to perform analyses over small sampling areas; however, landing sites for these missions are selected based on large-scale, low-resolution remote data. The use of Earth analogue environments to estimate the multi-scale spatial distributions of key signatures of habitability can help ensure mission science goals are met. A main goal of FELDSPAR is to conduct field operations analogous to Mars sample return in its science, operations, and technology from landing site selection, to in-field sampling location selection, remote or stand-off analysis, in situ analysis, and home laboratory analysis. Lava fields and volcanic regions are relevant analogues to Martian landscapes due to desiccation, low nutrient availability, and temperature extremes. Operationally, many Icelandic lava fields are remote enough to require that field expeditions address several sampling constraints that are experienced in robotic exploration, including in situ and sample return missions. The Fimmvruhls lava field was formed by a basaltic effusive eruption associated with the 2010 Eyjafjallajkull eruption. Mlifellssandur is a recently deglaciated plain to the north of the Myrdalsjkull glacier. Holuhraun was formed by a 2014 fissure eruptions just north of the large Vatnajkull glacier. Dyngjusandur is an alluvial plain apparently kept barren by repeated mechanical weathering. Informed by our 2013 expedition, we collected samples in nested triangular grids every decade from the 10 cm scale to the 1 km scale (as permitted by the size of the site). Satellite imagery is available for older sites, and for Mlifellssandur, Holuhraun, and Dyngjusandur we obtained overhead imagery at 1 m to 200 m elevation. PanCam-style photographs were taken in the field by sampling personnel. In-field reflectance spectroscopy was also obtained with an ASD spectrometer in Dyngjusandur. All sites chosen were 'homogeneous' in apparent color, morphology, moisture, grain size, and reflectance spectra at all scales greater than 10 cm. Field lab assays were conducted to monitor microbial habitation, including ATP quantification, qPCR for fungal, bacterial, and archaeal DNA, and direct cell imaging using fluorescence microscopy. Home laboratory analyses include Raman spectroscopy and community sequencing. ATP appeared to be significantly more sensitive to small changes in sampling location than qPCR or fluorescence microscopy. Bacterial and archaeal DNA content were more consistent at the smaller scales, but similarly variable across more distant sites. Conversely, cell counts and fungal DNA content have significant local variation but appear relatively homogeneous over scales of 1 km. ATP, bacterial DNA, and archaeal DNA content were relatively well correlated at many spatial scales. While we have observed spatial variation at various scales and are beginning to observe how that variation fluctuates over time as biodiversity recovers after an eruption, we do not yet fully understand what parameters lead to the observed spatial variation. Home laboratory analyses will help us further understand the elemental and structural composition of the basaltic matrices, but further field analyses are vital for the understanding how temperature, moisture, incident radiation, and so forth influence the habitability of a microclimate.

Field↗

DOE OSTI2024

Swift heavy ion irradiation effects in zirconium and hafnium carbides

The behavior of microcrystalline zirconium carbide (ZrC) and hafnium carbide (HfC) was studied under highly ionizing irradiation conditions at room temperature. The induced structural modifications were characterized via synchrotron-based X-ray diffraction experiments. Unit-cell expansion and buildup of microstrain were determined across a wide fluence range and linked to chemical compositions of the target material. The observed swelling resulting from irradiation with 198 MeV Xe ions in both carbide materials is characterized by two distinct mechanisms that operate within different fluence regimes. Unit-cell expansion initially proceeds by a direct-impact behavior that reaches saturation, followed at higher fluences by a second, linear swelling regime. The overall behavior, particularly the direct-impact regime, is similar for ZrC and HfC, with a more pronounced second defect accumulation process in HfC. Swelling in ZrC shows the same two distinct mechanisms upon irradiation with 198 MeV Xe ions and 946 MeV Au ions, but swelling induced by the lower-energy ions is greater across the entire fluence series. Accounting for the difference in energy deposition density between the two irradiation conditions reveals that the first swelling mechanism (direct-impact behavior) is likely related to the formation of more simple defects. In contrast, the second damaging mechanism at higher fluences (linear increase) cannot be fully explained by the induced energy density, and swelling remains somewhat higher for the low-velocity Xe irradiation. This may suggest that more complex defects and defect clusters are responsible for this swelling regime, with either their size and/or morphology modified at different energy densities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS2007

Comparison of the Atomic Oxygen Erosion Depth and Cone Height of Various Materials at Hyperthermal Energy

Atomic oxygen readily reacts with most spacecraft polymer materials exposed to the low Earth orbital (LEO) environment. If the atomic oxygen arrival comes from a fixed angle of impact, the resulting erosion will foster the development of a change in surface morphology as material thickness decreases. Hydrocarbon and halopolymer materials, as well as graphite, are easily oxidized and textured by directed atomic oxygen in LEO at energies of approx.4.5 eV. What has been curious is that the ratio of cone height to erosion depth is quite different for different materials. The formation of cones under fixed direction atomic oxygen attack may contribute to a reduction in material tensile strength in excess of that which would occur if the cone height to erosion depth ratio was very low because of greater opportunities for crack initiation. In an effort to understand how material composition affects the ratio of cone height to erosion depth, an experimental investigation was conducted on 18 different materials exposed to a hyperthermal energy directed atomic oxygen source (approx.70 eV). The materials were first salt-sprayed to provide microscopic local areas that would be protected from atomic oxygen. This allowed erosion depth measurements to be made by scanning microscopy inspection. The polymers were then exposed to atomic oxygen produced by an end Hall ion source that was operated on pure oxygen. Samples were exposed to an atomic oxygen effective fluence of 1.0x10(exp 20) atoms/sq cm based on Kapton H polyimide erosion. The average erosion depth and average cone height were determined using field emission scanning electron microscopy (FESEM). The experimental ratio of average cone height to erosion depth is compared to polymer composition and other properties.

Waters, Deborah L.↗

DOE OSTI2022

Adatom-Driven Oxygen Intermixing during the Deposition of Oxide Thin Films by Molecular Beam Epitaxy

Thin film deposition from the vapor phase is a complex process involving adatom adsorption, movement, and incorporation into the growing film. While simulations have been able to capture key aspects of these processes to reproduce film morphology, these models typically ignore any subsurface diffusion that occurs. The results of these diffusion and intermixing processes are often observed experimentally, but cannot be explained by invoking bulk lattice diffusion at the deposition temperature. In this work, we present quantitative experimental data that reveals anion and cation intermixing over long length scales during the deposition of epitaxial Fe 2 O 3 and Cr 2 O 3 films and heterostructures by oxygen-plasma-assisted molecular beam epitaxy. We track this diffusion by incorporating well-defined tracer layers containing 18 O and/or 57 Fe, and measure their redistribution on the nanometer scale with atom probe tomography. Molecular dynamics simulations suggest potential intermixing events, which are then examined via nudged elastic band calculations. These reveal that adatoms on the film surface act to “pull up” subsurface O and Fe. Subsequent ring-like rotation mechanisms involving both adatom and subsurface anions then facilitate their mixing. A simple model incorporating these events qualitatively agrees with the experimental intermixing results. In addition to film deposition, these intermixing mechanisms may to be operant during other surface-mediated processes such as heterogeneous catalysis and corrosion.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS1990

Kinetics and thermodynamics of ceramic/metal interface reactions related to high T(sub c) superconducting applications

Superconducting ceramic materials, no matter what their form, size or shape, must eventually make contact with non-superconducting materials in order to accomplish current transfer to other parts of a real operating system, or for testing and measurement of properties. Thus, whether the configuration is a clad wire, a bulk superconducting disc, tape, or a thick or thin superconducting film on a substrate, the physical and mechanical behavior of interface (interconnections, joints, etc.) between superconductors and normal conductor materials of all kinds is of extreme importance to the technological development of these systems. Fabrication heat treatments associated with the particular joining process allow possible reactions between the superconducting ceramic and the contact to occur, and consequently influence properties at the interface region. The nature of these reactions is therefore of great broad interest, as these may be a primary determinant for the real capability of these materials. Research related both to fabrication of composite sheathed wire products, and the joining contacts for physical property measurements, as well as, a review of other related literature in the field are described. Comparison are made between 1-2-3, Bi-, and Tl-based ceramic superconductors joined to a variety of metals including Cu, Ni, Fe, Cr, Ag, Ag-Pd, Au, In, and Ga. The morphology of reaction products and the nature of interface degradation as a function of time will be highlighted.

Notis, Michael R.↗

NASA NTRSDate not supplied

Fabrication and Performance Characterization of Electrospun Nanofibers for Terrestrial and Space Applications

Passive thermal control is vital in space, especially for extended missions involving cryogen storage needing protection from sunlight. This presentation covers the development of a thermal coating with wavelength-selective characteristics using polymeric materials that scatter sunlight with minimal absorption, resulting in high solar reflectance. Furthermore, these coatings allow emission in infrared wavelengths, making them suitable for deep-space missions requiring extended storage. The study chose polymer and surface morphology suitable as solar reflectors that are lightweight, compact, and easily manufacturable, focusing on different multilayered nanofibers made using polytetrafluoroethylene and polyethylene-oxide (PTFE-PEO), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), and silica (SiO2). To understand how these materials interact with sunlight, we analyze light propagation through several layers of electrospun nanofibers to determine spectral reflectance, absorptance, and transmittance by solving the Maxwell equations. The model is also compared with measurements of spectral reflectance and transmittance of the various electrospun nanofibers using spectrophotometers interfaced with integrating spheres in the ultraviolet, visible, near-infrared, and mid-infrared wavelengths. The presentation will also describe the design and analysis, fabrication of the nanofibers using electrospinning, and several experimental characterization techniques to determine suitability for space applications. The nanofibers are tested using various tools to determine their suitability for cryogenic applications in space. Lastly, the samples were tested under low vacuum conditions and exposing them to sunlight inside a vacuum chamber maintained at 300 K. Relative to the incoming solar flux (1000 W/m2), only 1% of the energy was absorbed under these operating conditions. With further optimization and testing under high vacuum cryogenic environments, the samples could demonstrate much lower absorption or higher reflection of incoming solar radiation, which can translate to low temperatures suitable for cryogen storage.

Chieloka Ibekwe↗

NASA NTRS2004

Numerical Simulation of Nanostructure Growth

Nanoscale structures, such as nanowires and carbon nanotubes (CNTs), are often grown in gaseous or plasma environments. Successful growth of these structures is defined by achieving a specified crystallinity or chirality, size or diameter, alignment, etc., which in turn depend on gas mixture ratios. pressure, flow rate, substrate temperature, and other operating conditions. To date, there has not been a rigorous growth model that addresses the specific concerns of crystalline nanowire growth, while demonstrating the correct trends of the processing conditions on growth rates. Most crystal growth models are based on the Burton, Cabrera, and Frank (BCF) method, where adatoms are incorporated into a growing crystal at surface steps or spirals. When the supersaturation of the vapor is high, islands nucleate to form steps, and these steps subsequently spread (grow). The overall bulk growth rate is determined by solving for the evolving motion of the steps. Our approach is to use a phase field model to simulate the growth of finite sized nanowire crystals, linking the free energy equation with the diffusion equation of the adatoms. The phase field method solves for an order parameter that defines the evolving steps in a concentration field. This eliminates the need for explicit front tracking/location, or complicated shadowing routines, both of which can be computationally expensive, particularly in higher dimensions. We will present results demonstrating the effect of process conditions, such as substrate temperature, vapor supersaturation, etc. on the evolving morphologies and overall growth rates of the nanostructures.

Hwang, Helen H.↗