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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Interfacial Charge Transfer and Substrate-Dependent Oxidation States Drive SMSI Enhancements in Cobalt Oxide Films

Here, we investigated the mechanisms underlying strong metal-support interactions in CO oxidation using model systems where noble metal crystals support reducible, monolayer-thick CoO x films. The effect of the Co oxidation state, film thickness, and substrate identity were studied in varying reaction conditions using ambient pressure X-ray photoelectron spectroscopy. At low O 2 pressures, the same oxide phase forms on both Pt(111) and Au(111) surfaces. But when heated at higher O 2 pressures, the oxide phase depends on the substrate. We found that CoO x /Pt is more active for the CO oxidation reaction than CoO x /Au, even when both surfaces stabilize the same oxide phase. DFT calculations on these and related noble-metal-supported CoO x films reveal an SMSI-induced reactivity enhancement that strongly depends on the oxide film thickness and which is mediated by charge transfer between the metal and oxide. Charge transfer is also found to correlate with the reaction energy and activation barrier for CO oxidation. This effect was found to be greatest for oxide films on Pt, decreasing on other noble metal supports in the order Pt > Pd > Au > Ag, in agreement with the experiments. The role of charge transfer in the activation barriers and reaction energies provides insight into the nature of SMSI-induced catalytic activity, and suggests that the noble metal work function can serve as an indicator for the strength of SMSI effects.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evolution of spin excitations from bulk to monolayer FeSe

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

36 MATERIALS SCIENCE↗
DOE 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 OSTI2021

Controllable Thin‐Film Approaches for Doping and Alloying Transition Metal Dichalcogenides Monolayers

Abstract Two‐dimensional (2D) transition metal dichalcogenides (TMDs) exhibit exciting properties and versatile material chemistry that are promising for device miniaturization, energy, quantum information science, and optoelectronics. Their outstanding structural stability permits the introduction of various foreign dopants that can modulate their optical and electronic properties and induce phase transitions, thereby adding new functionalities such as magnetism, ferroelectricity, and quantum states. To accelerate their technological readiness, it is essential to develop controllable synthesis and processing techniques to precisely engineer the compositions and phases of 2D TMDs. While most reviews emphasize properties and applications of doped TMDs, here, recent progress on thin‐film synthesis and processing techniques that show excellent controllability for substitutional doping of 2D TMDs are reported. These techniques are categorized into bottom–up methods that grow doped samples on substrates directly and top–down methods that use energetic sources to implant dopants into existing 2D crystals. The doped and alloyed variants from Group VI TMDs will be at the center of technical discussions, as they are expected to play essential roles in next‐generation optoelectronic applications. Theoretical backgrounds based on first principles calculations will precede the technical discussions to help the reader understand each element's likelihood of substitutional doping and the expected impact on the material properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Dual–Interface–Reinforced Flexible Perovskite Solar Cells for Enhanced Performance and Mechanical Reliability

Two key interfaces in flexible perovskite solar cells (f-PSCs) are mechanically reinforced simultaneously: one between the electron-transport layer (ETL) and the 3D metal-halide perovskite (MHP) thin film using self-assembled monolayer (SAM), and the other between the 3D-MHP thin film and the hole-transport layer (HTL) using an in situ grown low-dimensional (LD) MHP capping layer. The interfacial mechanical properties are measured and modeled. This rational interface engineering results in the enhancement of not only the mechanical properties of both interfaces but also their optoelectronic properties holistically. As a result, the new class of dual-interface-reinforced f-PSCs has an unprecedented combination of the following three important performance parameters: high power-conversion efficiency (PCE) of 21.03% (with reduced hysteresis), improved operational stability of 1000 h T90 (duration at 90% initial PCE retained), and enhanced mechanical reliability of 10 000 cycles n88 (number of bending cycles at 88% initial PCE retained). Furthermore, the scientific underpinnings of these synergistic enhancements are elucidated.

14 SOLAR ENERGY↗
DOE OSTI2021

Picometer sensitivity metrology for EUV absorber phase

With growing interest in EUV attenuated phase-shift masks due to their superior image quality for applications such as dense contact and pillar arrays, it is becoming critical to model, measure, and monitor the intensity and relative phase of multilayer and absorber reflections. We present a solution based on physical modeling of reflectometry data, which can achieve single picometer phase precision and sensitivity to changes in average film thickness below one atomic monolayer. We measure absorber and multilayer reflectivity to determine thin-film parameters with a multidimensional optimization and then acquire a new measurement of either multilayer or absorber to determine perturbations in surface contamination thickness. While it is difficult to assess the accuracy of the first step, the simplicity of the second step allows us to characterize our sensitivity to changes in contamination thickness. Thus, we apply this analysis using an initial set of measurements and repeated measurements after a period of storage. For the multilayer, the total contamination growth was 1068 pm, which occurred almost exclusively during storage (1085 pm) and decreased very slightly during repeated measurements (-17 pm). For the absorber, the behavior was quite different, with a total growth of 126 pm, which occurred much less during storage (28 pm) and primarily during repeated measurements (98 pm). Ultimately, the change in relative phase (absorber minus multilayer) was -0.86 deg for the multilayer and -1.12 deg for the absorber. We estimate the precision of the surface contamination measurement to be 3σ < 6 pm for measuring thickness and 3σ < 0.2 deg for measuring phase.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Sieving Hydrogen Isotopes via Machine Learning Assisted Chemical Vapor Deposition (CVD) of High‐Quality Monolayer Hexagonal Boron Nitride (h‐BN) on Iron Foils

Atomically thin two-dimensional (2D) ceramics, such as monolayer hexagonal boron nitride (h-BN), present potential for disruptive advances in separations. However, sub-atomic scale separation of hydrogen isotopes (H + /D + ) require near pristine 2D material membranes, and scalable synthesis of such high-quality h-BN comparable to mechanically exfoliated crystals remains a significant challenge. Here, we report a scalable Fe-catalyzed chemical vapor deposition (CVD) process for bottom-up synthesis of large-area, high-quality monolayer h-BN films, overcoming key limitations of conventional ammonia-based routes. By leveraging mechanistic insights and higher CVD temperatures, we suppress multilayer formation and achieve uniform monolayer h-BN coverage on commercially available Fe foils. Machine learning enables systematic exploration of the complex, multi-dimensional CVD parameter space (growth time, temperature, precursor temperature, multilayer faction, coverage), providing data-driven approaches to visualize and identify process regimes facilitating predominantly monolayer h-BN growth with minimal secondary nuclei/ad-layers. The optimized Fe-catalyzed CVD h-BN membranes show high-quality as observed by proton/deuteron (H + /D + ) selectivity ≈8.45, approaching the highest quality benchmark of mechanically exfoliated h-BN (H + /D + selectivity ≈10) as well as significantly outperforming Cu-catalyzed CVD h-BN membranes (H + /D + selectivity ≈3.62, control selectivity ≈1.7). Our work provides a scalable cost-effective route for high-quality monolayer h-BN synthesis for sub-atomic scale separations (H + /D + ) and demonstrates the broader potential of machine learning-guided optimization of CVD for advancing synthesis of 2D materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Uptake of Pb and the Formation of Mixed (Ba,Pb)SO 4 Monolayers on Barite During Cyclic Exposure to Lead-Containing Sulfuric Acid

Barite (BaSO 4 ) is a common additive in lead-acid batteries, where it acts as a nucleating agent to promote the reversible formation and dissolution of PbSO 4 during battery cycling. However, little is known about the molecular-scale mechanisms the nucleation and cyclic evolution of PbSO 4 over a battery’s lifetime. In this study, we explore the responses of a barite (001) surface to cycles of high and low lead concentrations in the presence of 100 mM sulfuric acid using in-situ atomic force microscopy and high-resolution X-ray reflectivity. Here we find that PbSO 4 epitaxial films readily nucleate on the barite surface, even from solutions that are undersaturated relative to bulk PbSO 4 . Despite this, barite (001) proves to be an ineffective nucleator of bulk PbSO 4 , as multilayer growth is suppressed even in highly supersaturated solutions. Instead, we find evidence that Pb 2+ ions can directly exchange with Ba 2+ to create mixed (Ba,Pb)SO 4 surfaces. These chemically mixed surfaces do not host PbSO4 monolayers as readily as pristine barite, and the original reactivity is not regained until a fresh surface is reestablished by aggressive etching. Our results can be partly explained by traditional models of Stranski-Krastanov (S-K) growth, in which monolayer films are stabilized by a reduction in surface energy, but multilayer growth is inhibited by epitaxial strain. Complementary density functional theory calculations confirmed the basic energetic-terms of traditional S-K models, but also showed evidence form more complex, thickness-dependent, energetics than would be predicted from the S-K models. The experimental results can be better understood by extending the S-K model to consider the formation of mixed surfaces and films, which can have reduced strain and interfacial energies relative to pure films, while also being stabilized by entropy of mixing. These insights into non-stoichiometric heteroepitaxy will enable better predictions of how barite affects PbSO 4 nucleation in battery environments.

25 ENERGY STORAGE↗
DOE OSTI2023

Engineering Self-Assembled Domain Asymmetry in Solvent Vapor Annealed Block Copolymer–Homopolymer Blend Films

Thin-film block copolymer (BCP) self-assembly is a powerful approach to generate highly uniform nanopatterns across large areas, yet the symmetries of these nanopatterns are constrained by the relative volume occupied by each polymer block. Here, we present a conceptually new approach to circumvent this limitation by combining homopolymer (HP) blending with solvent vapor annealing (SVA), demonstrated here for ternary blends of a near-symmetric BCP with athermal, low molar mass HPs. Screening of BCP–HP interactions by a weakly selective solvent promotes entropically driven delocalization of HP throughout both blocks and enables assembly of metastable lamellae for volume fractions as high as 0.78. Subsequent brief thermal annealing induces HPs to withdraw to their enthalpically favored domains, sharpening domain interfaces on a time scale much shorter than pattern coarsening. This renders lamellar nanopatterns with tunable widths that can be transferred to other materials with high fidelity. Furthermore, the persistence of the metastable asymmetric lamellae upon thermal annealing is sensitive to film confinement, as they are preserved in submonolayer films but transition to horizontal cylinders in films more than one monolayer thick. SVA using a strongly selective solvent results in assembled morphologies aligned closely with expectations based on the total polymer blend composition, underscoring the key role of BCP–HP interactions in dictating domain asymmetry. Overall, this work details important principles for using SVA to mediate BCP–HP interactions in thin films, thereby presenting opportunities to engineer pathways for the assembly of well-ordered nanopatterns with designer feature asymmetry for lithographic or nanotexturing applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Water film-driven Mn (oxy)(hydr)oxide nanocoating growth on rhodochrosite

Minerals exposed to moist air stabilize thin water films that drive a score of chemical reactions of great importance to water-unsaturated terrestrial environments. In this study, we identified Mn (oxy)(hydr)oxide nanocoatings formed by the dissolution, oxidation and precipitation of Mn in oxygenated water films grown on rhodochrosite (MnCO 3 ) microparticles. Nanocoatings that could be identified by vibrational spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and (scanning and transmission) electron microscopy formed in water films containing the equivalent of at least 7 monolayers (~84 H 2 O/nm 2 ). These films were formed by exposing microparticles to moist air with at least 50% relative humidity (RH). Films of neutral pH reacted up to 14% of the Mn II located in the topmost ~5 nm region of the microparticles in atmospheres of up to 90% RH for 7 d. These reactions produced MnOOH, birnessite (MnO 2 ) and hausmannite (Mn 3 O 4 ) nanoparticles of low crystallinity, while exposure to atmospheric air for 1 yr. converted only 2% of Mn II in this region to MnOOH. In contrast, reactions in alkaline water films converted up to ~75% of the Mn II but only after 16 d of reaction. These films produced MnOOH and MnO 2 of low crystallinity, as well as crystalline hausmannite. Kinetic modeling of the time-resolved growth of the Mnsingle bondO stretching vibrational bands of these nanocoatings revealed two concurrent reaction processes. A 1 rst -order process was assigned to nucleation events terminating only after a few hours, and a 0-order process was assigned to the sustained growth of nanocoatings from these nuclei over longer reaction time. By identifying nanocoatings formed by water film-driven reactions on rhodochrosite, our study adds new insight into mineralogical transformations relevant to anoxic–oxic boundaries in water-unsaturated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

One-Step Transfer of Symmetric and Asymmetric Contacts for Large-Scale 2D Electronics and Optoelectronics

Two-dimensional (2D) semiconductors are highly promising candidates for thin-film transistor applications due to their scalability, transferability, atomic thickness, and relatively high carrier mobility. However, a substantial performance gap remains between individual devices based on single-crystalline 2D films and wafer-scale integrated circuits, primarily due to defects introduced during conventional fabrication processes. Here, we report a diamond-assisted electrode transfer technique for the van der Waals integration of wafer-scale prefabricated electrode arrays onto 2D materials, enabling scalable electronics and optoelectronics. Implemented on metal–organic chemical vapor deposition-grown monolayer molybdenum disulfide, this method forms ultraclean metal–semiconductor interfaces, yielding field-effect transistors with excellent ohmic contacts, a low contact resistance of 400 Ω·μm, and a Schottky barrier height of only 9 meV. Furthermore, we demonstrate a scalable transistor array on monolayer molybdenum disulfide with excellent device performance uniformity, achieving an average field-effect mobility of 30 cm 2 V –1 s –1 and an on/off current ratio exceeding 105. Additionally, high photocurrent and responsivity were demonstrated in the array devices, showing their potential for excellent image detection. We further demonstrate the versatility of this technique by fabricating a Schottky diode array through a single-step transfer of asymmetric electrodes─low work function aluminum and high work function gold─onto monolayer tungsten diselenide. This approach provides a clean, effective solution for contact engineering in 2D materials, offering a viable pathway toward wafer-scale, high-performance 2D electronics, optoelectronics, and integrated circuits.

2D electronics↗
DOE OSTI2022

Core-level binding energy shifts between interior, terrace and edge atoms in MnO(001) thin films

Understanding the physical origin of core-level photoemission line shapes can offer valuable information about the chemical and physical properties of surfaces. For instance, in a large number of transition metals oxides, changes in the line shape allow the accurate determination of their oxidation states and cation site symmetry. Yet, despite this importance, experimental investigations on core-level shifts have been much neglected in recent years. In order to provide further evidence of the physical relevance, we have, in this contribution, introduced a new aspect of interior-, terrace- and edge- atom core-level binding energy shifts to describe monolayers of MnO(001) films grown on an Au(111) substrate. By this means we were able to distinguish the line shape contributions related to different types of atomic sites. Here we show that their relative intensities and energy shifts are able to provide information about the relative amount of under coordinated atoms on the surface and, thus give insights into their catalytic properties. Our findings reveal the importance of a detailed surface science characterization to provide the correct interpretation of distinct photoemission line shapes when considering thin film samples as well as nanostructures in general.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Growth of Low-Defect WSe 2 Film via High-Purity van der Waals Crystal Precursor

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) exhibit exceptional electrical and optical properties, empowering their promising prospects for future nanoelectronics. Despite major advances in n-type 2D semiconductors, the field has yet to synthesize high-mobility p-type 2D TMDs, in particular WSe 2 , and systematically query the influence of defects. In this study, we unveil the pivotal role of substitutional impurity defects vis-à-vis the precursor used and growth method employed in defining the quality of 2D p-type WSe 2 . Density functional theory calculations suggest the adverse effect of Fe-, Co-, Ni- and Si-substituted W impurity defects on the mobility of WSe 2 , whereas defects such as O-, S-substituted Se and Mo-substituted W pose negligible impact. Guided by the theory, we pinpoint van der Waals (vdW) crystals, commonly used in mechanical exfoliation, as the optimal precursor, and develop a facile vdW crystal physical vapor deposition (PVD) method to grow high-purity monolayer 2D WSe 2 film (VPVD-WSe 2 ) that is continuous across a centimeter scale. A suite of spectroscopies confirms the markedly reduced defect density of the as-synthesized WSe 2 compared to those by typical chemical vapor deposition methods, and by PVD with commercial or hydrothermal precursors. Scanning tunneling microscopy further evidence the ultralow substitutional impurity defect density of VPVD-WSe 2 , greatly outperforming the control samples and approaching the mechanically exfoliated counterparts. The VPVD-WSe 2 based field-effect transistors exhibit notable electrical performance with record-high field-effect hole mobility up to 112 cm 2 V –1 s –1 at room temperature, exceeding the best-reported monolayer WSe 2 synthesized by chemical vapor deposition and rivaling the mechanically exfoliated 2D WSe 2 flakes.

WSe2↗
DOE OSTI2021

Growth and Development of Quantum Materials

Topological insulators (TIs) display a new state of quantum matter, which is broadly known as quantum materials. The TIs have a unique property of being an insulator as a bulk property and having conducting surface states, which are symmetry-protected Dirac Fermions and well isolated from the bulk valence and conduction bands. Ideally, these topological surface states and bulk electronic states should act independently. The degree to which they intermix depends on the crystalline quality, composition and defects present in the material. These materials thus demand very high-quality crystals to observe the desired quantum properties. We proposed growth of high-quality single crystals and thin films to enhance the ability to fabricate devices with unique performance attributes. Two separate approaches will be made to make the thin films, one is exfoliation of 2D monolayer from the grown single crystals and the second is thin films grown by pulsed laser deposition. Both techniques will subsequently allow for fabrication of meso structures using a Focused Ion Beam technique.

36 MATERIALS SCIENCE↗
NASA NTRS1974

The oxidation of titanium films saturated with nitrogen at 300 K

In a two-chamber system designed for physical adsorption studies, a titanium film was deposited and exposed to nitrogen. Oxygen was then admitted into the system. However, the presence of oxygen could not be detected by the mass spectrometer during the first 300 seconds of oxygen admission. On the basis of the data it is assumed that the capture probability of the nitrogen-saturated titanium film for oxygen is very nearly 1. Based on this assumption, the titanium film adsorbed approximately 3 monolayers of oxygen.

Outlaw, R. A.↗
NASA NTRS1988

Applications of surface analysis and surface theory in tribology

Tribology, the study of adhesion, friction and wear of materials is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture and friction are discussed.

Ferrante, John↗
NASA NTRS1989

Applications of surface analysis and surface theory in tribology

Tribology, the study of adhesion, friction and wear of materials, is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science, and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid-state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture, and friction are discussed.

Ferrante, John↗