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Results for “interfacial structures”

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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Interfacial Ga-As suboxide: Structural and electronic properties

The structural and electronic properties of Ga-As suboxide representative of the transition region at the GaAs/oxide interface are studied through density functional calculations. Two amorphous models generated by quenches from the melt are taken under consideration. The absence of As–O bonds indicates that the structure is a mixture of GaAs and Ga-oxide, in accordance with photoemission experiments. The band edges of the models are found to be closely aligned to those of GaAs. The simulation of charging and discharging processes leads to the identification of an As-related defect with an energy level at ∼0.7 eV above the GaAs valence band maximum, in good agreement with the experimental density of interface states.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Structure and reactivity of highly reduced titanium oxide surface layers on TiO 2 : A first-principles study

Titanium oxide structures featuring highly reduced TiO x films on top of nearly stoichiometric TiO 2 hold promise for applications ranging from photocatalysis to resistance switching devices. In this article, we focus on titanium monoxide (TiO) layers on anatase TiO 2 (001) and use first principles calculations to investigate their structure and properties as well as their interface with liquid water. We find that only a single TiO layer can grow epitaxially on anatase (001) and subsequent growth leads to the formation of TiO islands. The TiO layers decrease the work function and enhance the surface conductivity in comparison to pure anatase, two features that can improve the TiO 2 performance in photocatalytic hydrogen evolution but are thermodynamically unstable relative to pure TiO 2 in humid/aqueous environment. Furthermore, first principles molecular dynamics simulations of the TiO (001)-water and anatase (001)-water interfaces show that unlike the multilayer structure of interfacial water on the anatase surface, a very dense and tightly packed first water layer is present on the surface of TiO, which could represent the first stage of partial surface reoxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Monovalent ion–graphene oxide interactions are controlled by carboxylic acid groups: Sum frequency generation spectroscopy studies

Graphene oxide (GO) is a two-dimensional, mechanically strong, and chemically tunable material for separations. Elucidating GO–ion–water interactions at the molecular scale is highly important for predictive understanding of separation systems. However, direct observations of the nanometer region by GO surfaces under operando conditions are not trivial. Therefore, thin films of GO at the air/water interface can be used as model systems. With this approach, we study the effects of alkali metal ions on water organization near graphene oxide films at the air/water interface using vibrational sum frequency generation (SFG) spectroscopy. Here, we also use an arachidic acid Langmuir monolayer as a benchmark for a pure carboxylic acid surface. Theoretical modeling of the concentration-dependent sum frequency signal from graphene oxide and arachidic acid surfaces reveals that the adsorption of monovalent ions is mainly controlled by the carboxylic acid groups on graphene oxide. An in-depth analysis of sum frequency spectra reveals at least three distinct water populations with different hydrogen bonding strengths. The origin of each population can be identified from concentration dependent variations of their SFG signal. Interestingly, an interfacial water structure seemed mostly insensitive to the character of the alkali cation, in contrast to similar studies conducted at the silica/water interface. However, we observed an ion-specific effect with lithium, whose strong hydration prevented direct interactions with the graphene oxide film.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Effects of confinement and pressure on the structure and dynamics of carbon dioxide in silica slit pores

An understanding of carbon dioxide fluid properties within geological mesopores is important in applications ranging from carbon sequestration to shale oil recovery. Here, a molecular dynamics study is presented that aims to shed light on these systems by simulation of CO 2 fluid confined in β-cristobalite silica slit pores with different pore widths and pressure conditions. The weakly associating nature of carbon dioxide leads to little difference in structural and interfacial dynamical properties for different pore sizes and pressures. Rather, the behavior is found to be dominated by the entropic effects, namely, how the CO 2 organizes next to the silica surface. The CO 2 self-diffusion coefficient shows the strongest pore size dependence. It is strongly diminished in small pores and does not reach the bulk fluid value even in 6 nm pores. It also decreases with pressure, yielding an activation volume that increases with pore size. These results provide new insight into the behavior of a compressible fluid in nanoscale confinement.

Godahewa, Sahan M. [Univ. of Kansas, Lawrence, KS ↗
DOE OSTI2015

Interfacial Magnetism in Complex Oxide Heterostructures Probed by Neutrons and X-rays

Magnetic complex-oxide heterostructures are of keen interest because a wealth of phenomena at the interface of dissimilar materials can give rise to fundamentally new physics and potentially valuable functionalities. Altered magnetization, novel magnetic coupling and emergent interfacial magnetism at the epitaxial layered-oxide interfaces have all been intensively investigated, which shapes our understanding on how to utilize those materials, particularly for spintronics. Neutron and x-ray based techniques have played a decisive role in characterizing interfacial magnetic structures and clarifying the underlying physics in this rapidly developing field. Here we review some recent experimental results, with an emphasis on those studied via polarized neutron reflectometery and polarized x-ray absorption spectroscopy. We conclude with some perspectives.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Theoretical Insights for Improving the Schottky-Barrier Height at the Ga2O3/Pt Interface

In this work, we study the Schottky-barrier height (SBH) at the junction between ..beta..-Ga2O3 and platinum, a system of great importance for the next generation of high-power and high-temperature electronic devices. Specifically, we obtain interfacial atomic structures at different orientations using our structure-matching algorithm and compute their SBH using electronic structure calculations based on hybrid density-functional theory.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,P↗
DOE OSTI2020

Stabilization of Hydroxide Ions at the Interface of a Hydrophobic Monolayer on Water via Reduced Proton Transfer

We report a joint study using surface-specific sum-frequency vibrational spectroscopy and ab initio molecular dynamics simulations, respectively, on a pristine hydrophobic (sub)monolayer hexane-water interface, namely, the hexane/water interface with varied vapor pressures of hexane and different pHs in water. We show clear evidence that hexane on water revises the interfacial water structure in a way that stabilizes the hypercoordinated solvation structure and slows down the migration of hydroxide ion (OH – ) relative to that in bulk water. Furthermore, this mechanism effectively attracts the OH – to the water-hydrophobic interface with respect to its counterion. The result illustrates the striking difference of proton transfer of hydrated OH – at the interface and in the bulk, which is responsible for the intrinsic charging effect at the hydrophobic interface.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Investigating the Crosslinking, Degradation, and Adhesion Behavior of Photovoltaic Encapsulants Under Thermal Accelerated Aging

Degradation of photovoltaic (PV) module encapsulant characteristics that lead to mechanical embrittlement and delamination remains a cause of failure in solar installations. A multiscale reliability model connecting the encapsulant mechanical and fracture properties to the degraded molecular structure and interfacial bonding to adjacent solar cell and glass substrates was previously published. The model, developed primarily for poly(ethylene-co-vinyl acetate) acetate (EVA) encapsulants, remains to be experimentally validated. Determining the degradation and crosslinking kinetics of alternative encapsulants, such as polyolefin elastomer (POE) and EVA/POE/EVA composites (EPE), can generalize the model. In this work, we subject fully cured EVA, POE, and EPE encapsulants to accelerated thermal aging to determine how high temperatures impact reaction kinetics. An increase in gel content (crosslinking) and decrease in crystallinity of the encapsulants under hot-aerobic (90 degrees C, 22% RH) and hot-anaerobic (90 degrees C, sealed in N 2 air) aging were observed, even in the absence of UV and crosslinking initiators. Fourier transform infrared spectroscopy (FTIR)-attenuated total reflectance analysis showed insignificant encapsulant degradation, demonstrating the critical role of UV and moisture in accelerating degradation. Adhesion testing performed on coupon-level specimens (cell/encapsulant/glass laminates) showed decreases in adhesion energy, Gc , from 5000 h of hot-dry (90 degrees C, ~1% RH) and hot-humid (90 degrees C, 60% RH) aging. POE coupons demonstrated the best stability, followed by EPE then EVA. For EVA and POE, hot-humid aged coupons experienced a larger decrease in Gc due to enhanced hydrolytic degradation. Hot-dry aging condition demonstrated that thermal degradation of the interface could be significant even if the encapsulant experiences negligible degradation in the absence of UV and elevated humidity.

accelerated aging↗
DOE OSTI2021

First Principles Predictions of SnO2/CdTe and SnO2/CdCl2/CdTe Interface Structures

Interfaces become increasingly the limiting factor of solar cell efficiency, raising the interest in computational models. However, explicit atomic structure models from microscopy are rare, and hypothetical assumptions about the atomic structure become ambiguous for incoherent or highly lattice mismatched interfaces. Adopting a bulk crystal structure prediction algorithm to interfacial systems enables explicit structure models for the bare and CdCl 2 treated SnO 2 /CdTe interface.

CdTe↗
DOE OSTI2016

Role of HfO 2 /SiO 2 thin-film interfaces in near-ultraviolet absorption and pulsed laser damage

Here, the role of thin-film interfaces in the near-ultraviolet (near-UV) absorption and pulsed laser-induced damage was studied for ion-beam-sputtered and electron-beam-evaporated coatings comprised from HfO 2 and SiO 2 thin-film pairs. To separate contributions from the bulk of the film and from interfacial areas, absorption and damage threshold measurements were performed for a one-wave (355-nm wavelength) thick, HfO 2 single-layer film and for a film containing seven narrow HfO 2 layers separated by SiO 2 layers. The seven-layer film was designed to have a total optical thickness of HfO 2 layers, equal to one wave at 355 nm and an E-field peak and average intensity similar to a single-layer HfO 2 film. Absorption in both types of films was measured using laser calorimetry and photothermal heterodyne imaging. The results showed a small contribution to total absorption from thin-film interfaces as compared to HfO 2 film material. The relevance of obtained absorption data to coating near-UV, nanosecond-pulse laser damage was verified by measuring the damage threshold and characterizing damage morphology. The results of this study revealed a higher damage resistance in the seven-layer coating as compared to the single-layer HfO 2 film in both sputtered and evaporated coatings. The results are explained through the similarity of interfacial film structure with structure formed during the codeposition of HfO 2 and SiO 2 materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The role of film interfaces in near-ultraviolet absorption and pulsed-laser damage in ion-beam-sputtered coatings based on HfO 2 /SiO 2 thin-film pairs

The role of thin-film interfaces in the near-ultraviolet absorption and pulsed-laser–induced damage was studied for ion-beam–sputtered and electron-beam–evaporated coatings comprised from HfO 2 and SiO 2 thin-film pairs. To separate contributions from the bulk of the film and from interfacial areas, absorption and damage-threshold measurements were performed for a one-wave (355-nm wavelength) thick, HfO 2 single-layer film and for a film containing seven narrow HfO 2 layers separated by SiO 2 layers. The seven-layer film was designed to have a total optical thickness of HfO 2 layers, equal to one wave at 355 nm and an E-field peak and average intensity similar to a single-layer HfO 2 film. Absorption in both types of films was measured using laser calorimetry and photothermal heterodyne imaging. The results showed a small contribution to total absorption from thin-film interfaces, as compared to HfO 2 film material. The relevance of obtained absorption data to coating near-ultraviolet, nanosecond-pulse laser damage was verified by measuring the damage threshold and characterizing damage morphology. The results of this study revealed a higher damage resistance in the seven-layer coating as compared to the single-layer HfO 2 film in both sputtered and evaporated coatings. Here, the results are explained through the similarity of interfacial film structure with structure formed during the co-deposition of HfO 2 and SiO 2 materials.

36 MATERIALS SCIENCE↗
DOE OSTI2016

A Spinel-integrated P2-type Layered Composite: High-rate Cathode for Sodium-ion Batteries

Sodium-ion batteries (SIB) are being intensively investigated, owing to the natural abundance and low cost of Na resources. However, the SIBs still suffer from poor rate capability due to the large ionic radius of Na+ ion and the significant kinetic barrier to Na+-ion transport. Here, we present an Fd-3m spinel-integrated P2-type layered composite (P2 + Fd-3m) material as a high-rate cathode for SIBs. The P2 + Fd-3m composite material Na0.50Ni1/6Co1/6Mn2/3O2 shows significantly enhanced discharge capacity, energy density, and rate capability as compared to the pure P2-type counterpart. The composite delivers a high capacity of 85 mA h g-1 when discharging at a very high current density of 1500 mA g-1 (10C rate) between 2.0 and 4.5 V, validating it as a promising cathode candidate for high-power SIBs. The superior performance is ascribed to the improved kinetics in the presence of the integrated-spinel phase, which facilitates fast electron transport to coordinate with the timely Na+-ion insertion/extraction. The findings of this work also shed light on the importance of developing lattice doping, surface coating, and electrolyte additives to further improve the structural and interfacial stability of P2-type cathode materials and fully realize their practical applications in sodium-ion batteries.

Zheng, Jianming↗
DOE OSTI2023

In operando neutron imaging characterizations of all-solid-state batteries

The surge in electric vehicle demand has propagated the extensive application of lithium-ion batteries (LIBs) in recent years. Gaining significant traction due to their promising high-energy density and elevated safety over traditional LIBs, all-solid-state Li batteries (ASLBs) have nonetheless been faced with hurdles relating to battery performance. These include concerns with interfacial compatibility, structural stability, Li dendrite inhibition, and large-scale manufacturing. To tackle these issues, it is necessary to employ advanced characterization methods to comprehend the intrinsic mechanisms within ASLBs. In this article, we advocate for the use of neutron imaging as a nondestructive approach for the operando visualization of ASLBs. We draw comparisons with other operando visualization strategies, underline the benefits of neutron imaging, and discuss its potential applicability in the scrutiny of all-solid-state Li metal batteries and all-solid-state Li-sulfur batteries. Neutron imaging provides valuable insights into the dynamics of Li concentration, reaction mechanisms, and transport constraints in ASLBs. These insights are pivotal in contributing to the evolution of high-performance all-solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2017

Monodispersed Zinc Oxide Nanoparticle-Dye Dyads and Triads

The overall energy conversion efficiency of photovoltaic cells depends on the combined efficiencies of light absorption, charge separation and charge transport. Dye-sensitized solar cells are photovoltaic devices in which a molecular dye absorbs light and uses this energy to initiate charge separation. The most efficient dye-sensitized solar cells (DSSCs) use nanocrystal titanium dioxide films to which are attached ruthenium complexes. Numerous studies have provided valuable insight into the dynamics of these and analogous photosystems, but the lack of site homogeneity in binding dye molecules to metal oxide films and nanocrystals (NCs) is a significant impediment to extracting fundamental details about the electron transfer across the interface. Although zinc oxide is emerging as a potential semiconducting component in DSSCs, there is less known about the factors controlling charge separation across the dye/ZnO interface. Zinc oxide crystallizes in the wurtzite lattice and has a band gap of 3.37 eV. One of the features that makes ZnO especially attractive is the remarkable ability to control the morphology of the films. Using solution deposition processes, one can prepare NCs, nanorods and nanowires having a variety of shapes and dimensions. This project solved problems associated with film heterogeneity through the use of dispersible sensitizer/ZnO NC ensembles. The overarching goal of this research was to study the relationship between structure, energetics and dynamics in a set of synthetically controlled donor-acceptor dyads and triads. These studies provided access to unprecedented understanding of the light absorption and charge transfer steps that lie at the heart of DSSCs, thus enabling significant future advances in cell efficiencies. The approach began with the construction of well-defined dye-NC dyads that were sufficiently dispersible to allow the use of state of the art pulsed laser spectroscopic and kinetic methods to understand the charge transfer events at a fundamental level. This was combined with the synthesis of a broad range of sensitizers that provide systematic variation of the energetics, excited state dynamics, structure and interfacial bonding. The key is that the monodisperse nature and high dispersibility of the ZnO NCs made these experiments reproducible; in essence, the measurements were on discrete molecular species rather than on the complicated mixtures that resulted from the typical fabrication of functional photovoltaic cells. The monodispersed nature of the NCs also allowed the use of quantum confinement to investigate the role of donor/acceptor energetic alignment in chemically identical systems. The results added significantly to our basic understanding of energy and charge transfer events at molecule-semiconductor interfaces and will help the R&D community realize zinc oxide's full potential in solar cell applications.

14 SOLAR ENERGY↗
DOE OSTI2023

Chemical controls on the propagation and healing of subcritical fractures

Human activities involving subsurface reservoirs—resource extraction, carbon and nuclear waste storage—alter thermal, mechanical, and chemical steady-state conditions in these systems. Because these systems exist at lithostatic pressures, even minor chemical changes can cause chemically assisted deformation. Therefore, understanding how chemical effects control geomechanical properties is critical to optimizing engineering activities. The grand challenge in predicting the effect of chemical processes on mechanical properties lays in the fact that these phenomena take place at molecular scales, while they manifest all the way to reservoir scales. To address this fundamental challenge, we investigated chemical effects on deformation in model and real systems spanning molecular- to centimeter scales. We used theory, experiment, molecular dynamics simulation, and statistical analysis to (1) identify the effect of simple reactions, such as hydrolysis, on molecular structures in interfacial regions of stressed geomaterials; (2) quantify chemical effects on the bulk mechanical properties, fracture and displacement for granular rocks and single crystals; (3) develop initial understanding of universal scaling for individual displacement events in layered geomaterials; and (4) develop analytic approximations for the single-chain mechanical response utilizing asymptotically correct statistical thermodynamic theory. Taken together, these findings advance the challenging field of chemo-mechanics.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Understanding controls on interfacial wetting at epitaxial graphene: Experiment and Theory

The interaction of interfacial water with graphitic carbon at the atomic scale is studied as a function of the hydrophobicity of epitaxial graphene. High resolution x-ray reflectivity shows that the graphene-water contact angle is controlled by the average graphene thickness, due to the fraction of the film surface expressed as the epitaxial buffer layer whose contact angle (contact angle {Theta}{sub c} = 73{sup o}) is substantially smaller than that of multilayer graphene ({Theta}{sub c} = 93{sup o}). Classical and ab initio molecular dynamics simulations show that the reduced contact angle of the buffer layer is due to both its epitaxy with the SiC substrate and the presence of interfacial defects. This insight clarifies the relationship between interfacial water structure and hydrophobicity, in general, and suggests new routes to control interface properties of epitaxial graphene.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗