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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

Unveiling the influence of selective-area-regrowth interfaces on local electronic properties of GaN p-n junctions for efficient power devices

Here, we report correlated nanoscale mapping of the structure, composition, and properties of regrown GaN p-n junctions to identify how etching and non-planar regrowth processes limit diode performance via the introduction of unintentional dopants and defect states. p-GaN was selectively regrown in n-GaN trenches with SiO 2 masks of variable mask-to-trench-width ratio. Dilute Al layers were periodically introduced during regrowth as markers of the growth interface. Correlated nanoscale mapping of doping, conductivity, and dopant complexes was achieved with atom probe tomography (APT), scanning spreading resistance microscopy (SSRM), and cathodoluminescence (CL) spectroscopy, respectively. The Al marker layers, detected by APT, enabled reconstruction of the faceted growth interface and correlation of the dopant concentration with position and time. The p-GaN growth rate is proportional to the mask-to-trench width ratio while the dopant incorporation rate is invariant. At trench edges, magnesium incorporation is suppressed, and oxygen incorporation enhanced, due to preferential incorporation on the semi-polar growth surface, leading to compensation and less abrupt p-n junctions; the SiO 2 mask is a source of oxygen. Residual etch damage below the regrowth interface induces n-type and p-type conductivity, creating leakage pathways. The non-uniform Mg incorporation is driven by crystal anisotropy and is thus inherent to non-planar regrowth, but can be mitigated by engineering the regrowth interface and process parameters. The unprecedented integration of spatially resolved mapping of dopants, impurities, conductivity, and carrier type is a powerful approach to discriminating distinct factors that limit the performance of regrown diodes, enabling the rational optimization of process and device design.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Water Desalination Using Nanoporous Single-Layer Graphene with Tunable Pore Size

Graphene has great potential to serve as a separation membrane due to its unique properties such as chemical and mechanical stability, flexibility and most importantly its one-atom thickness. In this study, we demonstrate first experimental evidence of the use of single-layer porous graphene as a desalination membrane. Nanometer-sized pores are introduced into single layer graphene using a convenient oxygen plasma etching process that permits tuning of the pore size. The resulting porous graphene membrane exhibited high rejection of salt ions and rapid water transport, thus functioning as an efficient water desalination membrane. Salt rejection selectivity of nearly 100% and exceptionally high water fluxes exceeding 105 g m-2 s-1 at 40 C were measured using saturated water vapor as a driving force.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Formation and Ripening of Self-Assembled Multilayers from the Vapor-Phase Deposition of Dodecanethiol on Copper Oxide

Here, the vapor-phase reaction of dodecanethiol (DDT) with copper oxide surfaces and the molecular level composition and structure of the resulting films were examined. Atomic force microscopy, cross-sectional transmission electron microscopy, and electron energy loss/electron dispersive spectroscopy reveal that, instead of forming self-assembled monolayers, DDT etches CuO surfaces to create ~8 nm thick Cu-thiolate multilayers. These layers are composed of surprisingly well-ordered crystallites, oriented either parallel or perpendicular to the substrate surface. Pre-etching of the CuO to expose the underlaying copper metal is shown to prevent the formation of multilayers and instead allow for the formation of the expected monolayers. Water contact angle and Fourier transform infrared spectroscopy are further shown to be ineffective at distinguishing the multilayer and monolayer thiol films. Interestingly, the multilayer films are unstable in air, ripening into particles 20 μm wide and several hundred nanometers tall over the course of a week. Air exposure also leads to the slow oxidation of the sulfur and copper within the films at a rate similar to what has been seen before for DDT monolayers. As a result, the multilayers show no significant improvement over monolayers in the prevention of oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Isolating GaSb membranes grown metamorphically on GaAs substrates using highly selective substrate removal etch processes

The etch rates of NH 4 OH:H 2 O 2 and C 6 H 8 O 7 :H 2 O 2 for GaAs and GaSb have been investigated to develop a selective etch for GaAs substrates and to isolate GaSb epilayers grown on GaAs. The NH 4 OH:H 2 O 2 solution has a greater etch rate differential for the GaSb/GaAs material system than C 6 H 8 O 7 :H 2 O 2 solution. The selectivity of NH 4 OH:H 2 O 2 for GaAs/GaSb under optimized etch conditions has been observed to be as high as 11471 ± 1691 whereas that of C 6 H 8 O 7 :H 2 O 2 has been measured up to 143 ± 2. The etch contrast has been verified by isolating 2 μm thick GaSb epi-layers that were grown on GaAs substrates. GaSb membranes were tested and characterized with high-resolution X-Ray diffraction (HR-XRD) and atomic force microscopy (AFM).

36 MATERIALS SCIENCE↗
DOE OSTI2019

Modifications of Textured Silicon Surface Morphology and Its Effect on Poly-Si/SiO x Contact Passivation for Silicon Solar Cells

High-efficiency crystalline silicon (c -Si) solar cells require textured surfaces for efficient light trapping. However, passivation of a textured pyramidal surface to reduce carrier recombination is challenging due to the presence of sharp tips, edges, and valleys. Using electrical and surface microscopies combined with lifetime measurements, we report on the effect of HF:HNO3 etching on the pyramidal textured Si surface morphology, and on poly-Si/SiOx contact performance. Preferential rounding of either the valleys between pyramids, or the pyramid tips is obtained depending on the HF:HNO3 solution temperature. Both these morphologies make the pyramid shape irregular, with the pyramid faces no longer being predominantly a Si(111) surface. Our atomic force microscopy measurements further show that the nanoscale roughness over the pyramid face also reduces after HF:HNO3 etching. Thus, etching affects the microscopic pyramidal shape, the dominant crystallographic orientation, and the nanoscale roughness of the surface. We speculate that these three surface effects result in the improvement of surface passivation via poly-Si/SiOx contacts. However, this improved passivation is accompanied by increased reflectance of the HF:HNO3-etched textured surface. Finally, our electron-beam-induced current measurements reveal thickness nonuniformities in the thermally grown SiOx layer on the HF:HNO3-etched textured Si surface: SiO x is thicker near the pyramid tips, edges, and faces as compared with near the valleys between pyramids. This nonuniformity in the SiOx layer may explain the poorer passivation obtained on a KOH-textured and HF:HNO3-etched textured surface as compared with a planar surface.

14 SOLAR ENERGY↗
DOE OSTI2017

Selective Nanoscale Mass Transport across Atomically Thin Single Crystalline Graphene Membranes

Atomically thin single crystals, without grain boundaries and associated defect clusters, represent ideal systems to study and understand intrinsic defects in materials, but probing them collectively over large area remains nontrivial. In this study, the authors probe nanoscale mass transport across large-area (≈0.2 cm 2 ) single-crystalline graphene membranes. A novel, polymer-free picture frame assisted technique, coupled with a stress-inducing nickel layer is used to transfer single crystalline graphene grown on silicon carbide substrates to flexible polycarbonate track etched supports with well-defined cylindrical ≈200 nm pores. Diffusion-driven flow shows selective transport of ≈0.66 nm hydrated K + and Cl - ions over ≈1 nm sized small molecules, indicating the presence of selective sub-nanometer to nanometer sized defects. This work presents a framework to test the barrier properties and intrinsic quality of atomically thin materials at the sub-nanometer to nanometer scale over technologically relevant large areas, and suggests the potential use of intrinsic defects in atomically thin materials for molecular separations or desalting.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Realization of highly crystallographic three-dimensional nanosheets by a stress-induced oriented-diffusion method

Morphologically controlled nanostructures have been increasingly important because of their strongly shape dependent physical and chemical properties. Formation of nanoscale silicon based structures that employ high levels of strain, intentional, and unintentional twins or grain boundaries can be dramatically different from the commonly conceived bulk processes. We report, realization of highly crystallographic 3D nanosheets with unique morphology and ultra-thin thickness by a stress-induced oriented-diffusion method, based on plasma processing of metal layer deposited on Si substrate and its post deep reactive ion etching. Annealing in plasma ambient creates rod-like metal alloy precursors which induce stress at its interface with Si substrate due to the mismatch of lattice constants. This stress opens facilitated gateways for orientated-diffusion of metal atoms in 〈110〉 directions and leads to formation of NSs (nanosheets) with [111] crystalline essence. Nanosheets are mainly triangular, hexagonal, or pseudo hexagonal in shape and their thicknesses are well controlled from several to tens of nanometers. The structural and morphological evolution of features were investigated in detail using transmission electron microscope, atomic force microscope, scanning electron microscope and possible mechanism is proposed to explain the formation of the thermodynamically unfavorable morphology of nanosheets. Significant photoemission capability of NSs was also demonstrated by photoluminescence spectroscopy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Transformation of 2D group-III selenides to ultra-thin nitrides: enabling epitaxy on amorphous substrates

Here, the experimental realization of two-dimensional (2D) gallium nitride (GaN) has enabled the exploration of 2D nitride materials beyond boron nitride. Here we demonstrate one possible pathway to realizing ultra-thin nitride layers through a two-step process involving the synthesis of naturally layered, group-III chalcogenides (GIIIC) and subsequent annealing in ammonia (ammonolysis) that leads to an atomic-exchange of the chalcogen and nitrogen species in the 2D-GIIICs. The effect of nitridation differs for gallium and indium selenide, where gallium selenide undergoes structural changes and eventual formation of ultra-thin GaN, while indium selenide layers are primarily etched rather than transformed by nitridation. Further investigation of the resulting GaN films indicates that ultra-thin GaN layers grown on silicon dioxide act as effective 'seed layers' for the growth of 3D GaN on amorphous substrates.

2D materials↗
DOE OSTI2015

Cerium Oxide Nanoclusters on Graphene/Ru(0001): Intercalation of Oxygen via Spillover

Cerium oxide is an important catalytic material known for its ability to store and release oxygen, and as such, it has been used in a range of applications, both as an active catalyst and as a catalyst support. Using scanning tunneling microscopy and Auger electron spectroscopy, we investigated oxygen interactions with CeOx nanoclusters on a complete graphene monolayer-covered Ru(0001) surface at elevated temperatures (600 – 725 K). Under oxidizing conditions (P_(O_2 ) = 1 × 10-7 Torr), oxygen intercalation under the graphene layer is observed. Time dependent studies demonstrate that the intercalation proceeds via spillover of oxygen from CeOx nanoclusters through the graphene (Gr) layer onto the Ru(0001) substrate and extends until the Gr layer is completely intercalated. Atomically resolved images further show that oxygen forms a p(2×1) structure underneath the Gr monolayer. Temperature dependent studies yield an apparent kinetic barrier for the intercalation of 1.26 eV. This value correlates well with the theoretically determined value for the reduction of small CeO2 clusters reported previously. At higher temperatures, the intercalation is followed by a slower etching of the intercalated graphene (apparent barrier of 1.64 eV). Vacuum annealing of the intercalated Gr leads to the formation of carbon monoxide, causing etching of the graphene film, demonstrating that the spillover of oxygen is not reversible. In agreement with previous studies, no intercalation is observed on a complete graphene monolayer without CeOx clusters, even in the presence of a large number of point defects. These studies demonstrate that the easily reducible CeOx clusters act as intercalation gateways capable of efficiently delivering oxygen underneath the graphene layer.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2021

Phase-Controllable Synthesis of Ultrathin Molybdenum Nitride Crystals Via Atomic Substitution of MoS 2

MXenes are emerging members in the two-dimensional (2D) material family and are highlighted by their high electrical conductivity. Among different MXenes, molybdenum-based MXenes, especially molybdenum nitrides (MoN x ), are rarely accessible through the common synthetic approach of selective etching due to the absence of stable MAX phase precursors. In this work, we apply the atomic substitution approach to synthesize two phases of ultrathin nonlayered molybdenum nitrides (i.e., Mo 5 N 6 and δ-MoN) from 1.6 to 42.9 nm thickness by converting layered MoS 2 under different temperatures. The morphology and 2D nature of MoS 2 are well remained in both phases. These newly created 2D materials are further characterized using Raman spectroscopy, high-resolution transmission electron microscopy, and electrical measurements, suggesting that both phases are highly crystalline and highly conductive down to the thickness of a few nanometers. Moreover, Ohmic contacts are formed between the ultrathin nitrides and Cr/Au electrodes, suggesting the great potential of the obtained nitrides for nanoelectronic device applications. The stability test shows that the Ohmic contact is well maintained after 4 weeks under ambient conditions with a slight degradation in conductivity. Furthermore, this study extends the 2D family by providing highly conductive members, offering desired building blocks for solid-state nanoelectronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

In Situ Analysis of Electron-Induced Chemical Transformations in Vapor-Phase-Synthesized Al-Based Inorganic–Organic Hybrid Thin Films for EUV Resist Platform

The rapid advancement and stringent requirements of extreme ultraviolet (EUV) lithography technology necessitate the development of advanced photoresist systems for next-generation microelectronics. Recent studies have demonstrated that inorganic-based hybrid photoresists offer notable improvements in EUV sensitivity, etch resistance, and greater insusceptibility to pattern collapse compared to their purely organic counterparts. However, variations in the synthesis/coating approaches and chemistry of inorganic–organic photoresists can result in distinct exposure mechanisms. In this work, an Al-based hybrid thin film resist system synthesized via molecular (atomic) layer deposition (MLD or MALD) is explored, focusing on its electron-beam and EUV patterning mechanisms. The Al-based hybrid thin films are deposited using trimethylaluminum (TMA) and the organic precursor hydroquinone, exhibiting a saturated growth rate within the temperature range of 150–200°C. In diluted tetramethylammonium hydroxide (TMAH)-based developer solutions, the electron-irradiated Al-based hybrid thin film system behaves as a negative tone resist, achieving a sensitivity of 10.4 mC/cm 2 at 0.1 kV electron beam lithography (EBL). Chemical changes induced by electron exposure are also analyzed in this study using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and a unique infrared spectroscopy setup, revealing the potential cross-linking pathways. To further correlate the electron-induced chemical transformations with those mediated by EUV irradiations, a combination of X-ray photoemission electron microscopy/low-energy electron microscopy (XPEEM/LEEM) system is also employed. In conclusion, this study provides critical insights into the mechanisms underlying solubility switching and contributes to the design of advanced resist materials for EUV lithography.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Long Range Chiral Imprinting of Cu(110) by Tartaric Acid

Restructuring of metals by chiral molecules represents an important route to inducing and controlling enantioselective surface chemistry. Tartaric acid adsorption on Cu(110) has served as a useful system for understanding many aspects of chiral molecule adsorption and ordering on a metal surface, and a number of chiral and achiral unit cells have been reported. Herein, we show that given the appropriate annealing treatment, singly deprotonated tartaric acid monolayers can restructure the Cu metal itself, and that the resulting structure is both highly ordered and chiral. Molecular resolution scanning tunneling microscopy reveals that singly deprotonated tartaric acid extracts Cu atoms from the Cu(110) surface layer and incorporates them into highly ordered, chiral adatom arrays capped by a continuous molecular layer. Further evidence for surface restructuring comes from images of atom-deep trenches formed in the Cu(110) surface during the process. These trenches also run in low symmetry directions and are themselves chiral. Simulated scanning tunneling microscopy images are consistent with the appearance of the added atom rows and etched trenches. The chiral imprinting results in a long-range, highly ordered unit cell covering the whole surface as confirmed by low energy electron diffraction. Details of the restructuring mechanism were further investigated via time-lapse imaging at elevated temperature. This work reveals the stages of nanoscale surface restructuring and offers an interesting method for chiral modification of an achiral metal surface.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Scanning Kelvin Probe Microscopy: A Tool to Investigate Nano-Scale Doping Non-Uniformities in Poly-Si/SiOx Contacts: Preprint

Monocrystalline Si (c-Si) solar cells with passivated contacts based on the ultrathin SiOx and doped polycrystalline Si (poly-Si) layers in a poly-Si/SiOx/c Si structure show high solar cell efficiencies that are ~26%. Excellent surface passivation using these contacts is achieved via the combined effects of chemical passivation of the SiOx/c-Si interface by the SiOx layer and field-effect passivation from the heavily doped poly-Si layer. These contacts give best performance only when annealed to temperatures higher than 850 degrees C. Structural changes in the SiOx layer and dopant diffusion from poly-Si into the underlying c-Si wafer occur during this step which are hard to investigate using conventional characterization techniques. In this work we investigate poly-Si/SiOx contacts with both a 1.5 (tunneling transport) and 2.2 (pinhole transport) nm SiOx layer using atomic force microscopy techniques. Conductive AFM on n+-poly-Si/SiOx/p-Si structures show significant spatial variations for both contact types, likely due to non-uniformities in the poly-Si layer itself. The electrical and structural variations deeper into the contact were revealed by scanning Kelvin probe microscopy after precisely etching away the poly-Si and SiOx layers and few nanometers of c-Si surface. This etching was performed using tetramethylammonium hydroxide and dilute HF solutions. The resulting surface potential maps appear similar for both contacts, and show less than 500 nm size heavily-doped regions. However, further etching of the c-Si surface reveals these heavily-doped regions to be less than 200 nm deep for the 2.2 nm SiOx contact and greater than 200 nm deep for the 1.5 nm SiOx contact.

14 SOLAR ENERGY↗
DOE OSTI2016

Poly(cyclohexylethylene)- block -Poly(lactide) Oligomers for Ultrasmall Nanopatterning Using Atomic Layer Deposition

Poly(cyclohexylethylene)-block-poly(lactide) (PCHE–PLA) block polymers were synthesized through a combination of anionic polymerization, heterogeneous catalytic hydrogenation and controlled ring-opening polymerization. Ordered thin films of PCHE–PLA with ultrasmall hexagonally packed cylinders oriented perpendicularly to the substrate surface were prepared by spin-coating and subsequent solvent vapor annealing for use in two distinct templating strategies. In one approach, selective hydrolytic degradation of the PLA domains generated nanoporous PCHE templates with an average pore diameter of 5 ± 1 nm corroborated by atomic force microscopy and grazing incidence small-angle X-ray scattering. Alternatively, sequential infiltration synthesis (SIS) was employed to deposit Al 2 O 3 selectively into the PLA domains of PCHE–PLA thin films. A combination of argon ion milling and O2 reactive ion etching (RIE) enabled the replication of the Al 2 O 3 nanoarray from the PCHE–PLA template on diverse substrates including silicon and gold with feature diameters less than 10 nm.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Metal-Confined Synthesis of ZnS 2 Monolayer Catalysts for Dinitrogen Electroreduction

Atomically thin two-dimensional (2D) materials are of great significance in catalytic, energy storage, and electronic devices. So far, such materials are limited to several categories with layered structures. Herein, we predict an unusual atomically thin ZnS2 monolayer and exploit a metal-confined chemical vapor deposition strategy for the successful preparation of such an unprecedented 2D material, where a sulfide monolayer was first grown on metal nanosheets to form a sulfide/metal/sulfide sandwich structure, and then, the metal core was etched out to obtain freestanding sulfide monolayers. As shown in this work, the ZnS 2 monolayer possesses unique electron-deficient properties related to the atomic structure and exhibits high catalytic activity for dinitrogen electroreduction. Our work will enable creating 2D TMD materials that were previously inexistent or inaccessible.

2D Materials↗
DOE OSTI2013

In situ study of the role of substrate temperature during atomic layer deposition of HfO{sub 2} on InP

The dependence of the “self cleaning” effect of the substrate oxides on substrate temperature during atomic layer deposition (ALD) of HfO{sub 2} on various chemically treated and native oxide InP (100) substrates is investigated using in situ X-ray photoelectron spectroscopy. The removal of In-oxide is found to be more efficient at higher ALD temperatures. The P oxidation states on native oxide and acid etched samples are seen to change, with the total P-oxide concentration remaining constant, after 10 cycles of ALD HfO{sub 2} at different temperatures. An (NH{sub 4}){sub 2} S treatment is seen to effectively remove native oxides and passivate the InP surfaces independent of substrate temperature studied (200 °C, 250 °C and 300 °C) before and after the ALD process. Density functional theory modeling provides insight into the mechanism of the changes in the P-oxide chemical states.

36 MATERIALS SCIENCE↗