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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Characterizing the Three-Dimensional Structure of Block Copolymers via Sequential Infiltration Synthesis and Scanning Transmission Electron Tomography

Understanding and controlling the three-dimensional structure of block copolymer (BCP) thin films is critical for utilizing these materials for sub-20 nm nanopatterning in semiconductor devices, as well as in membranes and solar cell applications. Combining an atomic layer deposition (ALD) based technique for enhancing the contrast of BCPs in transmission electron microscopy (TEM) together with scanning TEM (STEM) tomography reveals and characterizes the three-dimensional structures of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) thin films with great clarity. Sequential infiltration synthesis (SIS), a block-selective technique for growing inorganic materials in BCPs films in ALD, and an emerging tool for enhancing the etch contrast of BCPs, was harnessed to significantly enhance the high-angle scattering from the polar domains of BCP films in the TEM. The power of combining SIS and STEM tomography for three dimensional (3D) characterization of BCPs films was demonstrated with the following cases: self-assembled cylindrical, lamellar, and spherical PS-PMMA thin films. In all cases, STEM tomography has revealed 3D structures that were hidden underneath the surface, including: 1) the 3D structure of defects in cylindrical and lamellar phases, 2) non-perpendicular 3D surface of grain boundaries in the cylindrical phase, and 3) the 3D arrangement of spheres in body centered cubic (BCC) and hexagonal closed pack (HCP) morphologies in the spherical phase. The 3D data of the spherical morphologies was compared to coarse-grained simulations and assisted in validating the simulations’ parameters. STEM tomography of SIS-treated BCP films enables the characterization of the exact structure used for pattern transfer, and can lead to better understating of the physics which is utilized in BCP lithography.

Block copolymers↗
DOE OSTI2026

Nanoionics Drastically Accelerating Mass Transfer at Elevated Temperatures over 750 °C

Nanoionics were previously considered thermally unstable and infeasible for devices operating above 500 °C. Here, we elucidate the design principle for establishing stable nanoionics from various oxides. We utilized reversible solid oxide cells (SOCs) as the test bed and implemented nanoionics using atomic layer deposition (ALD). We demonstrate a straightforward, interface-controlled, practical approach to render a conformal, ∼15 nm thick ALD film, which initially thermodynamically favors the formation of a solid solution with the substrate into surface nanoionics with single or double layers of nanograins with random crystal orientations. The nanoionics exhibited conductivity estimated to be 7 orders of magnitude higher than that of their bulk-scale counterpart. They demonstrated conformability with uniform grain sizes of ∼15 nm, even after electrochemical operation for ∼500 h at 750 °C and 1000 h at 850 °C. The thermal stability and conductivity of such nanoionics represent a conceptual and technological framework in nanoionics.

atomic layer deposition↗
DOE OSTI2026

Polymer-Derived Amorphous Aluminosilicate Nanomembranes for H 2 Purification

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

36 MATERIALS SCIENCE↗
DOE OSTI2017

Rational Design of Hyperbranched Nanowire Systems for Tunable Superomniphobic Surfaces Enabled by Atomic Layer Deposition

A method for tunable control of geometry in hyperbranched ZnO nanowire (NW) systems is reported, which enables the rational design and fabrication of superomniphobic surfaces. Branched NWs with tunable density and orientation were grown via a sequential hydrothermal process, in which atomic layer deposition (ALD) was used for NW seeding, disruption of epitaxy, and selective blocking of NW nucleation. This approach allows for the rational design and optimization of three-level hierarchical structures, in which the geometric parameters of each level of hierarchy can be individually controlled. We demonstrate the coupled relationships between geometry and contact angle for a variety of liquids, which is supported by mathematical models of structural superomniphobicity. The highest performing superomniphobic surface was designed with three levels of hierarchy and achieved the following advancing/receding contact angles, water: 172°/170°, hexadecane: 166°/156°, octane: 162°/145°, and heptane: 160°/130°. Low surface tension liquids were shown to bounce off the surface from a height of 7 cm without breaking through and wetting. This approach demonstrates the power of ALD as an enabling technique for hierarchical materials by design, spanning the macro, micro, and nano length scales.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Oxygen-Free Atomic Layer Deposition of Indium Sulfide

Atomic layer deposition (ALD) of indium sulfide (In2S3) films was achieved using a newly synthesized indium precursor and hydrogen sulfide. We obtain dense and adherent thin films free from halide and oxygen impurities. Self-limiting half-reactions are demonstrated at temperatures up to 200°C, where oriented crystalline thin films are obtained without further annealing. Low temperature growth of 0.89 Å/cycle is observed at 150°C while higher growth temperatures gradually reduce the per-cycle growth rate. Rutherford backscattering spectroscopy (RBS) together with depth-profiling Auger electron spectroscopy (AES) reveal a S/In ratio of 1.5 with no detectable carbon, nitrogen, halogen, or oxygen impurities. The resistivity of thin films prior to air exposure decreases with increasing deposition temperature, reaching <1 ohm-cm for films deposited at 225°C. Hall measurements reveal n-type conductivity due to free electron concentrations up to 1018 cm-3 and mobilities of order 1 cm2/(V*s). The digital synthesis of In2S3 via ALD at temperatures up to 225°C may allow high quality thin films to be leveraged in optoelectronic devices including photovoltaic absorbers, buffer layers, and intermediate band materials.

Atomic layer deposition↗
DOE OSTI2014

Fabrication of Transparent-Conducting-Oxide-Coated Inverse Opals as Mesostructured Architectures for Electrocatalysis Applications: A Case Study with NiO

Highly ordered, and conductive inverse opal arrays were made with silica and subsequently coated with tin-doped indium oxide (ITO) via atomic layer deposition (ALD). We demonstrate the utility of the resulting mesostructured electrodes by further coating them with nickel oxide via ALD. The NiO-coated arrays are capable of efficiently electrochemically evolving oxygen from water. These modular, crack-free, transparent, high surface area, and conducting structures show promise for many applications including electrocatalysis, photocatalysis, and dye-sensitized solar cells.

Williams, Vennesa O.↗
DOE OSTI2013

Dye Stabilization and Enhanced Photoelectrode Wettability in Water-Based Dye-Sensitized Solar Cells through Post-assembly Atomic Layer Deposition of TiO 2

Detachment (desorption) of molecular dyes from photoelectrodes is one of the major limitations for the long-term operation of dye-sensitized solar cells. Here we demonstrate a method to greatly inhibit this loss by growing a transparent metal oxide (TiO2) on the dye-coated photoelectrode via atomic layer deposition (ALD). TiO2-enshrouded sensitizers largely resist detachment, even in pH 10.7 ethanol, a standard solution for intentional removal of molecular dyes from photoelectrodes. Additionally, the ALD post-treatment renders the otherwise hydrophobic dye-coated surface hydrophilic, thereby enhancing photoelectrode pore-filling with aqueous solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Unveiling the Stability of Encapsulated Pt Catalysts Using Nanocrystals and Atomic Layer Deposition

Platinum exhibits desirable catalytic properties, but it is scarce and expensive. Optimizing its use in key applications such as emission control catalysis is important to reduce our reliance on such a rare element. Supported Pt nanoparticles (NPs) used in emission control systems deactivate over time because of particle growth in sintering processes. Here, in this work, we shed light on the stability against sintering of Pt NPs supported on and encapsulated in Al 2 O 3 using a combination of nanocrystal catalysts and atomic layer deposition (ALD) techniques. We find that small amounts of alumina overlayers created by ALD on preformed Pt NPs can stabilize supported Pt catalysts, significantly reducing deactivation caused by sintering, as previously observed by others. Combining theoretical and experimental insights, we correlate this behavior to the decreased propensity of oxidized Pt species to undergo Ostwald ripening phenomena because of the physical barrier imposed by the alumina overlayers. Furthermore, we find that highly stable catalysts can present an abundance of under-coordinated Pt sites after restructuring of both Pt particles and alumina overlayers at a high temperature (800 °C) in C 3 H 6 oxidation conditions. The enhanced stability significantly improves the Pt utilization efficiency after accelerated aging treatments, with encapsulated Pt catalysts reaching reaction rates more than two times greater than those of a control supported Pt catalyst.

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

Sintering-resistant Single-Site Nickel Catalyst Supported by Metal-Organic Framework

Developing supported single-site catalysts is an important goal in heterogeneous catalysis, since the well-defined active sites afford opportunities for detailed mechanistic studies, thereby facilitating the design of improved catalysts. We present herein a method for installing Ni ions uniformly and precisely on the node of a Zr-based MOF, NU-1000, in high density and large quantity (denoted as Ni-AIM) using atomic layer deposition (ALD) in a metal–organic framework (MOF) (AIM). Ni-AIM is demonstrated to be an efficient gas-phase hydrogenation catalyst upon activation. The structure of the active sites in Ni-AIM is proposed, revealing its single-site nature. More importantly, due to the organic linker used to construct the MOF support, the Ni ions stay isolated throughout the hydrogenation catalysis, in accord with its long-term stability. A quantum chemical characterization of the catalyst and the catalytic process complements the experimental results. With validation of computational modeling protocols, we further targeted ethylene oligomerization catalysis by Ni-AIM guided by theoretical prediction. Given the generality of the AIM methodology, this emerging class of materials should prove ripe for the discovery of new catalysts for the transformation of volatile substrates.

Li, Zhanyong↗
DOE OSTI2017

Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. We resolved the atomic structure of Ni-oxo species deposited in the MOF NU-1000 through atomic layer deposition using local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and difference envelope density analysis, with electron microscopy imaging and computational modeling.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2019

Colloidal Atomic Layer Deposition with Stationary Reactant Phases Enables Precise Synthesis of “Digital” II–VI Nano-heterostructures with Exquisite Control of Confinement and Strain

In contrast to molecular systems, which are defined with atomic precision, nanomaterials generally show some heterogeneity in size, shape, and composition. The sample inhomogeneity translates into a distribution of energy levels, band gaps, work functions, and other characteristics, which detrimentally affect practically every property of functional nanomaterials. Here, we introduce a novel synthetic strategy, colloidal atomic layer deposition (c-ALD) with stationary reactant phases, which largely circumvents the limitations of traditional colloidal syntheses of nano-heterostructures with atomic precision. This method allows for significant reduction of inhomogeneity in nanomaterials in complex nanostructures without compromising their structural perfection and enables the synthesis of epitaxial nano-heterostructures of unprecedented complexity. The improved synthetic control ultimately enables bandgap and strain engineering in colloidal nanomaterials with close to atomic accuracy. To demonstrate the power of the new c-ALD method, we synthesize a library of complex II–VI semiconductor nanoplatelet heterostructures. By combining spectroscopic and computational studies, we elucidate the subtle interplay between quantum confinement and strain effects on the optical properties of semiconductor nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Enhanced photoelectrochemical efficiency and stability using a conformal TiO 2 film on a black silicon photoanode

Black silicon (b-Si) is a surface-nanostructured Si with extremely efficient light absorption capability and is therefore of interest for solar energy conversion. However, intense charge recombination and low electrochemical stability limit the use of b-Si in photoelectrochemical solar-fuel production. Here we report that a conformal, ultrathin, amorphous TiO 2 film deposited by low-temperature atomic layer deposition (ALD) on top of b-Si can simultaneously address both of these issues. Combined with a Co(OH) 2 thin film as the oxygen evolution catalyst, this b-Si/TiO 2 /Co(OH) 2 heterostructured photoanode was able to produce a saturated photocurrent density of 32.3 mA cm –2 at an external potential of 1.48 V versus reversible reference electrode (RHE) in 1 M NaOH electrolyte. The enhanced photocurrent relative to planar Si and unprotected b-Si photoelectrodes was attributed to the enhanced charge separation efficiency as a result of the effective passivation of defective sites on the b-Si surface. The 8-nm ALD TiO 2 layer extends the operational lifetime of b-Si from less than half an hour to four hours.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Nanoionics and Nanocatalysts: Conformal Mesoporous Surface Scaffold for Cathode of Solid Oxide Fuel Cells

Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO 2 nanoionic network was formed on the surface of La 1–x Sr x MnO 3 /yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650–800 °C for 400 hours. The stable mesoporous ZrO 2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. As a result, the power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5–1.7 operated at 0.8 V at 750 °C.

25 ENERGY STORAGE↗
DOE OSTI2016

570 mV photovoltage, stabilized n-Si/CoO x heterojunction photoanodes fabricated using atomic layer deposition

Heterojunction photoanodes, consisting of n-type crystalline Si(100) substrates coated with a thin ~50 nm film of cobalt oxide fabricated using atomic-layer deposition (ALD), exhibited photocurrent-onset potentials of -205 ± 20 mV relative to the formal potential for the oxygen-evolution reaction (OER), ideal regenerative solar-to-O 2 (g) conversion efficiencies of 1.42 ± 0.20%, and operated continuously for over 100 days (~2500 h) in 1.0 M KOH(aq) under simulated solar illumination. The ALD CoO x thin film: (i) formed a heterojunction with the n-Si(100) that provided a photovoltage of 575 mV under 1 Sun of simulated solar illumination; (ii) stabilized Si photoanodes that are otherwise unstable when operated in aqueous alkaline electrolytes; and, (iii) catalyzed the oxidation of water, thereby reducing the kinetic overpotential required for the reaction and increasing the overall efficiency relative to electrodes that do not have an inherently electrocatalytic coating. The process provides a simple, effective method for enabling the use of planar n-Si(100) substrates as efficient and durable photoanodes in fully integrated, photovoltaic-biased solar fuels generators.

14 SOLAR ENERGY↗
DOE OSTI2016

Second-generation hexavalent molybdenum oxo-amidinate precursors for atomic layer deposition

Here, the synthesis of molybdenum oxo-amidinate complexes MoO 2 (R 2 AMD) 2 [AMD = N,N'-di-R-acetamidinate; R = Cy (2; cyclohexyl) and iPr (3)], and their characterization by 1 H, 13 C NMR, X-ray diffraction, and thermogravimetric analysis is reported. Quartz-crystal microbalance and X-ray photoelectron spectroscopic studies confirm that 3 is an improved ALD precursor versus the R = t-butyl derivative for MoO 3 film growth. Complex 3 is accessible in higher yields (80%+), is easier to handle without mass loss, and in conjunction with O 3 as the second ALD reagent, yields nitride-free MoO 3 films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Tuning the properties of metal–organic framework nodes as supports of single-site iridium catalysts: node modification by atomic layer deposition of aluminium

The metal–organic framework NU-1000, with Zr 6 -oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al( iii ) ions by ALD-like chemistry with [Al(CH 3 ) 2 (iso-propoxide)] 2 followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C 2 H 4 ) 2 (acac) (acac = acetylacetonate) and converted to Ir(CO) 2 complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly, the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al( iii ) ions are in qualitative agreement with some catalyst performance data.

catalysis (heterogeneous), materials and chemistry↗