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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 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Atomic layer deposition of tin oxide and zinc tin oxide using tetraethyltin and ozone

Silicon or glass substrates exposed to sequential pulses of tetraethyltin (TET) and ozone (O{sub 3}) were coated with thin films of SnO{sub 2}. Self-limiting deposition was found using 8 s pulse times, and a uniform thickness per cycle (TPC) of 0.2 nm/cycle was observed in a small, yet reproducible, temperature window from 290 to 320 °C. The as-deposited, stoichiometric SnO{sub 2} films were amorphous and transparent above 400 nm. Interspersing pulses of diethylzinc and O{sub 3} among the TET:O{sub 3} pulses resulted in deposition of zinc tin oxide films, where the fraction of tin, defined as [at. % Sn/(at. % Sn + at. % Zn)], was controlled by the ratio of TET pulses, specifically n{sub TET}:(n{sub TET} + n{sub DEZ}) where n{sub TET} and n{sub DEZ} are the number of precursor/O{sub 3} subcycles within each atomic layer deposition (ALD) supercycle. Based on film thickness and composition measurements, the TET pulse time required to reach saturation in the TPC of SnO{sub 2} on ZnO surfaces was increased to >30 s. Under these conditions, film stoichiometry as a function of the TET pulse ratio was consistent with the model devised by Elliott and Nilsen. The as-deposited zinc tin oxide (ZTO) films were amorphous and remained so even after annealing at 450 °C in air for 1 h. The optical bandgap of the transparent ZTO films increased as the tin concentration increased. Hall measurements established that the n-type ZTO carrier concentration was 3 × 10{sup 17} and 4 × 10{sup 18} cm{sup −3} for fractional tin concentrations of 0.28 and 0.63, respectively. The carrier mobility decreased as the concentration of tin increased. A broken gap pn junction was fabricated using ALD-deposited ZTO and a sputtered layer of cuprous oxide. The junction demonstrated ohmic behavior and low resistance consistent with similar junctions prepared using sputter-deposited ZTO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Influence of atomic layer deposition valve temperature on ZrN plasma enhanced atomic layer deposition growth

Atomic layer deposition (ALD) relies on a sequence of self-limiting surface reactions for thin film growth. The effect of non-ALD side reactions, from insufficient purging between pulses and from precursor self-decomposition, on film growth is well known. In this article, precursor condensation within an ALD valve is described, and the effect of the continuous precursor source from condensate evaporation on ALD growth is discussed. The influence of the ALD valve temperature on growth and electrical resistivity of ZrN plasma enhanced ALD (PEALD) films is reported. Increasing ALD valve temperature from 75 to 95 °C, with other process parameters being identical, decreased both the growth per cycle and electrical resistivity (ρ) of ZrN PEALD films from 0.10 to 0.07 nm/cycle and from 560 to 350 μΩ cm, respectively. Our results show that the non-ALD growth resulting from condensate accumulation is eliminated at valve temperatures close to the pressure corrected boiling point of precursor.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Atomic layer deposition of alternative glass microchannel plates

The technique of atomic layer deposition (ALD) has enabled the development of alternative glass microchannel plates (MCPs) with independently tunable resistive and emissive layers, resulting in excellent thickness uniformity across the large area (20 × 20 cm), high aspect ratio (60:1 L/d) glass substrates. Furthermore, the use of ALD to deposit functional layers allows the optimal substrate material to be selected, such as borosilicate glass, which has many benefits compared to the lead-oxide glass used in conventional MCPs, including increased stability and lifetime, low background noise, mechanical robustness, and larger area (at present up to 400 cm{sup 2}). Resistively stable, high gain MCPs are demonstrated due to the deposition of uniform ALD resistive and emissive layers on alternative glass microcapillary substrates. The MCP performance characteristics reported include increased stability and lifetime, low background noise (0.04 events cm{sup −2} s{sup −1}), and low gain variation (±5%)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Spatial atomic layer deposition on flexible porous substrates: ZnO on anodic aluminum oxide films and Al{sub 2}O{sub 3} on Li ion battery electrodes

Spatial atomic layer deposition (S-ALD) was examined on flexible porous substrates utilizing a rotating cylinder reactor to perform the S-ALD. S-ALD was first explored on flexible polyethylene terephthalate polymer substrates to obtain S-ALD growth rates on flat surfaces. ZnO ALD with diethylzinc and ozone as the reactants at 50 °C was the model S-ALD system. ZnO S-ALD was then performed on nanoporous flexible anodic aluminum oxide (AAO) films. ZnO S-ALD in porous substrates depends on the pore diameter, pore aspect ratio, and reactant exposure time that define the gas transport. To evaluate these parameters, the Zn coverage profiles in the pores of the AAO films were measured using energy dispersive spectroscopy (EDS). EDS measurements were conducted for different reaction conditions and AAO pore geometries. Substrate speeds and reactant pulse durations were defined by rotating cylinder rates of 10, 100, and 200 revolutions per minute (RPM). AAO pore diameters of 10, 25, 50, and 100 nm were utilized with a pore length of 25 μm. Uniform Zn coverage profiles were obtained at 10 RPM and pore diameters of 100 nm. The Zn coverage was less uniform at higher RPM values and smaller pore diameters. These results indicate that S-ALD into porous substrates is feasible under certain reaction conditions. S-ALD was then performed on porous Li ion battery electrodes to test S-ALD on a technologically important porous substrate. Li{sub 0.20}Mn{sub 0.54}Ni{sub 0.13}Co{sub 0.13}O{sub 2} electrodes on flexible metal foil were coated with Al{sub 2}O{sub 3} using 2–5 Al{sub 2}O{sub 3} ALD cycles. The Al{sub 2}O{sub 3} ALD was performed in the S-ALD reactor at a rotating cylinder rate of 10 RPM using trimethylaluminum and ozone as the reactants at 50 °C. The capacity of the electrodes was then tested versus number of charge–discharge cycles. These measurements revealed that the Al{sub 2}O{sub 3} S-ALD coating on the electrodes enhanced the capacity stability. This S-ALD process could be extended to roll-to-roll operation for the commercialization of S-ALD for coating Li ion battery electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Standing and sitting adlayers in atomic layer deposition of ZnO

The extent of reactivity of diethyl zinc (DEZ) with a hydroxylated surface during atomic layer deposition (ALD) of ZnO using DEZ and water is measured. Two adlayer configurations of DEZ are possible. The “standing” adlayer releases one ethyl group from DEZ. The “sitting” adlayer releases both ethyl groups, thus forming a Zn bridge between two O anions. Density functional theory calculations suggest the sitting configuration is more stable than the standing configuration by 790 meV. In situ quadrupole mass spectroscopy of by-product ethane generated in ALD half cycles indicate that ∼1.56 OH sites react with a DEZ molecule resulting in 71.6% of sitting sites. A simple simulation of a “ball-and-stick” DEZ molecule randomly collapsing on a neighboring site remarkably captures this adlayer behavior. It is concluded that DEZ fraction sitting is a competitive process of a standing DEZ molecule collapsing onto an available neighboring hydroxyl site, as sites vie for occupancy via adsorption and surface diffusion.

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

Effect of the chamber wall on fluorocarbon-assisted atomic layer etching of SiO{sub 2} using cyclic Ar/C{sub 4}F{sub 8} plasma

The authors studied the effect of the temperature and chemical state of the chamber wall on process performance for atomic layer etching of SiO{sub 2} using a steady-state Ar plasma, periodic injection of a defined number of C{sub 4}F{sub 8} molecules, and synchronized plasma-based Ar{sup +} ion bombardment. To evaluate these effects, the authors measured the quartz coupling window temperature. The plasma gas phase chemistry was characterized using optical emission spectroscopy. It was found that although the thickness of the polymer film deposited in each cycle is constant, the etching behavior changed, which is likely related to a change in the plasma gas phase chemistry. The authors found that the main gas phase changes occur after C{sub 4}F{sub 8} injection. The C{sub 4}F{sub 8} and the quartz window react and generate SiF and CO. The emission intensity changes with wall surface state and temperature. Therefore, changes in the plasma gas species generation can lead to a shift in etching performance during processing. During initial cycles, minimal etching is observed, while etching gradually increases with cycle number.

42 ENGINEERING↗
DOE OSTI2016

Fluorocarbon based atomic layer etching of Si{sub 3}N{sub 4} and etching selectivity of SiO{sub 2} over Si{sub 3}N{sub 4}

Angstrom-level plasma etching precision is required for semiconductor manufacturing of sub-10 nm critical dimension features. Atomic layer etching (ALE), achieved by a series of self-limited cycles, can precisely control etching depths by limiting the amount of chemical reactant available at the surface. Recently, SiO{sub 2} ALE has been achieved by deposition of a thin (several Angstroms) reactive fluorocarbon (FC) layer on the material surface using controlled FC precursor flow and subsequent low energy Ar{sup +} ion bombardment in a cyclic fashion. Low energy ion bombardment is used to remove the FC layer along with a limited amount of SiO{sub 2} from the surface. In the present article, the authors describe controlled etching of Si{sub 3}N{sub 4} and SiO{sub 2} layers of one to several Angstroms using this cyclic ALE approach. Si{sub 3}N{sub 4} etching and etching selectivity of SiO{sub 2} over Si{sub 3}N{sub 4} were studied and evaluated with regard to the dependence on maximum ion energy, etching step length (ESL), FC surface coverage, and precursor selection. Surface chemistries of Si{sub 3}N{sub 4} were investigated by x-ray photoelectron spectroscopy (XPS) after vacuum transfer at each stage of the ALE process. Since Si{sub 3}N{sub 4} has a lower physical sputtering energy threshold than SiO{sub 2}, Si{sub 3}N{sub 4} physical sputtering can take place after removal of chemical etchant at the end of each cycle for relatively high ion energies. Si{sub 3}N{sub 4} to SiO{sub 2} ALE etching selectivity was observed for these FC depleted conditions. By optimization of the ALE process parameters, e.g., low ion energies, short ESLs, and/or high FC film deposition per cycle, highly selective SiO{sub 2} to Si{sub 3}N{sub 4} etching can be achieved for FC accumulation conditions, where FC can be selectively accumulated on Si{sub 3}N{sub 4} surfaces. This highly selective etching is explained by a lower carbon consumption of Si{sub 3}N{sub 4} as compared to SiO{sub 2}. The comparison of C{sub 4}F{sub 8} and CHF{sub 3} only showed a difference in etching selectivity for FC depleted conditions. For FC accumulation conditions, precursor chemistry has a weak impact on etching selectivity. Surface chemistry analysis shows that surface fluorination and FC reduction take place during a single ALE cycle for FC depleted conditions. A fluorine rich carbon layer was observed on the Si{sub 3}N{sub 4} surface after ALE processes for which FC accumulation takes place. The angle resolved-XPS thickness calculations confirmed the results of the ellipsometry measurements in all cases.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Tailoring nanopore formation in atomic layer deposited ultrathin films [Nanopore formation in atomic layer deposited ultrathin films]

Selectivity is a critical attribute of catalysts used in manufacturing of essential and fine chemicals. An excellent way to induce selectivity in catalysts is by using ultrathin films with tailored nanoporosity. For instance, nanopores can be created in atomic layer deposition (ALD) ultrathin over-coatings on supported metal nanoparticles by subjecting the coatings to high temperature annealing. These nanopores expose the active surface of the underlying metal nanoparticles. The dimensions of these nanopores can be tuned to impart shape selectivity: only reactants or products with a specific size or shape can fit inside the pore. In this work, the authors explore the underlying mechanism driving nanopore formation in ALD films. Ultrathin films of ALD TiO 2 (similar to 2.5 nm thick) and ALD Al 2 O 3 (similar to 4.9 nm thick) were deposited on nonporous gamma-Al 2 O 3 nanoparticles. The pore formation and evolution were monitored in situ during thermal annealing using small-angle x-ray scattering (SAXS), and the crystallinity was monitored by in situ x-ray diffraction. A correlation between the nanopore formation and amorphous to crystalline phase transitions in the ALD layers was observed. The authors hypothesize that the pores form through the relaxation of stress induced by densification of the ALD films during the phase transitions. In conclusion, the authors developed a mathematical model to evaluate this hypothesis and found remarkable agreement between the model and the SAXS measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Atomic layer deposition of molybdenum disulfide films using MoF 6 and H 2 S

Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF6) and hydrogen sulfide at 200 degrees C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46 angstrom/cycle and self-limiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS2 is the reaction product, and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS2 in the as-deposited films, and this might result from unreacted MoFx residues in the films. Annealing the films at 350 degrees C in a hydrogen rich environment yielded crystalline MoS2 and reduced the F concentration in the films. Optical transmission measurements yielded a bandgap of 1.3 eV. Finally, the authors observed that the MoS2 growth per cycle was accelerated when a fraction of the MoF6 pulses were substituted with diethyl zinc. Published by the AVS

Mane, Anil U.↗
DOE OSTI2015

Atomically thin two-dimensional organic-inorganic hybrid perovskites

Organic-inorganic hybrid perovskites, which have shown to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C 4 H 9 NH 3 ) 2 PbBr 4 with well-defined square shape and large size. Different from the other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials.

Dou, Letian↗
DOE OSTI2013

Defect-Driven Restructuring of TiO 2 Surface and Modified Reactivity Toward Deposited Gold Atoms

A partially reduced TiO 2 surface exhibits increasingly complex nature when forming various defects, whose stoichiometry, structure and properties are markedly different from those of bulk TiO 2 . Using scanning tunneling microscopy and density functional theory, we investigate different types of surface defects formed by Ti interstitials on TiO 2 (110) and their reactivity toward deposited gold atoms. Sub-stoichiometric strands greatly enhance bonding of Au by transferring the excess charges from the reduced Ti 3+ onto the strands. Thus the sub-stoichiometric strands behave as strong electron donor sites toward reactants. On the contrary, fully stoichiometric nanoclusters provide increased Au bonding through its 1-coordinated oxygen, which acts as a strong electron acceptor site. Specific interactions between Au and defects as well as the implication of electron donor/acceptor complexes for catalytic reactions are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗