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At least 109 records · Page 6

Surface characterization and methane activation on SnO x /Cu 2 O/Cu(111) inverse oxide/metal catalysts

To activate methane at low or medium temperatures is a difficult task and a pre-requisite for the conversion of this light alkane into high value chemicals. In this work, we report the preparation and characterizations of novel SnO x /Cu 2 O/Cu(111) interfaces that enable low-temperature methane activation. Scanning tunneling microscopy identified small, well-dispersed SnO x nanoclusters on the Cu 2 O/Cu(111) substrate with an average size of 8 Å, and such morphology was sustained up to 450 K in UHV annealing. Ambient pressure X-ray photoelectron spectroscopy showed that hydrocarbon species (CH x groups), the product of methane activation, were formed on SnO x /Cu 2 O/Cu(111) at a temperature as low as 300 K. An essential role of the SnO x –Cu 2 O interface was evinced by the SnO x coverage dependence. Systems with a small amount of tin oxide, 0.1–0.2 ML coverage, produced the highest concentration of adsorbed CH x groups. Calculations based on density functional theory showed a drastic reduction in the activation barrier for C–H bond cleavage when going from Cu 2 O/Cu(111) to SnO x /Cu 2 O/Cu(111). On the supported SnO x , the dissociation of methane was highly exothermic (ΔE ~ –35 kcal mol –1 ) and the calculated barrier for activation (~20 kcal mol –1 ) could be overcome at 300–500 K, target temperatures for the conversion of methane to high value chemicals.

36 MATERIALS SCIENCE↗

Optimum Platinum Loading In Pt/SnO2 CO-Oxidizing Catalysts

Platinum on tin oxide (Pt/SnO2) good catalyst for oxidation of carbon monoxide at or near room temperature. Catalytic activity peaks at about 17 weight percent Pt. Catalysts with platinum loadings as high as 46 percent fabricated by technique developed at Langley Research Center. Work conducted to determine optimum platinum loading for this type of catalyst. Major application is removal of unwanted CO and O2 in CO2 lasers.

Schryer, David R.↗

Chemical approaches to artificial photosynthesis: A molecular, dye-sensitized photoanode for O 2 production prepared by layer-by-layer self-assembly

We describe here the preparation of a family of photoanodes for water oxidation that incorporate an electron acceptor–chromophore–catalyst in single molecular assemblies on nano-indium tin oxide (nanoITO) electrodes on fluorine-doped tin oxide (FTO). The assemblies were prepared by using a layer-by-layer, Atomic Layer Deposition (ALD), self-assembly approach. In the procedure, addition of an electron acceptor viologen derivative followed by a Ru II (bpy) chromophore and a pyridyl derivative of the water oxidation catalyst [Ru(bda) (L) 2 ] (bda = 2,2'-bipyridine-6,6'-dicarboxylate) 2 , were linked by ALD by addition of the bridge precursors TiO 2 , ZrO 2 , and Al 2 O 3 as the bridging groups giving the assemblies, FTO|nanoITO|–MV 2+ –ALD MO 2 –RuP2 2+ –ALD M'O 2 –WOC. In a series of devices, the most efficient gave water oxidation with an incident photon to current efficiency of 2.2% at 440 nm. Transient nanosecond absorption measurements on the assemblies demonstrated that the slow step in the intra-assembly electron transfer is the electron transfer from the chromophore through the viologen bridge to the nanoITO electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interplay between Catalyst Corrosion and Homogeneous Reactive Oxygen Species in Electrochemical Ozone Production

In this study, electrochemical ozone production (EOP), a six-electron water oxidation reaction, offers promising avenues for creating value-added oxidants and disinfectants. However, progress in this field is slowed by a dearth of understanding of fundamental reaction mechanisms. In this work, we combine experimental electrochemistry, spectroscopic detection of reactive oxygen species (ROS), oxygen-anion chemical ionization mass spectrometry, and computational quantum chemistry calculations to determine a plausible reaction mechanism on nickel- and antimony-doped tin oxide (Ni/Sb–SnO 2 , NATO), one of the most selective EOP catalysts. Antimony doping is shown to increase the conductivity of the catalyst, leading to improved electrochemical performance. Spectroscopic analysis and electrochemical experiments combined with quantum chemistry predictions reveal that hydrogen peroxide (H 2 O 2 ) is a critical reaction intermediate. We propose that leached Ni 4+ cations catalyze hydrogen peroxide into solution phase hydroperoxyl radicals ( • OOH); these radicals are subsequently oxidized to ozone. Isotopic product analysis shows that ozone is generated catalytically from water and corrosively from the catalyst oxide lattice without regeneration of lattice oxygens. Further quantum chemistry calculations and thermodynamic analysis suggest that the electrochemical corrosion of tin oxide itself might generate hydrogen peroxide, which is then catalyzed to ozone. The proposed pathways explain both the roles of dopants in NATO and its lack of stability. Our study interrogates the possibility that instability and electrochemical activity are intrinsically linked through the formation of ROS. In doing so, we provide the first mechanism for EOP that is consistent with computational and experimental results and highlight the central challenge of instability as a target for future research efforts.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A surface acoustic wave hydrogen sensor with tin doped indium oxide layers for intermediate temperatures

We report high temperature surface acoustic wave (SAW) gas sensors with conducting sensing layers require tuning of the sheet conductivity for optimal response. Conducting metal oxides are attractive sensing materials for their tunable electronic properties and high thermal stability, amongst others. Here, we have investigated the application of indium oxide (IO) and indium tin oxide (ITO) films on langasite (LGS)-based SAW reflective delay line sensor devices for monitoring hydrogen at 350 °C. Specifically, we modeled the effect of the IO and ITO sensing layer thickness on the wave velocity, attenuation, and effective electromechanical coefficient. This was followed by an experimental demonstration of tuning of the ITO film sheet conductivity by controlling the dopant concentration and yielding an improvement in the sensor sensitivity. The current study provides a pathway towards the development of conductivity-based sensing layers for high temperature SAW gas sensors with improved sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deterministic modeling of hybrid nonlinear effects in epsilon-near-zero thin films

In nonlinear optics, significant effort is concentrated on improving the strength and efficiency of interactions; however, experimentally investigating nonlinear materials is a complex, time-consuming, and costly investment. Moreover, it is often challenging to isolate, study, and optimize material parameters in an experiment due to complexities in the growth process. Recently, epsilon-near-zero materials have received a great deal of attention as promising nonlinear optical materials, but like many up-and-coming materials, the ability to explore and optimize their properties has been challenging. Here, we establish a framework to rapidly evaluate the performance of nonlinear epsilon-near-zero materials for both inter- and intraband effects in silico, requiring only an energy-momentum (E-k) diagram, linear optical properties, and experimental conditions. Measured nonlinear reflection and transmission in gallium-doped zinc oxide films are compared to the numerical framework for both intra- and interband excitation to verify accuracy across wavelength and irradiance while two figures of merit (FoMs) are introduced to quickly evaluate the performance of films without a full numerical framework. This capability is used to predict the performance of highly doped gallium nitride, cadmium oxide, zinc oxide, and indium tin oxide films, and efficient intra- and interband operation conditions are identified. Through this numerical framework and the FoMs, the exploration of unstudied epsilon-near-zero materials is enabled without the need for a nonlinear experiment, thereby accelerating the search for more efficient nonlinear materials and excitation conditions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium diboride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Riedell, James A.↗

Methods of repairing a substrate

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium boride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Riedell, James A.↗

InP based solar cells for space application: Reduction of external losses

Although InP-based solar cells have considerable potential for space applications, it is necessary to improve efficiencies to around the level of GaAs or Si cells before their excellent radiation resistance can be regarded as a dominant advantage. The authors concentrate on indium-tin-oxide/InP cells, presenting data relating to reduction of the contact resistance of the rear surface metallization, reduction of reflectance losses by choosing indium-tin-oxide deposition conditions to give specific optical properties, and reduction of losses associated with the grid. Simultaneous optimization of all of these has led to improved values of Jsc. For devices of approximately 1 cm2 in area, the largest Jsc achieved to date is 28.1 mA/aq cm (AM1.5, SERI/NASA direct normal spectrum, 25 C, total area, 100 mW/sq cm). For this particular cell, the equivalent AM0 value of Jsc was 34.6 mA/sq cm, which appears to be the largest reported for any InP-based cell.

Wu, X.↗

Photonic near infrared heater

A multilayer photonic stack comprising a lower plurality of alternating layers comprising at least A and B and an upper plurality of alternating layers comprising at least C and D, layer A comprises at least one of Al, Au, W, Ag, Ni, Ti, Pt, and Cr, layer B comprises at least one of Al2O3, AlN, MgO, SiO2, TiO2, Si3N4, MgF2, Ta2O5, SiC, Si, Ge, and Indium Tin Oxide (ITO), and layers C and D comprise at least one of Al2O3, AlN, MgO, SiO2, TiO2, Si3N4, MgF2, Ta2O5, SiC, Si, Ge, and Indium Tin Oxide (ITO).

Prasher, Ravi Shankar↗

Mixed Tin-Titanium Oxides by Atomic Layer Deposition on Planar Substrates: Physical and Electronic Structure

Ternary atomic layer deposition of Sn-doped TiO x (Sn:TiO x ) and Ti-doped SnO x (Ti:SnO x ) was performed using tetrakisdimethylamidotitanium (IV) and tin(IV) with water at 150 °C on (1 0 0) Si and quartz substrates. The physical structure of the films was investigated using scanning electron, atomic force, and Kelvin probe force microscopies as well as spectroscopic ellipsometry, Raman spectroscopy, and X-ray diffraction. All as-deposited films are amorphous and possessed flat and conformal topographies with low surface roughness (<1 nm). Annealed Sn:TiO x and Ti:SnO x crystallize into the tetragonal anatase TiO 2 and cassiterite SnO 2 structures, respectively, without large variations to the film topography. The chemical composition of the as-deposited and annealed films was investigated through X-ray photoelectron spectroscopy. While dopants are homogenously mixed, the ternary ALD to form Sn:TiO x and Ti:SnO x surprisingly does not follow the rule of mixtures, despite similarities in both the growth rates of binary SnO x and TiO x and the precursors used. This finding is also supported by spectroscopic ellipsometry. Here, we postulate the deviation from the rule of mixtures is due to non-ideal surface chemistry of the binary ALD of SnO x . The optical bandgap of all films was quantified by the Tauc analysis and the valence band position was investigated by valence band X-ray photoelectron spectroscopy. Intra-bandgap states above the valence band maximum were observed for as-deposited Ti:SnO x and Sn:TiO x and ascribed to 5 s states from Sn 2+ ions. The presence of these intra-bandgap states induces enhanced visible absorption and bathochromic shifts to the apparent bandgap for all as-deposited films. Annealing the films removes the intra-bandgap states and increases the optical bandgap. Simplified band diagrams created using the data available demonstrated that the conduction and valence band positions did not vary between the positions of pure TiO 2 or SnO 2 with monotonic increases to the dopant incorporation.

36 MATERIALS SCIENCE↗

Polycrystalline SnSe with a thermoelectric figure of merit greater than the single crystal

Abstract Thermoelectric materials generate electric energy from waste heat, with conversion efficiency governed by the dimensionless figure of merit, ZT. Single-crystal tin selenide (SnSe) was discovered to exhibit a high ZT of roughly 2.2–2.6 at 913 K, but more practical and deployable polycrystal versions of the same compound suffer from much poorer overall ZT, thereby thwarting prospects for cost-effective lead-free thermoelectrics. The poor polycrystal bulk performance is attributed to traces of tin oxides covering the surface of SnSe powders, which increases thermal conductivity, reduces electrical conductivity and thereby reduces ZT. Here, we report that hole-doped SnSe polycrystalline samples with reagents carefully purified and tin oxides removed exhibit an ZT of roughly 3.1 at 783 K. Its lattice thermal conductivity is ultralow at roughly 0.07 W m –1 K –1 at 783 K, lower than the single crystals. The path to ultrahigh thermoelectric performance in polycrystalline samples is the proper removal of the deleterious thermally conductive oxides from the surface of SnSe grains. These results could open an era of high-performance practical thermoelectrics from this high-performance material.

36 MATERIALS SCIENCE↗

Lead-acid battery construction

The power characteristics of a lead-acid battery are improved by incorporating a dispersion of 1 to 10% by weight of a thermodynamically stable conductivity additive, such as conductive tin oxide coated glass fibers (34) of filamentary glass wool (42) in the positive active layer (32) carried on the grid (30) of the positive plate (16). The avoiding of positive plate reversal to prevent reduction of the tin oxide is accomplished by (a) employing an oversized positive plate and pre-charging it; (b) by pre-discharging the negative plate; and/or (c) by placing a circuit breaker (26) in combination with the plates (16, 18) and terminals (22, 24) to remove the load when the voltage of the positive plate falls below a pre-selected level.

Rowlette, John J.↗

Interconnect resistance of photovoltaic submodules

Small area amorphous silicon solar cells generally have higher efficiencies than large interconnected submodules. Among the reasons for the differences in performance are the lack of large area uniformity, the effect of nonzero tin oxide sheet resistance, and possibly pinholes in the various layers. Another and usually small effect that can contribute to reduced performance of interconnected cells is the resistance of the interconnection i.e., the series resistance introduced by the metal to tin oxide contact through silicon. Proper processing problems to avoid poor contacts are discussed.

Volltrauer, H.↗

Unitary plate electrode

The unitary electrode (10) comprises a porous sheet (12) of fiberglass the strands (14) of which contain a coating (16) of conductive tin oxide. The lower portion of the sheet contains a layer (18) of resin and the upper layer (20) contains lead dioxide forming a positive active electrode on an electrolyte-impervious layer. The strands (14) form a continuous conduction path through both layers (16, 18). Tin oxide is prevented from reduction by coating the surface of the plate facing the negative electrode with a conductive, impervious layer resistant to reduction such as a thin film (130) of lead or graphite filled resin adhered to the plate with a layer (31) of conductive adhesive. The plate (10) can be formed by casting a molten resin from kettle (60) onto a sheet of glass wool (56) overlying a sheet of lead foil and then applying positive active paste from hopper (64) into the upper layer (68). The plate can also be formed by passing an assembly of a sheet ( 80) of resin, a sheet (86) of sintered glass and a sheet (90) of lead between the nip (92) of heated rollers (93, 95) and then filling lead oxide into the pores (116) of the upper layer (118).

Rowlette, John J.↗

The Effect of Surface Induced Flows on Bubble and Particle Aggregation

Almost 20 years have elapsed since a phenomenon called "radial specific coalescence" was identified. During studies of electrolytic oxygen evolution from the back side of a vertically oriented, transparent tin oxide electrode in alkaline electrolyte, one of the authors (Sides) observed that large "collector" bubbles appeared to attract smaller bubbles. The bubbles moved parallel to the surface of the electrode, while the electric field was normal to the electrode surface. The phenomenon was reported but not explained. More recently self ordering of latex particles was observed during electrophoretic deposition at low DC voltages likewise on a transparent tin oxide electrode. As in the bubble work, the field was normal to the electrode while the particles moved parallel to it. Fluid convection caused by surface induced flows (SIF) can explain these two apparently different experimental observations: the aggregation of particles on an electrode during electrophoretic deposition, and a radial bubble coalescence pattern on an electrode during electrolytic gas evolution. An externally imposed driving force (the gradient of electrical potential or temperature), interacting with the surface of particles or bubbles very near a planar conducting surface, drives the convection of fluid that causes particles and bubbles to approach each other on the electrode.

Guelcher, Scott A.↗

Role of defects in ultra-high gain in fast planar tin gallium oxide UV-C photodetector by MBE

Here we report ultra-high responsivity of epitaxial (Sn x Ga 1–x ) 2 O 3 (TGO) Schottky UV-C photodetectors and experimentally identified the source of gain as deep-level defects, supported by first principles calculations. Epitaxial TGO films were grown by plasma-assisted molecular beam epitaxy on (–201) oriented n-type β-Ga 2 O 3 substrates. Fabricated vertical Schottky devices exhibited peak responsivities as high as 3.5 ×10 4 A/W at –5 V applied bias under 250 nm illumination with sharp cutoff shorter than 280 nm and fast rise/fall time in milliseconds order. Hyperspectral imaging cathodoluminescence (CL) spectra were examined to find the mid-bandgap defects, the source of this high gain. Irrespective of different tin mole fractions, the TGO epilayer exhibited extra CL peaks at the green band (~2.20 eV) not seen in β-Ga 2 O 3 along with enhancement of the blue emission-band (~2.64 eV) and suppression of the UV emission-band. Based on hybrid functional calculations of the optical emission expected for defects involving Sn in β-Ga 2 O 3 , V Ga –Sn complexes are proposed as potential defect origins of the observed green and blue emission-bands. Such complexes behave as acceptors that can efficiently trap photogenerated holes and are predicted to be predominantly responsible for the ultra-high photoconductive gain in the Sn-alloyed Ga 2 O 3 devices by means of thermionic emission and electron tunneling. Regenerating the V Ga –Sn defect complexes by optimizing the growth techniques, we have demonstrated a planar Schottky UV-C photodetector of the highest peak responsivity.

36 MATERIALS SCIENCE↗

Open‐Air Combustion Synthesis with Rapid Plasma Processing of Large‐Area Transparent Conducting Oxides

A vacuum-free, high-throughput synthesis of indium tin oxide (ITO) via Combustion Oxidation with Rapid Plasma Processing (CORP) utilizes a solution-based exothermic combustion reaction to generate the oxide with tunable control of either amorphous or crystalline phases. A subsequent open-air, forming gas plasma treatment is used to introduce oxygen vacancies and promote crystallization. Here, the evolution of the oxide structure is elucidated by extended X-ray absorption spectroscopy fine structure analysis. Using CORP, fabrication of 300 cm 2 of ITO possessing a champion sheet resistance of 38 Ω sq. −1 , visible transmission of 89%, conductivity stability for over 250 days, roughness < 2nm, and Haacke figure of merit (%T 550nm 10 /R s ) of 0.012 Ω −1 is achieved. Cost modeling of CORP demonstrates up to a 67% reduction in price for TCOs using fully continuous, in-line unit operations compared with vacuum sputtering. The work shows a path toward a low-cost, vacuum-free manufacturing method for TCOs at commercial scales.

42 ENGINEERING↗