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At least 289 records · Page 16

X-ray photoelectron spectroscopy study of the stability of Fomblin Z25 on the native oxide of aluminum

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum, and onto sapphire surfaces, and their behavior at different temperatures was studied using X-ray photoelectron spectroscopy and temperature desorption spectroscopy (TDS). The interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on the clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. The native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At higher temperatures (150 C), degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formation of a debris layer.

Herrera-Fierro, Pilar↗

Developmental status of thermionic materials.

Description of the reference materials selected for the major components of the unit cell of a thermionic pile element (TFE), the out-of-pile and in-pile test results, and current efforts for improving the life and performance of thermionic fuel elements. The component materials are required to withstand the fuel burnup and fast neutron fluence dictated by the thermionic reactor system. Tungsten was selected as the cladding material because of its compatibility with both the carbide and the oxide fuel materials. Niobium was selected as the collector material because its thermal expansion coefficient matches closely with that of the thin aluminum oxide layer used to electrically insulate the collector from the TFE sheath. An unfueled converter has performed stably over 41,000 hr. Accelerated irradiation tests have attained burnups equivalent to that for 40,000 hr of the thermionic reactor under consideration.

Yang, L.↗

In Situ deposition of YBCO high-T(sub c) superconducting thin films by MOCVD and PE-MOCVD

Metalorganic Chemical Vapor Deposition (MOCVD) offers the advantages of a high degree of compositional control, adaptability for large scale production, and the potential for low temperature fabrication. The capability of operating at high oxygen partial pressure is particularly suitable for in situ formation of high temperature superconducting (HTSC) films. Yttrium barium copper oxide (YBCO) thin films having a sharp zero-resistance transition with T( sub c) greater than 90 K and Jc approx. 10 to the 4th power A on YSZ have been prepared, in situ, at a substrate temperature of about 800 C. Moreover, the ability to form oxide films at low temperature is very desirable for device applications of HTSC materials. Such a process would permit the deposition of high quality HTSC films with a smooth surface on a variety of substrates. Highly c-axis oriented, dense, scratch resistant, superconducting YBCO thin films with mirror-like surfaces have been prepared, in situ, at a reduced substrate temperature as low as 570 C by a remote microwave-plasma enhanced metalorganic chemical vapor deposition (PE-MOCVD) process. Nitrous oxide was used as a reactant gas to generate active oxidizing species. This process, for the first time, allows the formation of YBCO thin films with the orthorhombic superconducting phase in the as-deposited state. The as-deposited films grown by PE-MOCVD show attainment of zero resistance at 72 K with a transition width of about 5 K. MOCVD was carried out in a commercial production scale reactor with the capability of uniform deposition over 100 sq cm per growth run. Preliminary results indicate that PE-MOCVD is a very attractive thin film deposition process for superconducting device technology.

Zhao, J.↗

In-situ deposition of YBCO high-Tc superconducting thin films by MOCVD and PE-MOCVD

Metal-Organic Chemical Vapor Deposition (MOCVD) offers the advantages of a high degree of compositional control, adaptability for large scale production, and the potential for low temperature fabrication. The capability of operating at high oxygen partial pressure is particularly suitable for in situ formation of high temperature superconducting (HTSC) films. Yttrium barium copper oxide (YBCO) thin films having a sharp zero-resistance transition with T(sub c) greater than 90 K and J(sub c) of approximately 10(exp 4) A on YSZ have been prepared, in situ, at a substrate temperature of about 800 C. Moreover, the ability to form oxide films at low temperature is very desirable for device applications of HTSC materials. Such a process would permit the deposition of high quality HTSC films with a smooth surface on a variety of substrates. Highly c-axis oriented, dense, scratch resistant, superconducting YBCO thin films with mirror-like surfaces have been prepared, in situ, at a reduced substrate temperature as low as 570 C by a remote microwave-plasma enhanced metal-organic chemical vapor deposition (PE-MOCVD) process. Nitrous oxide was used as a reactant gas to generate active oxidizing species. This process, for the first time, allows the formation of YBCO thin films with the orthorhombic superconducting phase in the as-deposited state. The as-deposited films grown by PE-MOCVD show attainment of zero resistance at 72 K with a transition width of about 5 K. MOCVD was carried out in a commercial production scale reactor with the capability of uniform deposition over 100 sq cm per growth run. Preliminary results indicate that PE-MOCVD is a very attractive thin film deposition process for superconducting device technology.

Zhao, J.↗

Atomic Force Microscope Mediated Chromatography

The atomic force microscope (AFM) is used to inject a sample, provide shear-driven liquid flow over a functionalized substrate, and detect separated components. This is demonstrated using lipophilic dyes and normal phase chromatography. A significant reduction in both size and separation time scales is achieved with a 25-micron-length column scale, and one-second separation times. The approach has general applications to trace chemical and microfluidic analysis. The AFM is now a common tool for ultra-microscopy and nanotechnology. It has also been demonstrated to provide a number of microfluidic functions necessary for miniaturized chromatography. These include injection of sub-femtoliter samples, fluidic switching, and sheardriven pumping. The AFM probe tip can be used to selectively remove surface layers for subsequent microchemical analysis using infrared and tip-enhanced Raman spectroscopy. With its ability to image individual atoms, the AFM is a remarkably sensitive detector that can be used to detect separated components. These diverse functional components of microfluidic manipulation have been combined in this work to demonstrate AFM mediated chromatography. AFM mediated chromatography uses channel-less, shear-driven pumping. This is demonstrated with a thin, aluminum oxide substrate and a non-polar solvent system to separate a mixture of lipophilic dyes. In conventional chromatographic terms, this is analogous to thin-layer chromatography using normal phase alumina substrate with sheardriven pumping provided by the AFM tip-cantilever mechanism. The AFM detection of separated components is accomplished by exploiting the variation in the localized friction of the separated components. The AFM tip-cantilever provides the mechanism for producing shear-induced flows and rapid pumping. Shear-driven chromatography (SDC) is a relatively new concept that overcomes the speed and miniaturization limitations of conventional liquid chromatography. SDC is based on a sliding plate system, consisting of two flat surfaces, one of which has a recessed channel. A fluid flow is produced by axially sliding one plate past another, where the fluid has mechanical shear forces imposed at each point along the channel length. The shear-induced flow rates are very reproducible, and do not have pressure or voltage gradient limitations. SDC opens up a new range of enhanced separation kinetics by permitting the sample confinement with submicron dimensions. Small, highly confined liquid is advantageous for chromatographic separation because the separation rate is known to scale according to the square of the confined sample diameter. In addition, because shear-driven flows are not limited by fluid velocity, shear-driven liquid chromatography may provide up to 100,000 plate efficiency.

Anderson, Mark S.↗

Thickness dependent OER electrocatalysis of epitaxial thin film of high entropy oxide

High entropy oxides (HEOs), which contain multiple elements in the same crystallographic site, are a promising platform for electrocatalysis in oxygen evolution reaction (OER). Investigating these materials in epitaxial thin film form expands the possibility of tuning OER activity by several means, which are not realizable in polycrystalline samples. To date, very few such studies have been reported. In this work, the OER activity of single-crystalline thin films of (La 0.2 Pr 0.2 Nd 0.2 Sm 0.2 Eu 0.2 )NiO 3 , grown on NdGaO 3 substrates have been investigated in 0.1 M KOH electrolyte as a function of film thickness. The OER activity increases with the thickness of the film. X-ray absorption spectroscopy measurements find an increase in Ni $d$-O $p$ covalency and a decrease in charge transfer energy with the increase in film thickness. These facilitate higher charge transfer between Ni and surface adsorbates, increasing OER activity. However, the OER process leads to excessive leaching of thicker films and the OER activity of a 75 unit cell thick film is found to be optimal in the present study. In conclusion, this work demonstrates that the thickness of perovskite oxides can be used as a parameter to enhance OER activity.

36 MATERIALS SCIENCE↗

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides

Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO 3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine-Guided Design of Oxidation-Resistant Superconductors for Quantum Information Applications

Decoherence in superconducting qubits has long been attributed to two-level systems arising from the surfaces and interfaces present in real devices. A recent significant step in reducing decoherence was the replacement of superconducting niobium by superconducting tantalum, resulting in a tripling of transmon qubit lifetimes (T1). The identity, thickness, and quality of the native surface oxide, is thought to play a major role, as tantalum only has one oxide whereas niobium has several. Here we report the development of a thermodynamic metric to rank materials based on their potential to form a well-defined, thin, surface oxide. We first computed this metric for known binary and ternary metal alloys using data available from the Materials Project and experimentally validated the strengths and limits of this metric through the preparation and controlled oxidation of eight known metal alloys. Then we trained a convolutional neural network to predict the value of this metric from atomic composition and atomic properties. This allowed us to compute the metric for materials that are not present in the Materials Project, including a large selection of known superconductors, and, when combined with Tc, allowed us to identify new candidate superconductors for quantum information science and engineering (QISE) applications. We tested the oxidation resistance of a pair of these predictions experimentally. Our results are expected to lay the foundation for the tailored and rapid selection of improved superconductors for QISE.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Fast imaging of laser ablation of cerium: Dependence of plasma plume dynamics and structure on native oxide growth

We have imaged the evolution of plasma following nanosecond pulsed laser ablation of cerium in air with sub-10 ns resolution. We find the ablated plasma plume expansion and shape to be strongly dependent on the time after mechanical polishing of the sample surface. After an initial shock front common to both new and aged samples (velocities up to 16 km s ₋1 ), we observe a second front that is relatively localized to the surface vicinity of newly polished samples, but in the case of older samples it moves outward at velocities of up to 4 km s ₋1 . We attribute this behavior to the formation and growth of a native oxide layer on the order of hours after polishing. These results demonstrate that plasma imaging can be used to diagnose the presence of, and evaluate the extent of, thin surface oxides or other compounds that form soon after exposure to some atmosphere. These findings also highlight the need to explicitly consider the presence of such overlayers when modeling laser/metal interaction, when making measurements of vapor phase chemistry, and when analyzing the composition, phase, and morphology of solid particulates formed after the ablation of reactive metals.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The oxidation of Ni-rich Ni-Al intermetallics

The oxidation of Ni-Al intermetallic alloys in the beta-NiAl phase field and in the two phase beta-NiAl/gamma'-Ni3Al phase field has been studied between 1000 and 1400 C. The stoichiometric beta-NiAl alloy doped with Zr was superior to other alloy compositions under cyclic and isothermal oxidation. The isothermal growth rates did not increase monotonically as the alloy Al content was decreased. The characteristically ridged alpha-Al2O3 scale morphology, consisting of cells of thin, textured oxide with thick growth ridges at cell boundaries, forms on oxidized beta-NiAl alloys. The correlation of scale features with isothermal growth rates indicates a predominant grain boundary diffusion growth mechanism. The 1200 C cyclic oxidation resistance decreases near the lower end of the beta-NiAl phase field.

Doychak, Joseph↗

The oxidation of Ni-rich Ni-Al intermetallics

The oxidation of Ni-Al intermetallic alloys in the beta-NiAl phase field and in the two phase beta-NiAl/gamma'-Ni3Al phase field has been studied between 1000 and 1400 C. The stoichiometric beta-NiAl alloy doped with Zr was superior to other alloy compositions under cyclic and isothermal oxidation. The isothermal growth rates did not increase monotonically as the alloy Al content was decreased. The characteristically ridged alpha-Al203 scale morphology, consisting of cells of thin, textured oxide with thick growth ridges at cell boundaries, forms on oxidized beta-NiAl alloys. The correlation of scale features with isothermal growth rates indicates a predominant grain boundary diffusion growth mechanism. The 1200 C cyclic oxidation resistance decreases near the lower end of the beta-NiAl phase field.

Doychak, J.↗

All Solid-State Li/LLZO/LCO Battery Enabled by Alumina Interfacial Coating

Li 7 La 3 Zr 2 O 12 (LLZO) garnet-type lithium-ion conductors are being investigated as a promising solid electrolyte for solid-state lithium batteries. To enable a functional all-solid-state configuration intensive investigations are needed to reduce the cathode/electrolyte interfacial resistance which contributes the most to cell performance loss. Among the commercial cathode materials investigated so far, LiCoO 2 (LCO) is one of the most stable with garnet electrolytes as only a superficial reaction has been detected between the two materials. However, even this minor reaction would block the Li-ion transport through the interface, resulting in deteriorated cell performance. In this work, we demonstrate that a thin aluminum oxide layer (5 nm) can be an effective interlayer to impede the formation of a harmful interphase and enable facile Li-ion transfer between LCO and the LLZO garnet. Room-temperature-sputtered LCO thin films were employed to form an interface with the garnet electrolyte and annealed at 800 °C to reveal the effect of the interfacial reaction on the Li-ion transfer across the interface. An aluminum oxide layer was then introduced between LCO and the garnet electrolyte by sputtering a metallic aluminum layer which is then annealed together with the upper LCO layer in oxygen, or by direct atomic layer deposition of the oxide. Compared to the LCO/LLZO/Li cells without an aluminum oxide interlayer, those with the interlayer exhibited improved performance, i.e., a stable discharge capacity of up to 90 mAh/(g LCO) at a C/10 rate, a rate capability up to 1.68C and a stable galvanostatic cycling at 0.1C for over 100 cycles with a discharge capacity fade rate of 0.15% per cycle. It was determined that aluminum diffused into the LCO layer after preventing the initial detrimental reaction between LCO and the LLZO garnet from happening during high temperature annealing, suggesting that the coating does not have to remain a physically blocking layer during cycling to function.

Electrochemistry↗

Oxidation of porous stainless steel supports for metal-supported solid oxide fuel cells

Here, oxidation behavior of porous P434L ferritic stainless steel, used for the fabrication of metal-supported solid oxide fuel cells (MS-SOFC), is studied under anodic and cathodic atmospheres. Temperature- and atmosphere-dependence is determined for as-sintered and pre-oxidized stainless steel. Pre-oxidation reduced the long-term oxidation rate. For pre-oxidized samples, the oxidation rate in air exceeds that in humid hydrogen for temperatures above 700 °C. The influence of PrOx, LSCF-SDC, and Ni-SDC coatings is also examined. The coatings do not dramatically impact oxide scale growth. Oxidation in C-free and C-containing anodic atmospheres is similar. Addition of CO 2 , CH 4 , and CO to humidified hydrogen to simulate ethanol reformate does not significantly impact oxidation behavior. Cr transpiration in humid air is greatly reduced by the PrOx coating, and a PrCrO 3 reaction product is observed throughout the porous structure. A dense and protective chromia-based scale forms on steel samples during oxidation in all conditions. A thin silica enriched oxide layer also forms at the metal-scale interface. In general, the oxidation behavior at 700 °C is found to be acceptable.

25 ENERGY STORAGE↗

Compatibility of Steels in Supercritical CO2 at 450°-650°C

Supercritical CO2 (sCO2) power cycles, particularly direct-fired cycles, have the possibility of revolutionizing clean fossil energy. However, in the lower temperature sections of the cycle, lower cost steels are needed in order to lower the cost of the sCO2 technology. Representative 9 and 12%Cr steels and conventional and advanced austenitic steels are being evaluated at 450-650°C using mass change, bulk carbon (C) content and room temperature tensile properties to determine the maximum use temperatures for both direct- and indirect-fired sCO2 cycles. After 1000 h exposures in research grade (RG) sCO2 at 300 bar and RG sCO2 with 1% O2 and 0.1% H2O additions, the results suggest that increasing the Cr content from 9 to 12% yielded no signficant benefit under these conditions but the higher Cr and Ni contents in S31025 provided better compatibility in RG sCO2 at 650°C but limited benefit at 550°C with impurities. For S31609, the formation of Fe-rich oxide after exposure to RG sCO2 at 650°C resulted in both an increase in the bulk C content and a large drop in room temperature ductility. The evidence suggests thin, protective oxides prevented C ingress in these conditions.

Pint, Bruce↗

Thin film design of amorphous hafnium oxide nanocomposites enabling strong interfacial resistive switching uniformity

A design concept of phase-separated amorphous nanocomposite thin films is presented that realizes interfacial resistive switching (RS) in hafnium-oxide-based devices. The films are formed by incorporating an average of 7% Ba into hafnium oxide during pulsed laser deposition at temperatures ≤400°C. The added Ba prevents the films from crystallizing and leads to ~20-nm-thin films consisting of an amorphous HfO x host matrix interspersed with ~2-nm-wide, ~5-to-10-nm-pitch Ba-rich amorphous nanocolumns penetrating approximately two-thirds through the films. This restricts the RS to an interfacial Schottky-like energy barrier whose magnitude is tuned by ionic migration under an applied electric field. Resulting devices achieve stable cycle-to-cycle, device-to-device, and sample-to-sample reproducibility with a measured switching endurance of ≥10 4 cycles for a memory window ≥10 at switching voltages of ±2 V. Each device can be set to multiple intermediate resistance states, which enables synaptic spike-timing–dependent plasticity. The presented concept unlocks additional design variables for RS devices.

36 MATERIALS SCIENCE↗

Data for "Gold-Induced Chemical Perturbations in CdTe-Based Photovoltaic Cells"

Back contacting p-type CdTe has been identified as one of the major areas of loss in CdTe photovoltaic (PV) power conversion efficiency (PCE). In research settings, Au is a common contact material due to its ease of use and decent performance. This work provides a detailed investigation into using gold for back contacting As-doped, CdCl2 treated, polycrystalline CdTe that has been exposed to air after absorber processing, another routine practice. First, X-ray photoemission spectroscopy (XPS) is used to determine the native oxide to be 1.6 nm of CdTeO3 using a combination of angle-resolved XPS and the cadmium modified Auger parameter. During gold metallization of CdTe, oxygen and oxidized tellurium are eliminated from the thin CdTeO3 native oxide. The fate of the released oxygen and possibly cadmium and tellurium are not known, but these reaction byproducts can enter the absorber bulk or grain boundaries, stay at the interface, or dissolve in the Au. Interfacial hole barriers between CdTe and Au are measured for samples with and without the native oxide present prior to metallization. Results show that the thin CdTeO3 alleviates the downward band bending by 40 meV from 470 meV to 430 meV even though it is consumed during interface formation. The implications of these chemical reactions on the device are assessed through photoluminescence (PL) spectroscopy which shows losses in internal open circuit voltage (iVoc) from 820 meV to 795 meV, carrier lifetime from 123 ns to 45 ns, and PL quantum yield from 2.9x10-5 to 1.2x10-5. Modeling time-resolved PL lifetimes demonstrates the back surface recombination velocity due to metallization reduces minority carrier lifetimes. These results identify the native oxide and show that it plays an important role in mediating downward band bending along with how the back interface reaction can negatively impact device-scale parameters and reduce PV PCE.

14 SOLAR ENERGY↗

Water vapor oxidation of SiC layer in surrogate TRISO fuel particles

Under accidental conditions for high temperature gas-cooled reactors (HTGR), the SiC layer in tri-structural-isotropic (TRISO) fuel particles can be exposed to water vapor. In this study, oxidation behaviors of surrogate TRISO fuel particles were investigated in a He-20 vol% water vapor mixed atmosphere at temperatures up to 1600 °C. The growth of the crystalline oxide passivation layer with cracks and pores followed a parabolic law with time, where the maximum was 2.3 μm at 1600 °C. The oxide layer and the SiC surface under the oxide became flattened with increasing temperature, as a function of the silica viscosity and the diffusion path of water vapor. Volatilization of the oxide layer was analyzed using a mechanistic model that an inert gas in oxidizing atmospheres could influence the magnitude of volatilization. The fracture load and strength of the oxidized and thinned SiC layer were numerically estimated to decrease from 2.27 to 1.69 N and from 317 to 299 MPa, respectively, with the SiC thickness decrease from 35 to 32 μm. This prediction indicates that the oxidized SiC layer should retain fission products. Additionally, the mechanical integrity of each layer in the TRISO fuel particle after oxidation was evaluated. The results in this work provide important data for the safety analysis of accidental scenarios in HTGRs.

36 MATERIALS SCIENCE↗