The effects of dielectric overcoating on electromigration in aluminum interconnections.
Dielectric overcoating effects on electromigration Al interconnections, showing dependence on thickness and surface passivation
Schwartz, S.↗
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Facet‐Selective Deposition of Ultrathin Al 2 O 3 on Copper Nanocrystals for Highly Stable CO 2 Electroreduction to Ethylene
Abstract Catalysts based on Cu nanocrystals (NCs) for electrochemical CO 2 ‐to‐C 2+ conversion with high activity have been a subject of considerable interest, but poor stability and low selectivity for a single C 2+ product remain obstacles for realizing sustainable carbon‐neutral cycles. Here, we used the facet‐selective atomic layer deposition (FS‐ALD) technique to selectively cover the (111) surface of Cu NCs with ultrathin Al 2 O 3 to increase the exposed facet ratio of (100)/(111), resulting in a faradaic efficiency ratio of C 2 H 4 /CH 4 for overcoated Cu NCs 22 times higher than that for pure Cu NCs. Peak performance of the overcoated catalyst (Cu NCs/Al 2 O 3 ‐10C) reaches a C 2 H 4 faradaic efficiency of 60.4 % at a current density of 300 mA cm −2 in 5 M KOH electrolyte, when using a gas diffusion electrode flow cell. Moreover, the Al 2 O 3 overcoating effectively suppresses the dynamic mobility and the aggregation of Cu NCs, which explains the negligible activity loss and selectivity degradations of Cu NCs/Al 2 O 3 ‐10C shown in stability tests.
Li, Hui↗
Facet-Selective Deposition of Ultrathin Al 2 O 3 on Copper Nanocrystals for Highly Stable CO 2 Electroreduction to Ethylene.
Catalysts based on Cu nanocrystals (NCs) for electrochemical CO 2 -to- 2+ conversion with high activity have been a subject of considerable interest, but poor stability and low selectivity for a single C 2+ product remain obstacles for realizing sustainable carbon-neutral cycles. In this study, we used the facet-selective atomic layer deposition (FS-ALD) technique to selectively cover the (111) surface of Cu NCs with ultrathin Al 2 O 3 to increase the exposed facet ratio of (100)/(111), resulting in a faradaic efficiency ratio of C 2 H 4 /CH 4 for overcoated Cu NCs 22 times higher than that for pure Cu NCs. Peak performance of the overcoated catalyst (Cu NCs/Al 2 O 3 -10C) reaches a C 2 H 4 faradaic efficiency of 60.4 % at a current density of 300 mA cm -2 in 5 M KOH electrolyte, when using a gas diffusion electrode flow cell. Moreover, the Al 2 O 3 overcoating effectively suppresses the dynamic mobility and the aggregation of Cu NCs, which explains the negligible activity loss and selectivity degradations of Cu NCs/Al 2 O 3 -10C shown in stability tests.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A brief review of the state of the art and some recent results on electromigration in integrated circuit aluminum metallization.
Dielectric overcoatings effect on Al interconnections electromigration in IC metallization, noting longer intervals between failures
Schwartz, S.↗
Atomic Layer Deposition Overcoating Improves Catalyst Selectivity and Longevity in Propane Dehydrogenation
Propylene, a precursor for commodity chemicals and plastics, is produced by propane dehydrogenation (PDH). An increase in PDH yield via added catalyst activity, lifetime, or selectivity represents significant energy and economic savings. Using Pt dispersed on Al2O3 extrudate supports as a commercially relevant model system, we demonstrate that atomic layer deposition (ALD) metal oxide overcoats, used to tailor metal-active sites, can increase PDH yield and selectivity. We investigate the interplay of Pt loading, ALD overcoat thickness, and Al 2 O 3 support surface area on PDH activity, selectivity, and catalyst stability to show that applying a 6-8 A thick layer of Al 2 O 3 on low-surface area Al 2 O 3 supports of similar to 90 m 2 /g surface area yields the optimal combination of stability and activity, while increasing propylene selectivity from 91 to 96%. Increased stability upon steaming deactivation occurs because the Al 2 O 3 overcoat prevents the Pt nanoparticles from sintering. We speculate that the ALD overcoat selectively binds to the undercoordinated sites on the Pt nanoparticles, while leaving the more selective terrace sites available for dehydrogenation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Optical surface degradation from combined ultraviolet radiation and outgassed materials.
Outgassed condensation effects in vacuum on magnesium difluoride overcoated UV irradiated Al mirrors, including temperature effects, Lyman alpha reflectance and IR analysis of deposits
Griffin, R. N.↗
Monitoring Structural and Electronic Changes of Supported Metal Catalysts Using Combined X‐Ray Techniques
Supported metal nanoparticle catalysts have become increasingly crucial for many catalytic applications. However, long-term catalyst stability remains a problem due to catalyst deactivation caused by coke formation and sintering. The deposition of a thin overcoating via atomic layer deposition (ALD) onto metal-supported nanoparticles has shown to greatly inhibit catalyst deactivation. This work utilizes a model catalyst system comprised of Pt nanoparticles supported on Al 2 O 3 to demonstrate the effect of an atomically thin overcoating on supported metal nanoparticles. Continuous operando small-angle X-ray scattering (SAXS) and X-ray absorption near edge spectroscopy (XANES) monitor structural and electronic changes to the catalyst and overcoating during calcination. SAXS data fitting reveals the formation of nanopores in the overcoating at high temperatures, while XANES monitors the oxidation state of the Pt catalyst. Herein, the usefulness of combined X-ray techniques is demonstrated to characterize supported metal catalysts to further understanding of the synergistic effects of the ALD overcoating to aid in the design of new catalyst materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effects on optical systems from interactions with oxygen atoms in low earth orbits
Modifications of material surface properties due to interactions with ambient atomic oxygen have been observed on surfaces facing the orbital direction in low earth orbits. Some effects are very damaging to surface optical properties while some are more subtle and even beneficial. Most combustible materials are heavily etched, and some coatings, such as silver and osmium, are seriously degraded or removed as volatile oxides. The growth of oxide films on metals and semiconductors considered stable in dry air was measured. Material removal, surface roughness, reflectance, and optical densities are reported. Effects of temperature, contamination, and overcoatings are noted.
Peters, P. N.↗
Reflectance of aluminum overcoated with MgF2 and LiF in the wavelength region from 1600 A to 300 A at various angles of incidence
Fluoride overcoated Al reflectance measurements and polarization effects at various angles of incidence, noting utilization in vacuum UV instrumentation
Hass, G.↗
Radio-frequency plasma chemical vapor deposition growth of diamond
Plasma chemical vapor deposition (CVD) at 13.56 MHz has been used to produce diamond particles in two different inductively coupled systems with a mixture of methane and hydrogen. The effect of a diamondlike carbon (DLC) overcoating on silicon, niobium, and stainless-steel substrates has been investigated and in the case of silicon has been found to enhance particle formation as compared to uncoated polished silicon. In addition the use of carbon monoxide in hydrogen has been found to produce well-defined individual faceted particles as well as polycrystalline films on quartz and DLC coated silicon substrates. Plasma CVD is a competitive approach to production of diamond films. It has the advantage over microwave systems of being easily scaled to large volume and high power.
Meyer, Duane E.↗
Ellipsometric analysis of materials degradation in space
The fundamentals of variable angle spectroscopic ellipsometry (VASE) are reviewed, and its usefulness in studying the effect of atomic oxygen on space coatings such as indium tin oxide (ITO), silicon dioxide, and aluminum oxide is discussed. Monolayer sensitive and nondestructive VASE is found to be an effective technique for monitoring the atomic oxygen diffusion through the aluminum oxide and silicon dioxide protective overcoatings on space reflectors. Ashing of ITO/silicon samples had the net effect of annealing the film inside the plasma. The annealing effect was supported both by structural changes as verified by X-ray diffraction measurements and by increased absorbance in the spectral range below 3 eV as measured by VASE.
Woollam, John A.↗
Germanium-overcoated niobium Dayem bridges
Overcoating constriction microbridges with semiconducting germanium provides additional thermal conductivity at liquid-helium temperatures to reduce the effects of self-heating in these Josephson junctions. Microwave-induced steps were observed in the I-V characteristics of an overcoated Dayem bridge fabricated in a 15-nm-thick niobium film; at least 20 steps could be counted at 4.2 K. No steps were observed in the I-V characteristics of the bridge prior to overcoating. In addition, the germanium overcoat can protect against electrical disturbances at room temperature.
Holdeman, L. B.↗
The effect of rocket plume contamination on the optical properties of transmitting and reflecting materials
The preliminary results of plume contamination from a 5-pound thrust single-doublet, bipropellant rocket engine on the transmittance of quartz and the reflectance of a silicon monoxide overcoated aluminum mirror are presented. Changes in quartz transmittance were found to be significant and were due to both absorption and scattering effects. Contaminant absorption effects were predominant at the short wavelengths and scattering effects were greatest in the visible wavelengths. Measured changes in mirror reflectance were due primarily to contaminant absorption. Scattering effects were found to be as much as 9 percent of the total reflected energy from the mirror. There were no noticeable chemical or erosion effects on either the quartz or the front surface mirror.
Jack, J. R.↗
The effect of rocket plume contamination on the optical properties of transmitting and reflecting materials.
The preliminary results of plume contamination from a 5-pound thrust single-doublet, bipropellant rocket engine on the transmittance of quartz and the reflectance of a silicon monoxide overcoated aluminum mirror have been presented. Changes in quartz transmittance were found to be significant and were due to both absorption and scattering effects. Contaminant absorption effects were predominant at the short wavelengths and scattering effects were greatest in the visible wavelengths. Measured changes in mirror reflectance were due primarily to contaminant absorption. Scattering effects were found to be as much as 9% of the total reflected energy from the mirror. There were no noticeable chemical or erosion effects on either the quartz or the front surface mirror.
Jack, J. R.↗
Effects of the LDEF orbital environment on the reflectance of optical mirror materials
Specimens of eight different optical mirror materials were flown in low earth orbit as part of the Long Duration Exposure Facility (LDEF) manifest to determine their ability to withstand exposure to the residual atomic oxygen and other environmental effects at those altitudes. Optical thin films of aluminum, gold, iridium, osmium, platinum, magnesium fluoride-overcoated aluminum and reactively deposited, silicon monoxide-protected aluminum, all of which were vacuum deposited on polished fused silica substrates, were included as part of Experiment S0010, Exposure of Spacecraft Coatings. Two specimens of polished, chemical vapor deposited (CVD) silicon carbide were installed in sites available in Experiment A0114, Interaction of Atomic Oxygen with Solid Surfaces at Orbital Altitudes, which included trays in two of the spacecraft bays, one on the leading edge and the other on the trailing edge. One of the silicon carbide samples was located in each of these trays. This paper will compare specular reflectance data from the preflight and postflight measurements made on each of these samples and attempt to explain the changes in light of the specific environments to which the experiments were exposed.
Herzig, Howard↗
Effects of Shuttle bay environment on UV sensitive photographic film - Instrumentation for Get-Away-Special
An account is given of a Get-Away-Special experiment flown on Space Shuttles 7 and 8 investigating the effect of the space environment on Shumann emulsions. Shumann emulsions, having low gelatin content and no protective gelatin overcoating, are useful detectors of ultraviolet radiation shorter than 2200 angstroms but are extremely sensitive to environmental conditions and handling. The instrument required no interface with the Shuttle. It was turned on by an aneroid switch at an altitude of 50,000 feet. After that, its operation was controlled completely by a CMOS digital controller. Each hour, two temperatures and one voltage were read and stored in a CMOS programmable read only memory. At intervals, valves were opened and closed to expose SO 652 film strips of three sensitivities to the cargo bay environment for various time periods. The design and operation of the instrument package is described.
Kreplin, R. W.↗
Investigation to develop a method to apply diffusion barrier to high strength fibers
A radio frequency powered ion plating process was used to apply the diffusion barriers of aluminum oxide, yttrium oxide, hafnium oxide and titanium carbide to a substrate tungsten fiber. Each of the coatings was examined as to its effect on both room temperature strength and tensile strength of the base tungsten fiber. The coated fibers were then overcoated with a nickel alloy to become single cell diffusion couples. These diffusion couples were exposed to 1093 C for 24 hours, cycled between room temperature and 1093 C, and given a thermal anneal for 100 hours at 1200 C. Tensile testing and metallographic examinations determined that the hafnium oxide coating produced the best high temperature diffusion barrier for tungsten of the four coatings.
Veltri, R. D.↗
Effects of shuttle bay environment on UV sensitive photographic film results of measurements aboard STS-7 and STS-8
Schumann emulsions, having low gelatin content and no protective gelatin overcoating, are extremely sensitive to environmental conditions and handling. Experiments using this emulsion are to be flown on the space shuttle within the cargo-bay. Because the environment of the cargo-bay is unknown, a Get-Away-Special payload was designed to expose Kodak-type SO 652 Schumann emulsion to the residual atmosphere of the cargo-bay. The experiment was programmed to make exposures for various time periods to determine the maximum length of time the film could be exposed in making a measurement and what precautions would be required to preserve the film during ascent into orbit and reentry. The results of the STS-7 and STS-8 flights indicated that long exposures in the shuttle bay do not produce high fog levels in orbit. Observations of severe bleaching of the latent image makes protection of the emulsion during reentry manditory and increase of fog levels with time set a limit of four weeks (preferably less than three) between installation and recovery of the emulsion for processing.
Kreplin, R. W.↗