Publications

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Proton exchange membrane fuel cells are being extensively studied as power sources because of their technological advantages such as high energy efficiency and environmental friendliness. The most effective catalyst in these systems consists of nanoparticles of Pt or Pt-based alloys on carbon supports. Understanding the role of the nanoparticle size and structure on the catalytic activity and degradation is needed to optimize the fuel cell performance and reduce the noble metal loading. One of the more significant causes of fuel cell performance degradation is the cathode catalyst deactivation. There are four mechanisms considered relevant to the loss of electrochemically active surface area of Pt in the fuel cell electrodes that contribute to cathode catalyst degradation including: catalyst particle sintering such as Ostwald ripening, migration and coalescence, carbon corrosion and catalyst dissolution. Most approaches to study this catalyst degradation utilize membrane electrode assemblies (MEAs), which results in a complex system where it is difficult to deconvolute the effects of the metal nanoparticles. Our research addresses catalyst degradation by taking a fundamental approach to study electrocatalyst using model supports. Nanostructured particle arrays are engineered directly onto planar glassy carbon electrodes. These model electrocatalyst structures are applied to electrochemical activity measurements using a rotating disk electrode and surface characterization by scanning electron microscopy. Sample transfer between these measurement techniques enables examination of the same catalyst area before and after electrochemical cycling. This is useful to probe relationships between electrochemical activity and catalyst structure such as particle size and spacing. These model systems are applied to accelerated aging studies of activity degradation. We will present our work demonstrating the mechanistic aspects of catalyst degradation using this simplified geometric system. The active surface area loss observed in repeated cyclic voltammetry is explained through characterization and imaging of the same RDE electrode structures throughout the aging process.

The mechanisms governing D loss in ErD2 films with and without a Mo diffusion barrier on kovar substrates were studied between 200 and 600 °C via in-situ Ion Beam Analysis (IBA). Significant intermixing between kovar and Er was observed above 450°C and between kovar and ErD2 above 500 °C. The D loss mechanism in ErD2 films was found to change from intermixing between kovar and ErD2 at low temperatures (< 500 °C) to thermal decomposition at higher temperatures (> 500 °C). Diffusion between kovar and ErD2 was measured isothermally at 500 and 550 °C. An activation energy of 2.1 eV and a pre-exponential factor of 0.071 cm2/s were determined. Diffusion between the kovar components and ErD2 film was inhibited by depositing a 200 nm Mo diffusion barrier between the kovar substrate and the ErD2 film. The processing of the Mo diffusion barrier was shown to impact its performance. Intermixing between the kovar / Mo / ErD2 stack becomes significant between 500 and 550 °C with a sputter deposited Mo diffusion barrier and between 550 and 600 °C for an electron-beam evaporated Mo diffusion barrier. Copyright © 2009 ASM International® All rights reserved.

{sm_bullet}Mixing from some thermal process steps thought to drive H,D,T loss - This does not appear to be a problem with the Mo/Er occluder stacks {sm_bullet}Diffusion barriers investigated to prevent mixing

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Friction and wear are major concerns in the performance and reliability of micromechanical (MEMS) devices. While a variety of lubricant and wear resistant coatings are known which we might consider for application to MEMS devices, the severe geometric constraints of many micromechanical systems (high aspect ratios, shadowed surfaces) make most deposition methods for friction and wear-resistance coatings impossible. In this program we have produced and evaluate highly conformal, tribological coatings, deposited by atomic layer deposition (ALD), for use on surface micromachined (SMM) and LIGA structures. ALD is a chemical vapor deposition process using sequential exposure of reagents and self-limiting surface chemistry, saturating at a maximum of one monolayer per exposure cycle. The self-limiting chemistry results in conformal coating of high aspect ratio structures, with monolayer precision. ALD of a wide variety of materials is possible, but there have been no studies of structural, mechanical, and tribological properties of these films. We have developed processes for depositing thin (<100 nm) conformal coatings of selected hard and lubricious films (Al2O3, ZnO, WS2, W, and W/Al{sub 2}O{sub 3} nanolaminates), and measured their chemical, physical, mechanical and tribological properties. A significant challenge in this program was to develop instrumentation and quantitative test procedures, which did not exist, for friction, wear, film/substrate adhesion, elastic properties, stress, etc., of extremely thin films and nanolaminates. New scanning probe and nanoindentation techniques have been employed along with detailed mechanics-based models to evaluate these properties at small loads characteristic of microsystem operation. We emphasize deposition processes and fundamental properties of ALD materials, however we have also evaluated applications and film performance for model SMM and LIGA devices.

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The synthesis and characterization of crystalline tungsten disulphide (WS2) solid lubricant thin films grown by atomic layer deposition (ALD) using WF6 and H2S gas precursors was studied. A new catalytic route was established to promote nucleation and growth of WS2 films on silicon surfaces with native oxide. Scanning electron microscopy with energy dispersive spectroscopy and Raman spectroscopy were used to determine the film morphology, composition, and crystallinity. The films exhibited solid lubricating behavior with a steady-state friction coefficient of 0.04 in a dry nitrogen environment.

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The stress of scandium dideuteride, ScD{sub 2}, thin films is investigated during each stage of vacuum processing including metal deposition via evaporation, reaction and cooldown. ScD{sub 2} films with thin Cr underlayers are fabricated on three different substrate materials: molybdenum-alumina cermet, single crystal sapphire and quartz. In all experiments, the evaporated Cr and Sc metal is relatively stress-free. However, reaction of scandium metal with deuterium at elevated temperature to form a stoichiometric dideuteride phase leads to a large compressive in-plane film stress. Compression during hydriding results from an increased atomic density compared with the as-deposited metal film. After reaction with deuterium, samples are cooled to ambient temperature, and a tensile stress develops due to mismatched coefficients of thermal expansion (CTE) of the substrate-film couple. The residual film stress and the propensity for films to crack during cooldown depends principally on the substrate material when using identical process parameters. Films deposited onto quartz substrates show evidence of stress relief during cooldown due to a large CTE misfit; this is correlated with crack nucleation and propagation within films. All ScD{sub 2} layers remain in a state of tension when cooled to 30 C. An in-situ, laser-based, wafer curvature sensor is designed and implemented for studies of ScD{sub 2} film stress during processing. This instrument uses a two-dimensional array of laser beams to noninvasively monitor stress during sample rotation and with samples stationary. Film stress is monitored by scattering light off the backside of substrates, i.e., side opposite of the deposition flux.