Polymer electrolyte membrane fuel cells (PEMFCs) have recently acquired much attention as alternatives to combustion engines for power conversion. The primary interest in fuel cell technology is the possibility of 60% power conversion efficiency as compared to the 30% maximum theoretical efficiency limited to combustion engines and turbines. Although originally conceived to work with hydrogen as a fuel, difficulties relating to hydrogen storage have prompted much effort in using other fuels. Small organic molecules such as alcohols and formic acid have shown promise as alternatives to hydrogen in PEMFCs due to their higher stability at ambient conditions. The drawbacks for using these fuels in PEMFCs are related to their incomplete oxidation mechanisms, which lead to the production of carbon monoxide (CO). When carbon monoxide is released in fuel cells it binds strongly to the platinum anode thus limiting the adsorption and subsequent oxidation of more fuel. In order to promote the complete oxidation of fuels and limit poisoning due to CO, various metal and metal oxide catalysts have been used. Motivated by promising results seen in fuel cell catalysis, this research project is focused on the design and fabrication of novel platinum-composite catalysts for the electrooxidation of methanol, ethanol and formic acid. Various Pt-composites were fabricated including Pt-Au, PtRu, Pt-Pd and Pt-CeO2 catalysts. Electrochemical techniques were used to determine the catalytic ability of each novel composite toward the electrooxidation of methanol, ethanol and formic acid. This study indicates that the novel composites all have higher catalytic ability than bare Pt electrodes. The increase in catalytic ability is mostly attributed to the increase in CO poison tolerance and promotion of the complete oxidation mechanism of methanol, ethanol and iv formic acid. Formulations including bi- and tri-composite catalysts were fabricated and in many cases show the highest catalytic oxidation, suggesting tertiary catalytic effects. The combination of bi-metallic composites with ceria also showed highly increased catalytic oxidation ability. The following dissertation expounds on the relationship between composite material and the electrooxidation of methanol, ethanol and formic acid. The full electrochemical and material characterization of each composite electrode is provided.

This dissertation addresses the fundamental problem of how to build computing systems for the nanoscale. With CMOS reaching fundamental limits, emerging nanomaterials such as semiconductor nanowires, carbon nanotubes, graphene etc. have been proposed as promising alternatives. However, nanoelectronics research has largely focused on a `device-first' mindset without adequately addressing system-level capabilities, challenges for integration and scalable assembly. In this dissertation, we propose to develop an integrated nano-fabric, (broadly defined as nanostructures/devices in conjunction with paradigms for assembly, inter-connection and circuit styles), as opposed to approaches that focus on MOSFET replacement devices as the ultimate goal. In the `fabric-centric' mindset, design choices at individual levels are made compatible with the fabric as a whole and minimize challenges for nanomanufacturing while achieving system-level benefits vs. scaled CMOS. We present semiconductor nanowire based nano-fabrics incorporating these fabric-centric principles called NASICs and N3ASICs and discuss how we have taken them from initial design to experimental prototype. Manufacturing challenges are mitigated through careful design choices at multiple levels of abstraction. Regular fabrics with limited customization mitigate overlay alignment requirements. Cross-nanowire FET devices and interconnect are assembled together as part of the uniform regular fabric without the need for arbitrary fine-grain interconnection at the nanoscale, routing or device sizing. Unconventional circuit styles are devised that are compatible with regular fabric layouts and eliminate the requirement for using complementary devices. Core fabric concepts are introduced and validated. Detailed analyses on device-circuit co-design and optimization, cascading, noise and parameter variation are presented. Benchmarking of nanowire processor designs vs. equivalent scaled 16nm CMOS shows up to 22X area, 30X power benefits at comparable performance, and with overlay precision that is achievable with present-day technology. Building on the extensive manufacturing-friendly fabric framework, we present recent experimental efforts and key milestones that have been attained towards realizing a proof-of-concept prototype at dimensions of 30nm and below.

The realm of the nano-world begins when things start getting smaller in size than one thousandth of the thickness of the human hair. Surface patterning at the nanoscale has started to find applications in information storage, self-cleaning of surfaces due to the "lotus effect", biocompatible materials based on surface roughness and many more. Several methods such as particle-beam writing, optical lithography, stamping and various kinds of self-assembly are widely used to serve the purpose of patterning smaller surface structures. However, globally much research is going into developing more efficient, reproducible and simple methods of patterning surfaces and in better controlling the order of these nanostructures. Researchers have always looked upon Nature to get inspiration and to mimic its model in engineering novel architectures. One of the methods used by this greatest artist (Nature) to make beautiful patterns around is through reaction diffusion based non-linear processes. Non-linear systems driven away from equilibrium sustain pattern only during the continuous dissipation of a regular flow of energy and are different from equilibrium processes that are converging towards a minimum in free energy (a. k. a. self-assembly). Dissipative pattern formation from micrometer to kilometers scale has been known but ordered patterns at nanoscale have never been achieved. In the process of thoroughly characterizing suitable substrates for nanoelectronics applications, we came across a remarkable process leading to the formation of highly ordered arrays of dimples on tantalum. The pattern formation happens in a narrow electrochemical windows which are functions of many parameters such as concentration, external applied voltage, temperature etc. After investigating the formation of dimples by performing spatio-temporal studies, we found that the underlying principles behind this unique way of engineering nano-structures have their roots in nonlinear interaction/reaction electro-hydrodynamics. We then have demonstrated the generality of this process by extending it to titanium, tungsten and zirconium surfaces. The pattern similar to Rayleigh-Bernard convection cells originates inside the electrochemical solution due to coupling among electrolyte ions during their migration across the electrochemical double layer (Helmholtz layer) and simultaneously imprints on the surface due to dissolution of metal oxide via etching. Based on these results we further postulate that, given appropriate electropolishing chemistry; these patterns can be formed on virtually any metal or semiconductor surface. The application of these nanostructures as nanobeakers for placing metal nanoparticles is also elucidated Highly porous materials such as mesoporous oxides are of technological interest for catalytic, sensing, optical and filtration applications: the mesoporous materials (with pores of size 2-50 nm) in the form of thin films can be used as membranes due large surface area. In the second part of this thesis, a new technique of making detachable ultrathin membranes of transition metal oxides is presented. The underlying concepts behind the detachment of membranes from the underlying substrate surface are discussed. The control on the size of the pores by modulating the voltage and concentration is also elucidated. The method is generalized by showing the similar detachment behavior on other metal oxide membranes.Thus, the results of this work introduces new techniques of engineering nanostructures on surfaces based on reaction-diffusion adaptive systems and contribute to the better understanding of electrochemical self-organization phenomena due to migration coupling induced electro-hydrodynamics. / Thesis / Doctor of Philosophy (PhD)

No description available.

No description available.

No description available.

No description available.

No description available.

No description available.

No description available.