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Detection of explosive gas leaks such as hydrogen (H2) becomes key element in the wake of counter-terrorism threats, introduction of hydrogen powered vehicles and use of hydrogen as a fuel for space explorations. In recent years, a significant interest has developed on metal oxide nanostructured sensors for the detection of hydrogen gas. Gas sensors properties such as sensitivity, selectivity and response time can be enhanced by tailoring the size, the shape, the structure and the surface of the nanostructures. Sensor properties (sensitivity, selectivity and response time) are largely modulated by operating temperature of the device. Issues like instability of nanostructures at high temperature, risk of hydrogen explosion and high energy consumption are driving the research towards detection of hydrogen at low temperatures. At low temperatures adsorption of O2- species on the sensor surface instead of O- (since O- species reacts easily with hydrogen) result in need of higher activation energy for hydrogen and adsorbed species interaction. This makes hydrogen detection at room temperature a challenging task. Higher surface area to volume ratio (resulting higher reaction sites), enhanced electronic properties by varying size, shape and doping foreign impurities (by modulating space charge region) makes nanocrystalline materials ideal candidate for room temperature gas sensing applications. In the present work various morphologies of nanostructured tin oxide (SnO2) and indium (In) doped SnO2 and titanium oxide (titania, TiO2) were synthesized using sol-gel, hydrothermal, thermal evaporation techniques and successfully integrated with the micro-electromechanical devices H2 at ppm-level (as low as 100ppm) has been successfully detected at room temperature using the SnO2 nanoparticles, SnO2 (nanowires) and TiO2 (nanotubes) based MEMS sensors. While sensor based on indium doped tin oxide showed the highest sensitivity (S =Ra/Rg= 80000) and minimal response time (10sec.). Highly porous SnO2 nanoparticles thin film (synthesized using template assisted) showed response time of about 25 seconds and sensitivity 4. The one dimensional tin oxide nanostructures (nanowires) based sensor showed a sensitivity of 4 and response time of 20 sec. Effect of aspect ratio of the nanowires on diffusion of hydrogen molecules in the tin oxide nanowires, effect of catalyst adsorption on nanowire surface and corresponding effect on sensor properties has been studied in detail. Nanotubes of TiO2 prepared using hydrothermal synthesis showed a sensitivity 30 with response time as low as 20 seconds where as, TiO2 nanotubes synthesized using anodization showed poor sensitivity. The difference is mainly attributed to the issues related to integration of the anodized nanotubes with the MEMS devices. The effect of MEMS device architecture modulation, such as, finger spacing, number and length of fingers and electrode materials were studied. It has been found that faster sensor response (~ 10 sec) was observed for smaller finger spacing. A diffusion model is proposed for elucidating the effect of inter-electrode distance variation on conductance change of a nano-micro integrated hydrogen sensor for room temperature operation. Both theoretical and experimental results showed a faster response upon exposure to hydrogen when sensor electrode gap was smaller. Also, a linear increase in the sensor sensitivity from 500 to 80000 was observed on increasing the electrode spacing from 2 to 20 μm. The improvement in sensitivity is attributed to the higher reactive sites available for the gaseous species to react on the sensor surface. This phenomenon also correlated to surface adsorbed oxygen vacancies (O-) and the rate of change of surface adsorbed oxygen vacancies. This dissertation studied in detail dimensionality aspects of materials as well as device in detecting hydrogen at room temperature.

Advances in the interconnection technology have played a key role in the continued improvement of the integrated circuit (IC) density, performance and cost. Copper (Cu) metallization, dual damascenes processing and integration of copper with low dielectric constant material are key issues in the IC industries. Chemical mechanical planarization of copper (CuCMP) has emerged as an important process for the manufacturing of ICs. Usually, Cu-CMP process consists of several steps such as the removal of surface layer by mechanical action of the pad and the abrasive particles, the dissolution of the abraded particles in the CMP solution, and the protection of the recess areas. The CMP process occurs at the atomic level at the pad/slurry/wafer interface, and hence, slurries and polishing pads play critical role in its successful implementation. The slurry for the Cu-CMP contains chemical components to facilitate the oxidation and removal of excess Cu as well as passivation of the polished surface. During the process, these slurry chemicals also react with the pad. In the present study, investigations were carried out to understand the effect of hydrogen peroxide (H2O2) as an oxidant and benzotriazole (BTA) as an inhibitor on the CMP of Cu. Interaction of these slurry components on copper has been investigated using electrochemical studies, x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). In the presence of 0.1M glycine, Cu removal rate was found to be high in the solution containing 5% H2O2 at pH 2 because of the Cu-glycine complexation reaction. The dissolution rate of the Cu was found to increase due to the formation of highly soluble Cu-glycine complex in the presence of H2O2. Addition of 0.01M BTA in the solution containing 0.1M glycine and 5% H2O2 at pH 2 exhibited a reduction in the Cu removal rate due to the formation of Cu-BTA complex on the surface of the Cu further inhibiting the dissolution. XPS and SIMS investigations revealed the formation of such Cu-glycine complex, which help understand the mechanism of the Cu-oxidant-inhibitor interaction during polishing. Along with the slurry, pads used in the Cu-CMP process have direct influence an overall process. To overcome problems associated with the current pads, new application specific pad (ASP) have been developed in collaboration with PsiloQuest Inc. Using plasma enhanced chemical vapor deposition (PECVD) process; surface of such ASP pads were modified. Plasma treatment of a polymer surface results in the formation of various functional groups and radicals. Post plasma treatment such as chemical reduction or oxidation imparts a more uniform distribution of such functional groups on the surface of the polymer resulting in unique surface properties. The mechanical properties of such coated pad have been investigated using nanoindentation technique in collaboration with Dr. Vaidyanathan’s research group. The surface morphology and the chemistry of the ASP are studied using scanning electron microcopy (SEM), x-ray photoelectron spectroscopy (XPS), and fourier transform infrared spectroscopy (FTIR) to understand the formation of different chemical species on the surface. It is observed that the mechanical and the chemical properties of the pad top surface are a function of the PECVD coating time. Such PECVD treated pads are found to be hydrophilic and do not require being stored in aqueous medium during the not-in-use period. The metal removal rate using such surface modified polishing pad is found to increase linearly with the PECVD coating time. Overall, this thesis is an attempt to optimize the two most important parameters of the Cu-CMP process viz. slurry and pads for enhanced performance and ultimately reduce the cost of ownership (CoO).