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<p>In this work a modified polyol method was developed to synthesize in-house catalysts. The method was modified for maximum delivery of product and proved to be quick and efficient as well as cost effective. The series of IH catalysts were characterized using techniques such as UV-vis and FT-IR spectroscopy, TEM, XRD, ICP and CV.</p>

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<p> PAMAM dendrimers are a class of well-defined, hyperbranched polymeric nanocarriers that are being investigated for ocular drug and gene delivery. Their favorable properties such as small size, multivalency and water solubility can provide significant opportunities for many biologically unstable drugs and allows potentially favorable ocular biodistribution. This work exploits hydroxyl terminated dendrimers (G4-OH) as drug/gene delivery vehicles that can target retinal microglia and pigment epithelium via systemic delivery with improved efficacy at much lower concentrations without any side effects. </p><p> Two different drugs Triamcinolone acetonide (TA) and N-Acetyl Cysteine (NAC) conjugated to G4-OH dendrimers showed tailorable sustained release in physiological relevant solutions and were evaluated in-vitro and in-vivo. Dendrimer-TA conjugates enhanced the solubility of TA and were 100 fold more effective at lower concentrations than free TA in its anti-inflammatory activity in activated microglia and in suppressing VEGF production in hypoxic RPE cells. Dendrimers targeted activated microglia/macrophages and RPE and retained for a period of 21 days in I/R mice model. The relative retention of intravitreal and intravenous dendrimers was comparable, if a 30-fold intravenous dose is used; suggesting intravenous route targeting retinal diseases are possible with dendrimers. D-NAC when injected intravenously attenuated retinal and choroidal inflammation, significantly reduced (&sim;73%) CNV growth at early stage of AMD in rat model of CNV. A combination therapy of D-NAC + D-TA significantly suppressed microglial activation and promoted CNV regression in late stages of AMD without causing side-effects. </p><p> G4-OH was modified with linker having minimal amine groups and incorporation of TA as a nuclear localization enhancer resulted in compact gene vectors with favorable safety profile and achieved high levels of transgene expression in hard to transfect human retinal pigment epithelial cells (hRPE). Prepared dendrimer-gene complexes were non-toxic and achieved significant cell uptake and safe delivery of gene in to the nucleus. Further, polyethylene glycol (PEG) surface coating enhanced colloidal stability in physiological relevant solutions without affecting its transfection efficacy.</p>

In this thesis, investigations into fabricating tin oxide hydrogen gas sensors from films assembled by the deposition of tin clusters are reported. The tin clusters were formed in a UHV compatible cluster apparatus by DC magnetron sputtering and inert gas aggregation. Through SEM imaging, it was found that the morphology of tin cluster assembled films deposited onto silicon nitride substrates was highly coalesced. The coalescence between the clusters was significantly reduced by reacting the clusters with nitrogen before they were deposited. This resulted in granular films with a grain size close to that of the deposited clusters. The coalesced and granular tin films were used to fabricate tin oxide conducti-metric gas sensors. This was done by depositing the tin films onto gold contacts and then oxidising them by baking them at 250°C for 24 hours. The sensors were tested using a purpose built gas test rig. It was found that the sensors with the granular film morphology were much more sensitive to 500 ppm, 1000 ppm, and 5000 ppm of hydrogen at 200°C in ambient air with zero humidity. This was attributed to the smaller grain size and the larger surface area of the granular films.

<p> The rapidly evolving global information infrastructure requires ever faster data transfer within computer networks and stations. Integrated chip scale photonics can pave the way to accelerated signal manipulation and boost bandwidth capacity of optical interconnects in a compact and ergonomic arrangement. A key building block for integrated photonic circuits is an on-chip laser. In this dissertation we explore ways to reduce the physical footprint of semiconductor lasers and make them suitable for high density integration on silicon, a standard material platform for today's integrated circuits. We demonstrated the first room temperature metalo-dielectric nanolaser, sub-wavelength in all three dimensions. Next, we demonstrated a nanolaser on silicon, showing the feasibility of its integration with this platform. We also designed and realized an ultracompact feedback laser with edge-emitting structure, amenable for in-plane coupling with a standard silicon waveguide. Finally, we discuss the challenges and propose solutions for improvement of the device performance and practicality.</p>

<p> Chitosan is a naturally derived polymer, which represents one of the most technologically important classes of active materials with applications in a variety of industrial and biomedical fields. Polymeric materials can be regarded as promising candidates for next generation devices due to their low energy payback time. These devices can be fabricated by high-throughput processing methodologies, such as spin coating, inkjet printing, gravure and flexographic printing onto flexible substrates. However, the extensive applications of polymeric films are still limited because of disadvantages such as poor electromechanical properties, high brittleness with a low strain at break, and sensitivity to water. For certain critical applications the need for modification of physical, mechanical and electrical properties of the polymer is essential. When blends of polymer films with other materials are used, as is commonly the case, device performance directly depends on the nanoscale morphology and phase separation of the blend components. To prepare nanocomposite thin films with the desired functional properties, both the film composition and microstructure have to be thoroughly characterized and controlled.</p><p> Chitosan reinforced bio-nanocomposite films with varying concentrations of gold nanoparticles were prepared through a solution casting method. Gold nanoparticles (&sim; 32 nm diameter) were synthesized <i> via</i> a citrate reduction method from chloroauric acid and incorporated in the prepared Chitosan solution. Uniform distribution of gold nanoparticles was achieved throughout the chitosan matrix and was confirmed by SEM images. Synthesis outcomes and prepared nanocomposites were characterized using TEM, SAED, SEM, EDX, XRD, UV-Vis, particle size analysis, zeta potential and FT-IR for their physical, morphological and structural properties. Nanoscale mechanical properties of the nanocomposite films were characterized at room temperature, human body temperatures and higher temperatures using instrumented indentation techniques. The obtained films were confirmed to be biocompatible by their ability to support the growth and proliferation of human tissue cells <i> in vitro.</i> Statistical analysis on mechanical properties and biocompatibility results, were conducted. Results revealed significant enhancement on both the mechanical properties and cell adherence and proliferation. The results will enhance our understanding of the effect of nanostructures reinforcement on these important functional polymeric thin films for potential biomedical applications.</p>

With growing global energy demand there will be an increased need for sources of renewable energy such as solar cells. To make these photovoltaic technologies more competitive with conventional energy sources such as coal and natural gas requires further reduction in manufacturing costs that can be realized by solution processing and roll-to-roll printing. Colloidal quantum dots are a bandgap tunable, solution processible, semiconductor material which may offer a path forward to efficient, inexpensive photovoltaics. Despite impressive progress in performance with these materials, there remain limitations in photocarrier collection that must be overcome. This dissertation focuses on the characterization of charge recombination and transport in colloidal quantum dot photovoltaics, and the application of this knowledge to the development of new and better materials. Core-shell, PbS-CdS, quantum dots were investigated in an attempt to achieve better surface passivation and reduce electronic defects which can limit performance. Optimization of this material led to improved open circuit voltage, exceeding 0.6 V for the first time, and record published performance of 6% efficiency. Using temperature-dependent and transient photovoltage measurements we explored the significance of interface recombination on the operation of these devices. Careful engineering of the electrode using atomic layer deposition of ZnO helped lead to better TiO2 substrate materials and allowed us to realize a nearly two-fold reduction in recombination rate and an enhancement upwards of 50 mV in open circuit voltage. Carrier extraction efficiency was studied in these devices using intensity dependent current-voltage data of an operational solar cell. By developing an analytical model to describe recombination loss within the active layer of the device we were able to accurately determine transport lengths ranging up to 90 nm. Transient absorption and photoconductivity techniques were used to study charge dynamics by identifying states in these quantum dot materials which facilitate carrier transport. Thermal activation energies for transport of 60 meV or lower were measured for different PbS quantum dot bandgaps, representing a relatively small barrier for carrier transport. From these measurements a dark, quantum confined energy level was attributed to the electronic bandedge of these materials which serves to govern their optoelectronic behavior.

<p> High-speed photodiodes have diverse applications in wireless and fiber communications. They can be used as output stages for antenna systems as well as receivers for fiber optic networks. Silicon is an attractive substrate material for photonic components for a number of reasons. Low cost manufacturing in CMOS fabrication facilities, low material loss at telecommunications wavelengths, and relatively simple co-packaging with electronics are all driving interest in silicon photonic devices. Since silicon does not absorb light at telecommunications wavelengths, photodetector fabrication requires the integration of either III-V materials or germanium. Recent work on germanium photodetectors has focused on low-capacitance devices suitable for integration with silicon electronics. These devices have excellent bandwidth and efficiency, but have not been designed for the levels of photocurrent required by coherent and analog systems. This thesis explores the design, fabrication, and measurement of photodetectors fabricated on silicon with germanium absorbing regions for high speed and high power performance. </p><p> There are numerous design trade-offs between speed, efficiency, and output power. Designing for high bandwidth favors small devices for low capacitance. Small devices require abrupt absorption profiles for good efficiency, but design for high output power favors large devices with dilute absorption. The absorption profile can be controlled by the absorber layer thickness, but this will also affect the bandwidth and power handling. This work quantifies the trade-offs between high speed, high efficiency, and high power design. Intrinsic region thickness and absorption profile are identified as the most important design variables. For PIN structures, the absorption profile and intrinsic region thickness are both functions of the Ge thickness, but in uni-traveling carrier (UTC) structures the absorption profile and intrinsic region can be designed independently. This allows optimization of the absorption profile independently from the RC-limited frequency response and compression current and ultimately enables larger saturation current-bandwidth products. This thesis includes the first theory, fabrication, and measurement of a uni-traveling carrier photodiode on the Si/Ge platform. Key contributions include an accurate nonlinear device model and a complete set of processes and design rules for fabricating Ge devices in the UCSB nanofab. The UTC structure is shown to be useful in extending the bandwidth and power handling capabilities of waveguide-integrated photodiodes, especially at high frequencies.</p>

Label free detection techniques such as surface plasmon resonance, carbon nanotubes, nanowires, and interferometry have been progressing rapidly for biosensing applications. Surface plasmon resonance is considered one of the most promising label free optical techniques. The use of nanohole arrays in a metal film allows for extraordinary transmission and has been motivated by their application as biosensors. Nanohole arrays present several advantages like smaller foot print, dense integration, lower limits of detection, and collinear optical detection. This thesis presents the design parameters for the optimization of sensitivity and resolution of nanohole arrays for refractive index sensing. A systematic study is provided of the influence of the nanohole array periodicity, diameter, and gold thickness. Focused ion beam was used to fabricate the nanohole arrays. A microfluidic device with a set of embedded nanohole arrays was developed and used to measure the sensing characteristics. The results are encouraging for potential future biosensing tests. / Graduate