This thesis presents a study of lasing properties and optical amplification in semiconducting conjugated polymers and dendrimers. Configured as surface-emitting distributed feedback lasers, the effect of incorporating wavelength-scale microstructure on the output of the devices is examined along with the ability to create such structures using simplified fabrication processes such as soft lithography. Conjugated materials have received a great deal of interest due to their broad spectral absorption, emission, ability to exhibit gain and ease of processing from solution. As a result, they show great potential for a variety of applications such as photovoltaics, displays, amplifiers and lasers. To date however, there has only been one demonstration of a polymer optical amplifier. A broadband, solution based polymer amplifier is presented where the gain overlaps with the transmission window of polymer optical fibres. The effect of transitions that reduce the availability of gain in conjugated polymers is also examined by studying saturation of absorption in thin films. Producing wavelength scale microstructure is traditionally a slow, expensive technique. Here, solvent assisted micromoulding is used to pattern polymer films in less than two minutes. The effect of the variations in the pattern transfer on the laser characteristics is examined. The micromoulding technique is then applied to fabricating novel device types such as circular gratings and flexible plastic lasers. Encapsulation of the micromoulded laser is then shown to improve the lifetime of the device by over three orders of magnitude. The degradation effects witnessed during this extended operation are characterised quantitatively, an area of study where little data exists in the literature. A novel class of branched dendrimer materials whose properties can be independently tuned due to their modular architecture are configured as blue-emitting distributed feedback lasers. The ability to tune the emission wavelength by varying the film thickness is demonstrated. By changing the chemical groups contained within the molecule, further tuning of the emission can be obtained along with the demonstration of a highly efficient blue-emitting dendrimer laser. Chemosensing using dendrimer lasers is presented by demonstrating the incredibly sensitive response of the laser device to trace vapours of nitro-benzene compounds. The future application of which could be highly beneficial in the detection of explosives.

The high temperature oxidation of ferritic stainless steel interconnects results in chromium poisoning of the solid oxide fuel cell (SOFC) electrodes, which is a limiting factor for their utilisation as SOFC interconnects. Chromium-rich spinel materials were studied as electrode supports that would be situated at the interface between interconnect and electrode, in order to reduce the effect of chromium poisoning of the electrodes. The main goal of this thesis was to find chromium-rich spinel materials with good electrical conductivity (σ ≥ 0.1 S∙cm⁻¹) in air and reducing atmosphere, chemically and mechanically stable in SOFC testing conditions. The structure and properties of newly formulated chromium-rich spinels, such as Mn₁₊ₓCr₂₋ₓO₄ (x = 0, 0.5), MnFeₓCr₂₋ₓO₄ (x = 0.1, 1), MgMnCrO₄, MnLiₓCr₂₋ₓO₄ (x = 0.1) and MgMₓCr₂₋ₓO₄, (M = Li, Mg, Ti, Fe, Cu, Ga) were studied aiming at their application as electrode support material for solid oxide fuel cells. Cation distributions were determined by Rietveld refinement from X-ray diffraction (XRD), within the limits of XRD precision and correlated with electrical properties determined experimentally. The chemical stability in reducing conditions was studied and the reduction effects upon materials were evaluated by XRD phase analysis and microstructure analysis. It was found that MnMₓCr₂₋ₓO₄ materials have a limited stability to reduction, only MnCr₂O₄ proved to have good stability when reduced, with negative influence for its p-type semiconductor conductivity. Even though MnFeCrO₄ had limited stability to reduction, in reducing conditions the conductivity changed from p-type to n-type semiconductor. A similar behaviour to reduction was observed for MgFeCrO₄. Also the mechanical and chemical compatibility of some spinels with YSZ was studied in terms of thermal expansion coefficient (TEC/K⁻¹), sintering step and possible chemical reactions. Lithium titanate spinels, starting with LiCrTiO₄, were investigated in terms of structure, properties and spinel - ramsdellite phase transition temperature also with the purpose of new material development. For these materials positive results were obtained in conductivity and chemical stability in reducing conditions. The performance of MnFeCrO₄ and MgFeCrO₄ as electrode support materials was investigated when used alone or impregnated with (La₀.₇₅Sr₀.₂₅)₀.₉₇Cr₀.₅Mn₀.₅O₃, La₀.₈Sr₀.₂FeO₃, Ce₀.₉Gd₀.₁O₂, CeO₂ or Pd. Composite anodes for SOFC were prepared by aqueous infiltration of nitrate salts into porous MnFeCrO₄ and MgFeCrO₄ scaffolds and studied by electrochemical impedance spectroscopy (EIS) in symmetrical cell configuration. The performance of the composite anodes was evaluated in humidified 5%H₂/Ar in order to understand their stability and performance at 850 °C or lower temperature with respect to the porous substrates. It was found that all the impregnated phases adhere very well to the spinel and considerably enhance performance and stability to a level required for SOFC applications. An interesting next step in this work would be to apply such spinel materials on steel interconnects, integrate them into testing SOFC devices and evaluate their effect upon chromium poisoning of the electrodes.

Pyridazines are a heterocyclic aromatic compound containing a characteristic N-N bond that are utilized in many fields, including medicine and electronics. It is this latter field that Dr. Snyder's research group is focused upon. Organometallic compounds are a better conducting material than the current inorganic compounds used in electronics due to better conductance of electricity, lower production cost, and the ability to be formed into thin films. With this in mind, Dr. Snyder's research group has set out to synthesize organometallic compounds for this purpose. Following procedures set forth by Snyder etc, and altered to form an off-metal route, we have successfully synthesized a library of fulvenes, Thalium Cp salts, 5,6 fused pyridazines, and pyridazial complexes. Thalium Cp salts were converted to Rhenium and Magnenese complexes through transmetalation. We have had success with the off-metal route at both higher yields and greater purity than the previous published on-metal route. These compounds have been fully characterized by 1H NMR, 13C NMR, IR, and Elemental Analysis. In addition, progress has been initiated to form Bromo Thiophene complexes following procedures set forth in Snyder, etc and modified for the off-metal route. However only fulvenes, pyridazine, and Thalium Cp salts have been synthesized and characterized by 1H NMR and 13C NMR.

In the past decade, tremendous progress has been made in organic field effecttransistors. Fused oligothiophenes and anthracene molecules are fascinatingmacromolecules having unique optoelectronic properties. These compounds are successfully employed as active components in optoelectronic devices including field effect transistors. Our goal is to design and synthesize conjugated molecular materials, which are highly functionalized through structural modifications in order to enhance their electronic, photonic, and morphological properties. The main desire is to synthesize novel organic fused-arenes having efficient charge carrier mobilities, as well as to optimize optical properties for organic field effect transistors (OFETs). Novel series of fused arene molecules of 9,10-di(thiophen-3-yl)anthracene (1), trans-2,5-(dianthracene-9- vinyl)thiophene (2), trans-5,5’-(dianthracene-9-yl)vinyl)- 2,2’-bithiophene (3), 5,5’-di(2 thiophene)-2,2’-bithiophene (4) , 9,10-(divinyl)anthracene core with 1- phenylcarboxypyrene (6) and polymers of poly(anthracene-co-bithiophene) (5) and poly(anthracene) (7) have been synthesized as promising materials for organic field effect transistors (OFETs). These compounds were confirmed and characterized by 1H-NMR, FT-IR, and elemental analysis. Their optical, thermal, and electronic properties were investigated using UV-Vis and photoluminescence spectroscopy, and thermogravimetric analysis respectively. Future studies will focus on evaluating OFETs performance of these material.

This thesis presents a new theoretical formalism which incorporates dynamical effects in atomistic electronic structure and related calculations. This research, fundamental by nature, brings about a deeper understanding of the dynamical processes in a range of materials. This establishes technologically important correlation with experimentally measured macroscopic properties and materials characterization. This method—the first of its kind—is a natural and long overdue extension of customary adiabatically separated time-independent electronic structure methods. It accounts explicitly for atomic motion due to thermal and zero-point vibration. The approach developed requires no direct treatment of time dependence in the quantum mechanical calculations, making the method widely applicable utilizing currently available electronic structure and ab-initio molecular dynamics software. The formalism is extensively applied and demonstrated for the linear optical response of bulk gallium arsenide and electronic structure of the C(111) 2 x 1 surface. Both cases are complimented by comparison of key observables to experimental data which may be used to judge the quality of the results. The results are found to be in good agreement with experimental data, with most exceptions being readily explainable and well understood.

During a traumatic insult to the brain, tissue is subjected to large stresses at high rates which often surpass cellular thresholds leading to cell dysfunction or death. Cellular events that occur at the time of and immediately after an insult are poorly understood. Immediately following traumatic brain injury (TBI), the neuronal plasma membrane may become disrupted and potentiate detrimental pathways by allowing extracellular contents to gain access to the cytosol. In the current study, neuronal plasma membrane disruption was assessed in vivo following moderate unilateral controlled cortical impact in rats using a normally cell-impermeant fluorescent compound as a plasma membrane permeability marker. This fluorescent dye was injected into the cerebrospinal fluid and was allowed to diffuse into the brain. TBI caused a widespread acute disruption of neuronal membranes which was significantly different compared to uninjured brains. Affected cells were present in cortex and hippocampal regions. These findings were complemented by an in vitro model of TBI where membrane disruption was quantified and its mechanisms elucidated. Permeability marker(s) were added to neuronal cultures before the insult as indicators for increases in plasma membrane permeability. The percentage of cells containing the permeability marker was dependent on the molecular mass, as smaller molecules gained access to a higher percentage of cells than larger ones. Permeability increases were also positively correlated with the rate of insult. Membrane disruption was transient, evidenced by a robust resealing within the first minute after the insult. In addition, membrane resealing was found to be dependent on extracellular Ca2+, as chelation of the ion abolished a significant amount of resealing. We have also investigated the effects of mechanically-induced plasma membrane disruptions on neuronal network electrical activity. We have developed a multielectrode array system that allows the study of electrical activity before, during, and after a traumatic insult to neurons. Endogenous electrical activity of neuronal cultures presented a heterogeneous response following mechanical insult. Moreover, spontaneous firing dysfunction induced by injury outlasted the presence of membrane disruptions. This study provides a multi-faceted approach to elucidate the role of neuronal plasma membrane disruptions in TBI and its functional consequences.

Optical traveling-wave resonator architectures have shown promise for the realization of many compact photonic functionalities in different research disciplines. Realizing these resonator structures in high-index contrast silicon enables dense and large scale integration of large arrays of functionalized resonators in a CMOS-compatible technology platform. Based on these motivations, the main focus of this Ph.D. research has been on the device physics, modeling, implementations, and applications of planar ultra-high Q silicon traveling-wave microresonators in a silicon-on-insulator (SOI) platform. Microdisk, microring, and racetrack resonators are the three general traveling-wave resonator architectures of interests that I have investigated in this thesis, with greater emphasis on microdisks. I have developed efficient tools for the accurate modeling of these resonators. The coupling to these resonators has been through a nano-waveguide side coupled to them. For this purpose, I have developed a systematic method for engineering a waveguide-resonator structure for optimum coupling. I have addressed the development of nanofabrication techniques for these resonators with efficient interaction with a nano-waveguide and fully compatible with active electronic integration. The outcome of the theoretical design, fabrication, and characterization of these resonators is a world-record ultra-high Q (3×10[superscript 6]) with optimum waveguide-resonator interaction. I have investigated the scaling of these resonators toward the ultimate miniaturization and its impact on different physical properties of the resonators. As a result of these investigations, I have demonstrated miniaturized Si microdisk resonators with radii of ~ 1.5 micron and Q > 10⁵ with single-mode operation over the entire large free-spectral range. This is the highest Q (~ one order more than that in previously reported data) that has been obtained for a Si microdisk resonator with this size on a SiO₂ substrate. I have employed these resonators for more advanced functionalities such as large-scale integration of resonators for spectroscopic and filtering applications, as well as the design of flat-band coupled-resonator filter structures. By proposing a systematic method of design, I have shown ultra-compact coupled-resonator filters with bandwidths ranging from 0.4 to 1 nm. I have theoretically and experimentally investigated the performance of ultra-high Q resonators at high powers and in the presence of nonlinearities. At high powers, the presence of two-photon absorption, free-carrier generation, and thermo-optic properties of silicon results in a rich dynamic in the response of the resonator. In both theory and experiment, I have predicted and demonstrated self-sustained GHz oscillation on the amplitude of an ultra-high Q resonator pumped with a continuous-wave laser.

This work characterized an in vitro 3-D neural co-culture model electrophysiologically via multi electrode arrays (MEAs), and morphologically via immunocytochemistry. Since MEA surface insulation SU-8 2000 can be used in neural micro- and multi- electrode arrays, this investigation first developed techniques to make SU-8 2000 cytocompatible. The in vitro 3-D neural co-culture model was then used to study viability and electrophysiological responses to physical injury as well as drugs known to affect network signaling. 1) SU-8 2000 cytotoxicity to neuronal cultures was linked to both poor adhesive properties and toxic components, such as solvents and photo acid generator elements. Surface treatments of oxygen plasma or parylene coating following optimal combinations of heat and isopropanol sonication showed improvement in SU-8 2000 cytocompatibility. 2) The 3-D neural networks within the 3-D co-cultures maintained considerable process outgrowth and complex 3-D structure. The cultures were viable up to three weeks in vitro with functional synaptic connections and spontaneous electrophysiological activity that was responsive to chemical modulation. This electrophysiological activity was modulated by synaptic inhibition. 3) Injury experiments demonstrated that both shear and compression loading significantly increased acute membrane permeability of cells in a strain rate dependent manner. Cell death correlated with higher membrane permeability, and shear resulted in more death than compression in these 3-D cultures. While techniques were developed for making a major micro-fabrication material cytocompatible, engineering the 3-D neural co-culture resulted in a more physiologically-representative neural tissue platform, allowing an increased understanding of structure-function relationships. Overall, this research established and characterized a neural culture system for the mechanistic study of cell growth, cell-cell and cell-matrix interactions, as well as the responses to chemical or mechanical perturbations. This is the first investigation of the network-level electrophysiological activity of 3-D dissociated cultures. This system can be used to model various pathological states in vitro, testing various reparative drugs; cell-, and tissue-engineering based strategies; as well as for pre-animal and pre-clinical testing of neural implants.

A system packaging level approach on liquid crystal polymer (LCP) was proposed for low cost, lightweight, and compact wireless communication systems. Via technology was explored for V-band W-band transitions and an active cooling system that are essential for compact multilayer integration. RF MEMS switches were fabricated and integrated at the component level to enable multi-functional devices with optimal performance. A pattern reconfigurable antenna for MIMO applications and 3D phase shifters for phased array antennas that use RF MEMS switches were presented. In addition, a lightweight expandable array was designed and measured with up to 256 elements on multilayer LCP integrated at the system level. Furthermore, a 60 GHz multilayer transceiver front end device with simultaneous transmit and receive was designed and measured for low cost 60 GHz applications. The wide variety of multilayer LCP applications integrated at the system level shows a promising future for the next generation low cost lightweight wireless communication systems.

Ceramic-matrix composites of alumina and silicon carbide whiskers have recently found novel commercial application as electromagnetic absorbers. However, a detailed understanding of how materials issues influence the composite electrical response, which underpins this application, has been absent until now. In this project, such composites were electrically measured over a wide range of conditions and modeled in terms of various aspects of the microstructure in order to understand how they work. For this purpose, three types of composites were made by different methods from the same set of ceramic powder blends loaded with different volume fractions of whiskers. In doing so, the interfaces between whiskers, the preferred orientations of whiskers, and the structure of electrically-connected whisker clusters were varied; the whisker aspect-ratio distributions were the same for all methods. At the electrode interfaces, Schottky barriers at the junctions of the electrically-percolating wide-bandgap semiconductor whiskers on the surface were responsible for a significant portion of the total measured impedance. The associated electrical response was studied on the microscopic and macroscopic level, and the gap between these different scales was bridged. Also, a modeling approach was developed for the non-linear behavior of the composite which results from these barriers. In regards to the whiskers within the composite bulk, the effects of various factors on the wide-band frequency dependence of the dielectric response and dc conductivity were explained and contextualized for the electromagnetic absorber application. Such factors include whisker preferred orientation, electrical percolation and cluster structure, the interfaces between electrically-connected SiC whiskers, and porosity. A quantitative correlation between the anisotropy of the microstructure and that of the conductivity was found, and was understood in terms of the interfacial SiC-Al2O3-SiC conduction mechanism. This behavior was shown to differ from the behavior commonly observed for other disordered mixtures of relatively conductive particles dispersed inside insulating polymer hosts. A description of this new mechanism was developed based on an observed correlation between the temperature dependencies of the static and radio-frequency electrical responses. Also, the aforementioned non-linear response model was expanded upon to describe conduction through and across electrically-percolated clusters. The model demonstrates how loading and interface behavior influence the topology and the strength of the non-linear response of the clusters.