Developing a fundamental understanding of photocurrent generation processes at organic-inorganic interfaces is critical for improving hybrid solar cell efficiency and stability. This dissertation explores processes at these interfaces by combining data from photovoltaic device performance tests with characterization experiments conducted directly on the device. The dissertation initially focuses on exploring how morphologically and chemically modifying the organic-inorganic interface, between poly(3-hexylthiophene) (P3HT) as the electron donating light absorbing polymer and titanium dioxide (TiO₂) as the electron acceptor, can result in stable and efficient hybrid solar cells. Given the heterogeneity which exists within bulk heterojunction devices, stable interfacial prototypes with well-defined interfaces between bilayers of TiO₂ and P3HT were developed, which demonstrate tunable efficiencies ranging from 0.01 to 1.6 %. Stability of these devices was improved by using Cu-based hole collecting electrodes. Efficiency values were tailored by changing TiO₂ morphology and by introducing sulfide layers like antimony trisulfide (Sb₂S₃) at the P3HT-TiO₂ interface. The simple bilayer device design developed in this dissertation provides an opportunity to study the precise role played by nanostructured TiO₂ surfaces and interfacial modifiers using a host of characterization techniques directly on a working device. Examples introduced in this dissertation include X-ray photoelectron spectroscopy (XPS) depth profiling analysis of metal-P3HT and P3HT-TiO₂ interfaces and Raman analysis of bonding between interface modifiers like Sb₂S₃ and P3HT. The incompatibility of TiO₂ with P3HT was significantly reduced by using P3HT derivatives with -COOH moieties at the extremity of a polymer chain. The role of functional groups like -COOH in interfacial charge separation phenomena was studied by comparing the photovoltaic behavior of these devices with those based on pristine P3HT. Finally, for hybrid solar cells discussed in this dissertation to become commercially viable, high temperature processing steps of the inorganic TiO₂ layer must be avoided. Accordingly, this dissertation demonstrates the novel use of electromagnetic radiation in the form of microwaves to catalyze growth of anatase TiO₂ thin films at temperatures as low as 150 °C, which is significantly lower than that used in conventional techniques. This low temperature process can be adapted to a variety of substrates and can produce patterned films. Accordingly, the ability to fabricate TiO₂ thin films by the microwave process at low temperatures is anticipated to have a significant impact in processing devices based on plastics. / text

The widespread deployment of wireless sensors in our homes, offices, factories and infrastructure has opened the door for system designers to create novel approaches for powering wireless sensor nodes. In recent years, energy harvesting has emerged as the power supply of choice for embedded system designers, enabling wireless sensors to be used in applications that previously were not feasible with conventional battery-powered designs. This report details the design and development of an energy harvesting wireless sensor from concept to production. Design constraints included the requirement to operate reliably in a wide variety of environments, the use of commercially available components, and a visually appealing form factor. The result is a very power-efficient, solar-powered wireless sensor that measures temperature, voltage, and illumination level at the solar cell and has an ultra slim form factor. / text

Steps on a high index metal or semiconductor surface may play a fundamental role for electronic structure, adsorption, film growth, chemical reaction and catalysis. The surface atomic and electronic structures of stepped W(110) surfaces have been investigated by a few research groups during the past 20 years. But there is still a lot of controversy. We use high resolution core level photoemission to study several different stepped tungsten surfaces. Curve fittings of the spectra permit tests of core-level binding- energy shift models that relate local atomic coordination to binding -energy differences associated with terrace and step-edge atoms. For the first time we find a well resolved W4f₂/₇ peak associated with step edge atoms. We attribute previous failure to directly detect the step-edge effects in core level photoemission to contamination by hydrogen. The well resolved peaks for surface atoms with different coordinations can serve as a “finger print” for specific atoms. Experiments in which stepped surfaces are systematically dosed by H₂ clarify the role played by H contamination. We also grow Ag nanowires on the stepped W(110) surface and use angle resolved photoemission to study the band structure. We find distinct dispersion for the nanowires along the step edge direction while there is only little dispersion perpendicular to the wires. The second part of the research is core level photoemission study on Cesium film growth on Cu(100) surface. We study the phonon broadening effect for Cs at different temperatures. We compare our data with previous theoretical models and get good results on surface and bulk Debye temperatures and zero temperature phonon broadening. The binding energy shifts for the Cs 5p₂/₇ at different temperatures have also been investigated. The results fit the lattice expansion model very well except at temperature higher than 200 K. The higher temperature deviation is caused by thermal evaporation of Cs films. This conclusion is checked by the following coverage dependent core level peaks study on the Cs/Cu(100) system. / text

Compared with its inorganic counterpart, organic thin-film transistor (OTFT) has advantages such as low-temperature fabrication, adaptability to large-area flexible substrate, and low cost. However, they usually need high operating voltage and thus are not suitable for portable applications. Although reducing their gate–dielectric thickness can lower the operating voltage, it increases their gate leakage. A better way is making use of high-κ gate dielectric, which is the main theme of this research. Firstly, pentacene OTFTs with HfO2 gate dielectric nitrided in N2O or NH3 at 200 oC were studied. The NH3-annealed OTFT displayed higher carrier mobility, larger on/off current ratio, smaller sub-threshold swing and smaller Hooge?s parameter than the N2O-annealed device. All these advantages were attributed to more nitrogen incorporation at the dielectric surface by the NH3 annealing which provided stronger passivation of surface traps. The incorporation of lanthanum to hafnium oxide was demonstrated to realize enhanced interface in the pentacene OTFTs. Therefore, pentacene OTFTs with HfLaO gate dielectric annealed in N2, NH3, O2 or NO at 400 oC were investigated. Among the 4 devices, the NH3-annealed OTFT obtained the highest carrier mobility, smallest sub-threshold swing and smallest 1/f noise. All these should be attributed to the improved interface between the gate dielectric and the organic semiconductor associated with the passivation effects of the NH3 annealing on the dielectric surface. The processing temperature of OTFTs is a big concern because use of flexible or glass substrate is the trend in organic electronics. Therefore, the HfLaO gate dielectric was annealed in N2, NH3, or O2 at two different temperatures, 200 oC and 400 oC. For all the annealing gases, the OTFTs annealed at 400 oC achieved higher carrier mobility, which could be supported by SEM image that pentacene tended to form larger grains (thus less carrier scattering) on HfLaO annealed at 400 oC. Furthermore, the HfLaO film annealed at 400 oC achieved much smaller leakage because more thermal energy at higher annealing temperature could remove oxide defects more effectively. Fluorination of the HfLaO film (annealed in N2 or NH3 at 400 oC) in a plasma based on CHF3 and O2 was also proposed. For both annealing gases, the OTFT with a 100-s plasma treatment achieved higher carrier mobility and smaller 1/f noise than that without plasma treatment. All these improvements should be due to fluorine incorporation at the dielectric surface which passivated the traps there. By contrast, for longer time (300 s or 900 s) of plasma treatment, the performance of the OTFTs deteriorated due to damage of dielectric surface induced by excessive plasma treatment. Lastly, a comparative study was done on pentacene OTFTs with HfLaO or La2O3 as gate dielectric. For the same annealing gas (H2, N2, NH3, or O2 at 400 oC), the OTFT with La2O3 gate dielectric obtained lower carrier mobility, smaller on/off current ratio, and larger threshold voltage than that based on HfLaO. The worse performance of the OTFTs with La2O3 gate dielectric was due to the degradation of La2O3 film caused by moisture absorption. / published_or_final_version / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

Recently, the portfolio of compounds approved for inhalation therapy has expanded rapidly for lung disease therapies. The rationale for this delivery approach includes a more targeted and localized delivery to the diseased site with reduced systemic exposure, potentially leading to decreased adverse side effects. We have proposed that brittle matrix powders prepared by thin film freezing (TFF) are a suitable platform for pulmonary drug delivery which can achieve high lung concentrations while limit the corresponding systemic levels associated with toxicity, and enhanced physicochemical and aerodynamic properties can be obtained by varying TFF processing parameters. In Chapter 2, the in vitro and in vivo performance of an amorphous formulation prepared by TFF and a crystalline micronized formulation produced by milling was compared for Tacrolimus (TAC). TFF processed matrix powders was capable of achieving deep lung delivery due to its low density, highly porous and brittle characteristics. When emitted from a Miat® monodose inhaler, TFF processed TAC formulations exhibited a fine particle fraction (FPF) of 83.3% and a mass median aerodynamic diameter (MMAD) of 2.26 µm. Single dose 24-h pharmacokinetic studies in rats demonstrated that the TAC formulation prepared by TFF exhibited higher pulmonary bioavailability with a prolonged retention time in the lung, possibly due to decreased clearance (e.g., macrophage phagocytosis), compared to the micronized TAC formulation. Additionally, TFF formulation generated a lower systemic TAC concentration with smaller variability than the micronized formulation following inhalation, potentially leading to reduced side effects related to the drug in systemic circulation. Chapter 3 investigated the impact of processing parameters in the TFF process on the physicochemical and aerodynamic properties of the resulting formulations. All of these enhanced powder properties resulted from higher freezing rate contributed to a better aerodynamic performance of the obtaining formulations. Moreover, a decreasing trend of FPF was observed for these TFF powders when the initial solid concentrations increased. The variation of the freezing rate and initial solid loading in the TFF process enabled the production of formulations with enhanced physicochemical properties and improved aerodynamic performance. / text

Many vaccines require an adjuvant to induce a strong immune response. Aluminum–containing adjuvants have been approved by the United States Food and Drug Administration for human use for many years. There are two main aluminum-containing adjuvants, aluminum hydroxide and aluminum phosphate. Due to their favorable safety profile, aluminum-containing adjuvants have been widely used in human vaccines for decades. Many currently licensed and commercially available vaccines contain aluminum-containing adjuvants. However, aluminum-containing vaccine adjuvants suffer from two major limiting factors: (1) aluminum-containing adjuvants can only weakly or moderately potentiate antigen-specific antibody responses and are generally considered incapable of inducing cellular immune responses; (2) vaccines that contain aluminum-containing adjuvants require cold-chain refrigeration for storage and distribution, and may not be frozen, because freezing of the vaccine in dispersion causes irreversible coagulation that damages vaccines (e.g., loss in potency and stability). In this dissertation, the first limitation was addressed by reducing the size of the aluminum hydroxide from micrometers (3-10 micrometer) to nanometers of less than 200 nm, and the second limitation mentioned above was addressed by freeze-drying vaccines that contain aluminum salts as adjuvants into a dry powder using thin-film freeze-drying. In addition, using an improved experimental design, the vaccine adjuvant activities of nanoparticles of around 200 nm was compared to that of the nanoparticles of around 700 nm. The smaller 200 nm nanoparticles showed a more potent adjuvant activity than the larger nanoparticles. When dispersed in an aqueous medium, both aluminum hydroxide and aluminum phosphate are physically 1–20 micrometer particulates. There are data showing that particulate vaccine carriers of around 200 nm (or less) may be optimal in potentiating the immunogenicity of vaccines. Based on this finding, aluminum hydroxide nanoparticles of 112 nm were synthesized, and its adjuvant activity was compared to that of the traditional aluminum hydroxide adjuvant, which have particulates of 3-20 micrometer. Using ovalbumin and Bacillus anthracis protective antigen protein as model antigens, it was found that protein antigens adsorbed on the aluminum hydroxide nanoparticles induced stronger antigen-specific antibody responses than the same protein antigens adsorbed on the traditional aluminum hydroxide microparticles of around 9.3 µm. Importantly, the inflammation reactions induced by aluminum hydroxide nanoparticles in the injection sites were milder than that induced by microparticles. Simply reducing the particle size of the traditional aluminum hydroxide adjuvant in suspension from micrometers into nanometers represents a novel and effective approach to improve its potency. The second limitation was addressed by converting vaccines that contain an aluminum salt as an adjuvant from an aqueous dispersion into a dried powder using thin-film freeze-drying. There is evidence that aluminum-containing vaccines can be lyophilized to dry powders using high speed freezing methods. Thin-film freezing is a high speed freezing method with a freezing rate between 100 to 10,000 K/s, but the feasibility of using thin-film freeze-drying to freeze-dry vaccines that contain aluminum salts as adjuvants has not been tested before. In this dissertation, Using ovalbumin as a model protein antigen and aluminum hydroxide or aluminum phosphate as an adjuvant, it was confirmed that vaccines that are adjuvanted with aluminum hydroxide or aluminum phosphate can be freeze-dried with as low as 2% (w/v) of trehalose as a cryoprotectant by thin-film freeze-drying without causing vaccine aggregation while preserving the immunogenicity of the vaccine. Finally, the feasibility of using the thin-film freeze-drying method to freeze-drying vaccines that contain aluminum salts as adjuvants was further confirmed by drying a commercial aluminum salt-adjuvanted tetanus toxoid vaccine. Vaccines that contain aluminum salts as adjuvants may be converted to a dry powder using the thin-film freeze-drying method to avoid loss of potency due exposure to freezing conditions during transport and storage. / text

The filtered cathodic vacuum arc (FCVA) technique is a well established deposition method for wear resistant mechanical coatings. More recently, this method has attracted attention for growing ZnO based transparent conducting films. However, the potential of FCVA deposition to prepare ZnO layers for electronic devices is largely unexplored. This thesis addresses the use of FCVA deposition for the fabrication of active ZnO based electronic devices. The structural, electrical and optical characteristics of unintentionally doped ZnO films grown on different sapphire substrates were systematically investigated. The potential of FCVA to grow both polar and non-polar ZnO films was demonstrated. The resulting films showed considerable promise for device applications with properties including high transparency(> 90%), moderate intrinsic carrier concentrations (10¹⁷ - 10¹⁹ cm⁻³), electron mobilities up to 110 cm⁻²/Vs, low surface roughness (< 5 nm) and well-structured photoluminescence. Post-growth annealing in oxygen at temperatures up to 800 C produced significant improvements in the electronic and optical properties of these films, due to the formation of larger grains with lower inter-grain potential barriers. Silver oxide (AgOᵪ ) and iridium oxide (IrOᵪ) Schottky diodes fabricated on annealed FCVA ZnO films showed ideality factors as low as 1.20, barrier heights up to 0.85 eV and high sensitivity to ultraviolet light (up to ̴ 10⁻⁵ at -2 V). Transparent and opaque MESFETs fabricated on these films showed well defined field effect characteristics, channel mobilities up to 70 cm⁻²/Vs and insensitivity to 1 mW/cm⁻² visible light. These devices were further subjected to extensive bias and temperature stress tests. MESFET stability appeared to be strongly dependent on Schottky gate type, bias conditions and ZnO film morphology. Positive bias stress of AgOᵪ gated devices resulted in irreversible damage, that is thought to be due to Ag electromigration across the gate interface. Mapping of the surface potential of the ZnO channel material with Kelvin probe force microscopy suggested a strong relationship between the defect density at grain boundaries and both channel mobility and current stability. Interval growth techniques were found to reduce the density of defects at grain boundaries and produced MESFETs with higher current stability. IrOᵪ gated devices showed superior bias stability and temperature resilience from 25 C-195 C.

Silver, gold, and copper metallic nanoparticle films have been utilized in various MEMS devices due to not only their electrical but also their optical properties. The focus of this research is to study the detection at room temperature of carbon monoxide (CO) and hydrogen (H2) via Surface Plasmon Resonance (SPR) phenomenon of silver-embedded Yttrium Stabilized Zirconium (Ag-YSZ) nanocomposite film, gold (Au) nanoparticle film, and an alloy film of silver-copper (Ag-Cu) , grown by the Pulsed Laser Deposition (PLD). To determine the appropriate film materials for quick and accurate CO and H2 detection at room temperature with the PLD technique, the growth process was done repeatedly. Optical tools such as X-Ray Diffraction, Alpha Step 200 Profilometer, Atomic Force Microscopy, and Scanning Electron Microscopy were used to characterize thin films. The gas sensing performance was studied by monitoring the SPR band peak behavior via UV/vis spectrophotometer when the films were exposed to CO and H2 and estimating the percent change in wavelength. The metallic nanoparticle films were tested for concentration of CO (100 to 1000 ppm) and H2 (1 to 10%). Silver based sensors were tested for the cross-selectivity of the gases. Overall the sensors have a detection limit of 100 ppm for CO and show a noticeable signal for H2 in the concentration range as low as 1%. The metallic films show stable sensing over a one-hour period at room temperature. The SPR change by UV/vis spectrophotometer shows a significant shift of 623 nm wavelength between 100 ppm CO gas and dry air at room temperature for the alloy films of Ag-Cu with a wider curve as compared to silver and gold films upon their exposure to CO and H2 indicating an improvement in accuracy and quick response. The results indicate that in research of CO and H2 detection at room temperature, optical gas sensors rather than metal oxide sensors are believed to be effective due to not only the absence of chemical involvement in the process but also the sensitivity improvement and accuracy, much needed characteristics of sensors when dealing with such hazardous gases.

There is significant need to improve the sensitivity and selectivity for detecting chemical and biological agents. This need exists in a myriad of human endeavors, from the monitoring of production of consumer products to the detection of infectious agents and cancers. Although many well established methodologies for chemical and biological sensing exist, such as mass spectrometry, gas or liquid phase chromatography, enzymelinked immunosorbent (ELISA) assays, etc., it is the goal of the work described herein to outline aspects of two specific platforms which can add two very important features, low cost and portability. The platforms discussed in this dissertation are organic semiconductor field-effect transistors (OFETS), in various architectural forms and chemical modifications, and ion channels immobilized in tethered lipid bilayers integrated with solid state devices. They take advantage of several factors to make these added features possible, low cost manufacturing techniques for producing silicon and organic circuits, low physical size requirements for the sensing elements, the capability to run such circuits on low power, and the ability of these systems to directly transduce a sensing event into an electrical signal, thus making it easier to process, interpret and record a signal. In the most basic OFET functionality, many types of organic semiconductors can be used to produce transistors, each with a slightly different range of sensitivities. When used in concert, they can produce a reversible chemical "fingerprint". These OFETS can also be integrated with silicon transistors - in a hybrid device architecture - to enhance their sensitivity while maintaining their reversibility. The organic semiconductors themselves can be chemically altered with the use of small molecule receptors designed for specific chemicals or chemical functional groups to greatly enhance the interaction of these molecules with the transistor. This increases both sensitivity and selectivity for discrete devices. Specially designed nanoscale OFET configurations with individually addressable gates can enhance the sensitivity of OFETS as well. Finally, ion channels can be selected for immobilization in tethered lipid bilayer sensors which are already inherently sensitive to the analyte of choice or can be genetically modified to include receptors for many kinds of chemical or biological agents. / text

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