High performance multijunction solar cells based on polycrystalline thin films will require a wide bandgap top cell with at least 15% efficiency. With the bottom cell being CIGS which have already demonstrated the required efficiencies, this work aims to study the complete fabrication and performance of Cd1-xZnxTe solar cells with a bandgap of 1.7eV on glass and flexible polyimide substrates. Cd1-xZnxTe films were deposited by RF magnetron co-sputtering with CdTe and ZnTe sources. By varying the composition of Cd1-xZnxTe being deposited the required bandgap of 1.7eV was achieved. The optical and structural properties of the films were studied with optical transmission, SEM and XRD measurements. The films exhibited high optical transmission and pinhole free grain structure. CZT solar cells were fabricated on glass and flexible polyimide substrate and were analyzed by J-V and spectral response measurements. The effect of post deposition treatments and the effect of N2 during sputtering on CZT device performance were studied.

Rubbing alignment is widely used in display industry, Rubbing cause anisotropy in rubbed polyimide thin film influence the alignment of Liquid Crystal. The major part of this article is to analyze surface optical anisotropy of rubbed polyimide thin film. RAS signals and surface free energies of rubbed polyimide thin film with different rubbing strength are measured, and relationship between anisotropy of surface and rubbing strength is discussed. The mechanism of alignment can be understood by this work. Reflection Anisotropy Spectroscopy (RAS) has been used in Semiconductor as a tool to monitor crystal growth for many years. RAS is a non-contact and non-destructive measurement method. It only measures the difference of two orthogonal complex reflection signals and optical anisotropy of surface. It¡¦s very sensitive to the anisotropy of surface. In the current studies, RAS has been used to detect surface anisotropy of rubbed polymer. We measured the surface free energy of the rubbed polyimide thin films. It has been found that surface free energy is of anisotropy due to the application of mechanical rubbing to the polymer surface. Pretilt angle influences the alignment of liquid crystals. The molecule orientation of PI surface and anisotropy of rubbed PI surface effect pretilt angle¡CPretilt angles measured by pretilt angle measurement system compare with RAS signals. RAS signals, anisotropy of surface free energies, and pretilt angles are increasing with increasing rubbing strength.

Composite fibers comprised of 5:95 wt ratio of ultra-short single walled carbon nanotubes (US-SWCNT):polyacrylonitrile (PAN) were spun using a dry-jet wet-spinning method followed by oxidative stabilization at 285 °C. The as-spun and stabilized composite fibers exhibited a 50 and 40 % increase, respectively, in modulus when compared to neat PAN. The vacuum pressure impregnation (VPI) method was employed to reinforce SWCNT fibers. SWCNT fibers were impregnated with polyamic acid (PAA) solution at 100 psi followed by thermal imidization to obtain fibers reinforced with polyimide (PI). The tensile strength was increased form 68 to 215 MPa for SWCNT fibers after VPI and imidization. Surfactant-wrapped chemically converted graphene (CCG) sheets obtained from the hydrazine reduction of GO were functionalized by treatment with aryl diazonium salts. The functionalized nanosheets disperse readily in polar aprotic solvents. A one-pot method has also been developed for reducing GO and simultaneously functionalizing it with alkyl and aryl groups. The alkyl functionalized reduced GO shows higher solubility in organic solvents when compared to GO. Graphene-filled PI composite films were prepared by solution blending of GO and PAA, casting the mixture and imidizing the films by heating up to 400 °C resulting in composite films that exhibit up to a ∼75 % increase in modulus and low moisture uptake. At 2 wt % loading GO, the composite films exhibit a conductivity of 1.25 × 10 -5 S/cm. The layer-by-layer (LbL) assembly technique was also employed in the fabrication of thin film composites of CCG and PI. The assembly was driven by the acid-base interaction between the aniline moieties on functionalized CCG and the carboxyl groups of the PAA. A simple fluid-phase processing method to obtain single to few layers of graphene without the aid of sonication has been developed. Graphene is spontaneously exfoliated from graphite and dissolved at isotropic concentrations as high as ∼1000 ppm in chlorosulfonic acid. The dissolution mechanism in superacids is protonation and electrostatic repulsion. The utility of this simple exfoliation process is further extended to diazonium functionalization of graphene allowing access to edge-functionalized graphenes with a minimal disruption of the graphitic network on the basal plane.

Materials like asphalt, asphalt concrete and polyimides that are used in the transportation and aerospace industry show viscoelastic behavior. These materials in the working environment are subject to degradation due to temperature, diffusion of moisture and chemical reactions (for instance, oxidation) and there is need for a good understanding of the various degradation mechanisms. This work focuses on: 1) some topics related to development of viscoelastic fluid models that can be used to predict the response of materials like asphalt, asphalt concrete, and other geomaterials, and 2) developing a framework to model degradation due to the various mechanisms (such as temperature, diffusion of moisture and oxidation) on polyimides that show nonlinear viscoelastic solid-like response. Such a framework can be extended to model similar degradation phenomena in the area of asphalt mechanics and biomechanics. The thermodynamic framework that is used in this work is based on the notion that the 'natural configuration' of a body evolves as the body undergoes a process and the evolution is determined by maximizing the rate of entropy production. The Burgers' fluid model is known to predict the non-linear viscoelastic fluid-like response of asphalt, asphalt concrete and other geomaterials. We first show that different choices for the manner in which the body stores energy and dissipates energy and satisfies the requirement of maximization of the rate of entropy production that leads to many three dimensional models. All of these models, in one dimension, reduce to the model proposed by Burgers. A thermodynamic framework to develop rate-type models for viscoelastic fluids which do not possess instantaneous elasticity (certain types of asphalt show such a behavior) is developed next. To illustrate the capabilities of such models we make a specific choice for the specific Helmholtz potential and the rate of dissipation and consider the creep and stress relaxation response associated with the model. We then study the effect of degradation and healing due to the diffusion of a fluid on the response of a solid which prior to the diffusion can be described by the generalized neo-Hookean model. We show that a generalized neo-Hookean solid - which behaves like an elastic body (i.e., it does not produce entropy) within a purely mechanical context - creeps and stress relaxes when infused with a fluid and behaves like a body whose material properties are time dependent. A framework is then developed to predict the viscoelastic response of polyimide resins under different temperature conditions. The developed framework is further extended to model the phenomena of swelling due to diffusion of a fluid through a viscoelastic solid using the theory of mixtures. Finally, degradation due to oxidation is incorporated into such a framework by introducing a variable that represents the extent of oxidation. The data from the resulting models are shown to be in good agreement with the experiments for polyimide resins.

In this study, we extend the rigidity and resonance of benzobisthiazo- le for the application as second-order nonlinear optics. A novel nonlinear optical polyimide (NLO-PI) containing side-chained benzobisthiazole- based chromophore has been synthesized. A hydroxyl- containing PI (PHI) was first prepared using direct thermal imidization of 2,4-diaminophenol dihydrochloride and 4,4¡¦-(hexafluoroisopropylidene)diphthalic anhydride; the benzobisthiazole-based chromophore was then prepared using 2,5-diamino- 1,4-benzenedithiol dihydrochloride as the starting monomer. The final NLO-PI was obtained by the Mitsunobu reaction via ether linkage between PHI and the chromophore. This ether linkage is expected to provide chain flexibility for better orientation under electric field during poling. Formation of benzobisthiazole-based chromophore and the corresponding NLO-PI was evidenced by FTIR and UV-vis spectra. TGA and TMA reveal a thermal decomposition temperature and a glass transition temperature as high as 576 and 324oC, respectively. The electrooptic coefficient of the NLO-PI at a wavelength of 630nm was found to be r33 = 6.62 pm/V.

This study presents a novel polyimide-based self-assembly three dimensional micro blade using surface micromachining technology for the development of micro-fan chip. The high surface-tension-force of reflowed polyimide has can be used to lift the free-standing micro blade. In addition, the thesis introduces a micro hinge structure to effectively limit the maximum lifting angle of the micro blade and to accurately lock hinge-pin into the vertical position. Many parameters have been investigated its influence on the surface-tension- force of polyimide, including the thickness of polyimide and the temperature/time in reflow processing. Based on the experimental results, 18 £gm-thick polyimide can lift the micro blade at 70¢X angle under 380 ¢J/10 hrs reflow condition. On the other hand, 25 £gm-thick polyimide has demonstrated its maximum lifting angle can be achieved to 130¢X utilizing the very high surface-tension-force induced by over contraction and deformation when it was reflowed at higher temperature (400 ¢J). Finally, this dissertation has studied the relation between the position of polyimide elastic-joint and the deflection angle (£r). Furthermore, this thesis has successfully demonstrated a novel multi-joint and asymmetrical microstructure for the development of the spiral and out-of-plane 3D micro blade.

The glassy copolyimide 6FDA-DAM:DABA was investigated as a polymer backbone for membranes used in aggressive sour gas separation applications. An esterification crosslinking mechanism enabled the synthesis of materials with augmented H₂S/CH₄ selectivity and plasticization resistance. These materials make use of polyethylene glycol (PEG) crosslinking agents and are referred to as PEGMC polymers. Rigorous dense film characterization of the novel crosslinkable materials indicates that excellent H₂S/CH₄ selectivity (24) is achievable while still maintaining high CO₂/CH₄ selectivity (29) under high pressure ternary mixed gas (CO₂/H₂S/CH₄) feeds. Defect-free asymmetric hollow fiber membranes were formed and appropriate crosslinking conditions were determined, allowing for the characterization of these fibers under realistic sour gas feed conditions. Also, a PDMS post-treatment was used to give ultra-high permselectivity for aggressive feeds. Using several mixed gas feeds containing high concentrations of CO₂ and H₂S at feed pressures up to 700 psig, it is shown that the crosslinked asymmetric hollow fiber membranes developed and manufactured through this work are capable of maintaining excellent separation performance even under exceedingly taxing operating conditions. For example, CO₂/CH₄ and H₂S/CH₄ permselectivity values of 47 and 29, respectively, were obtained for a 5% H₂S, 45% CO₂, 50% CH₄ feed at 35°C with 700 psig feed pressure. An extremely aggressive 20% H₂S, 20% CO₂, 60% CH₄ mixed gas feed with 500 psig feed pressure was also used; the maximum CO₂/CH4 and H₂S/CH₄ permselectivity values were found to be 38 and 22, respectively.

Abstract The demands toward the development of simple and cost-effective fabrication methods of metallic structures with high lateral resolution on different substrates - applied in many fields of technology, such as in microelectronics, optoelectronics, micromechanics as well as in sensor and actuator applications - gave the idea to perform this research. Due to its simplicity, laser-assisted chemical liquid-phase deposition (LCLD) has been investigated and applied for the metallization of surfaces having practical importance (Si, GaAs, SiO2, Si3N4, etc.) since the beginning of the 80s. By the invention of novel substrates (polyimide, porous silicon), it was adequate to work out new precursors or just adopt old ones and optimise LCLD in order to fabricate metallic micro-patterns upon these materials for various purposes. According to the motivations mentioned above, LCLD was utilized for the fabrication of palladium (Pd) micro-patterns on polyimide (PI), polyimide/copper flexible printed circuit boards (PCBs), fused silica (SiO2) and silicon (Si). The selective metallization of porous silicon (PS) has been carried out with nickel (Ni). Depending on the types of lasers, either the focusing (Ar+ laser beam) or diaphragm projection (KrF and XeCl excimer laser pulses) method was employed. In the course of the work, various precursors of the corresponding metals have been investigated and utilized. In the beginning, the pyrolytic decomposition of palladium-amine complex ions ([Pd(NH3)4]2+) on PI by a scanned and focused Ar+ laser beam was optimised and discussed. Thick (up to several micrometers) and narrow (~ 10 μm) Pd conductor lines with electrical conductivity close to that of the bulk were obtained. In the continuation of these investigations, the precursor was developed further. [Pd(NH3)4]2+ was mixed with the solution of formaldehyde (HCOH) in order to induce the reduction of the metal complex ions. To our knowledge, we were the first - so far - who applied this solution and described the reaction. With the proper choice of the laser parameters, thin Pd films as catalyst layers for electroless copper plating were deposited utilizing Ar+ and excimer lasers as well. The chemically plated copper deposits - upon the obtained Pd film - have excellent electrical and good mechanical properties. In the second part of the thesis, three practical applications (metallization of via holes drilled in PI/Cu flexible PCBs, end-mirror fabrication on single-mode optical fibers, and carbon nanotube growth on Pd activated Si and Si/SiO2 substrates) of Pd LCLD were realized. The previously presented [Pd(NH3)4]2+ and [Pd(NH3)4]2+/HCOH precursors were employed for creating the catalyst Pd layers for the carbon nanotube chemical vapor-phase deposition and for the autocatalytic electroless chemical copper plating, respectively. Finally, a simple novel method was introduced for the area-selective metallization of PS. Since the surface of PS reduces spontaneously most metals from their aqueous solutions, it is difficult to realize localized metal deposition from liquid-phase precursors on it. We proposed the application of a stable Ni plating bath from which the metal deposits only when the PS is irradiated with photons having wavelength shorter than 689 nm, thus making possible an area-selective laser-assisted metal deposition. The deposited metal structures and patterns were analysed by field emission scanning electron microscopy (FESEM) equipped with energy dispersive spectrometer (EDS), by the milling and imaging modes of a focused ion beam system (FIB), optical microscopy, profilometry, resistance, and by reflectance measurements.

This research aimed to develop new polymeric materials for use in membrane or adsorption processes for carbon dioxide capture. In particular, it explored the synthesis, characterization and properties of polymers incorporating a spiro-center. A dianhydride containing a spiro-center (An-1), suitable for use in the preparation of polyimides, was synthesized using a previously reported procedure. The spiro-center makes the structure of the resulting polymers (PIM-PIs) similar to polymers of intrinsic microporosity (PIMs), which are known for their high internal surface area and outstanding membrane permeation properties. PIM-polyimides PIM-PI-1 and PIM-PI-5 were successfully synthesized and characterized, and membranes prepared for permeation studies. For PIM-PI-5, gas permeation data were obtained for the first time and were shown to be in reasonable agreement with values predicted by a group contribution method. To produce membranes with even better gas permeation properties, hydroxyl-containing PIM-polyimides were introduced. The presence of a hydroxyl group in the ortho position of the imide linkage made it possible to thermally rearrange the PIM-polyimide to a PIM-polybenzoxazole (PIM-PBO) at 450 oC in an inert atmosphere. PIM-PI-OH-1 with high enough molecular weight to form a freestanding membrane was successfully synthesized using two different synthetic methods: thermal imidization and one-step polycondensation. The PIM-PI-OH-1 polymers prepared by both synthetic methods were compared in terms of gas permeation properties and CO2 uptake capacity, before and after thermal rearrangement. As expected, for polymers prepared by both methods, a significant enhancement was observed in the membranes gas permeation properties upon thermal rearrangement. Ethanol treatment was also performed on the thermally rearranged polymers, which resulted in a large increase in their permeability. The effect of aging was investigated on the ethanol treated PIM-PBO-1 membranes. It was observed that the membranes gradually lose the extra permeability created upon ethanol treatment and return to close to their original permeability value. To increase the concentration of thermally rearrangeable sites in the polymers, a dianhydride (An-2) with a smaller structure and lower molecular weight comparing to the An-1 was synthesized. A copolymer (copolymer-OH(1-2)), was synthesized using An-1 and An-2 (1:1). Gas permeation measurements were performed on the thermally rearranged polymer before and after ethanol treatment. A slight enhancement in the polymer’s selectivity toward CO2/N2 and CO2/CH4 gas pairs was observed, while maintaining the permeability. Having the same aim, PIM-PI-OH-3 was prepared using a smaller and a more rigid diamine, compared to the diamine used in the preparation of PIM-PI-OH-1. Gas permeation studies of the thermally rearranged membrane before and after ethanol treatment showed a significant increase in O2/N2 selectivity, which passed the Robeson 2008 upper bound. In adsorption experiments, CO2 uptake was higher than for PIM-PI-OH-1 and its thermally rearranged product.

The development of a polyimide and metals multi-user surface micro-machining process for Micro-electro-mechanical Systems (MEMS) is presented. The process was designed to be as general as possible, and designed to be capable to fabricate different designs on a single silicon wafer. The process was not optimized with the purpose of fabricating any one specific device but can be tweaked to satisfy individual needs depending on the application. The fabrication process uses Polyimide as the structural material and three separated metallization layers that can be interconnected depending on the desired application. The technology allows the development of out-of-plane compliant mechanisms, which can be combined with six variations of different physical principles for actuation and sensing on a single processed silicon wafer. These variations are: electrostatic motion, thermal bimorph actuation, capacitive sensing, magnetic sensing, thermocouple-based sensing and radio frequency transmission and reception.