The layered honeycomb lattice iridate Na2IrO3 is a novel candidate material for either a topological insulator or spin liquid. These states of matter are one possible starting point for the future realization of scalable quantum computation, but may also find application in magnetic memory or low-power electronic devices. This thesis reports on the pulsed laser deposition of high-quality heteroepitaxial (001)-oriented Na2IrO3 thin films with well-defined in-plane epitaxial relationship on 5-by-5 and 10-by-10 square millimeter single-crystalline sapphire, YAlO3 and zinc oxide substrates. Three-dimensional Mott variable range hopping is the dominant conduction mechanism between 40 and 300 K. Moreover, a signature of the proposed topological insulator phase is found in magnetoresistance by observation of the weak antilocalization effect that is associated with topological surafce states. Compared to single crystals, a smaller, 200-meV optical gap in Na2IrO3 thin films is found by Fourier-transform infrared transmission spectroscopy.

In this work cadmium telluride thin film photovoltaic devices have successfully been produced using a novel closed-field magnetron sputtering technique. This technique offers the possibility of producing cells in an all-in-one vacuum process with the potential to provide a new lower cost production route. The sputtered cadmium telluride layers were characterised in detail using a range of advanced microscopy based techniques both in the as deposited and after the cadmium chloride treated state, a treatment that is necessary to produce a working cell. In the as deposited condition the cadmium telluride layer was seen to have a fine-grained columnar structure containing a high density of stacking faults. After the cadmium chloride treatment these grains recrystallized and the new grains were equiaxed with a much lower density of intragranular defects. Similar effects were also observed in samples prepared using close space sublimation. To understand this recrystallization behaviour during the cadmium chloride treatment, the key treatment parameters were systematically varied. Chemical analysis in Scanning Transmission Electron Microscopy (STEM) showed that chlorine travelled down the cadmium telluride grain boundaries and accumulated adjacent to the cadmium telluride/cadmium sulphide interface. This interface is where the cadmium telluride grains were found to recrystallise first during interrupted cadmium chloride treatments. The nature of the stacking faults was examined using High Resolution Transmission Electron Microscopy (HR-TEM). This showed that in localised regions up to one plane of atoms per sequence was missing based on the expected zinc blende structure. This changed the packing of the atoms such that a local change in crystal structure occurred. This local change in phase was successfully mapped using Electron Backscatter Diffraction in planar section produced using Focused Ion Beam milling. This was subsequently studied in more detail using Transmission Electron Backscatter Diffraction in the Scanning Electron Microscope, where the intra-granular arrangement of the phases was observed. HR-TEM was used to quantitatively measure the linear defects in the cadmium telluride layer after thermal annealing with and without the cadmium chloride present. This showed that annealing alone resulted in only a modest reduction in the density of linear defects and grain recrysallisation only occurred in the presence of cadmium chloride. Cadmium magnesium telluride (CMT) was successfully grown epitaxially onto the cadmium telluride as an electron reflector layer to improve cell performance. During deposition the cell experienced high temperatures and this caused the stacking faults to return in a cell that had been previously cadmium chloride treated. This resulted in a reduction in cell efficiency, providing another link between linear defects and a degradation in cell performance.

This dissertation investigates dissipation in microelectromechanical (MEMS) resonators via detailed analysis and modeling of the energy loss mechanisms and provides a framework toward creating resonant devices with ultra-low dissipation. Fundamental mechanisms underlying acoustic energy loss are explored, the results of which are applied to understanding the losses in resonant MEMS devices. Losses in the materials, which set the ultimate limits of the achievable quality factor of the devices, are examined. Other sources of loss, which are determined by the design of the resonator, are investigated and applied to example resonant MEMS structures. The most critical of these designable loss mechanisms are thermoelastic dissipation (TED) and support (or anchor) loss of acoustic energy through the attachment of the MEMS device to its external environment. The dissipation estimation framework enables prediction of the quality factor of a MEMS resonator, which were accurate within a factor of close to 2 for high-frequency bulk acoustic wave MEMS resonators, and represents a signficant step forward by closing one of the largest outstanding problems in MEMS devices: how to predict the quality factor for a given device. Dissipation mitigation approaches developed herein address the most critical dominant loss mechanisms identified using the framework outlined above. These approaches include design of 1D phononic crystals (PCs) and novel 3D MEMS structures to trap and isolate vibration energy away from the resonator anchors, optimization of resonator geometry to suppress thermoelastic dissipation, and analysis of required levels of surface polish to reduce surface dissipation. Phononic crystals can be used to manipulate the properties of materials. In the case of the 1D PC linear acoustic bandgap (LAB) structures developed here, this manipulation arises from the formation of frequency stop bands, or bandgapwhich convert silicon from a material capable of supporting acoustic waves to a material which rejects acoustic propagation at frequencies in the bandgap. The careful design of these LAB structures is demonstrated to be able to enhance the quality factor and insertion loss of MEMS resonators without significant detrimental effects on the overall device performance.

The work investigates the selective deposition of cobalt oxide via atomic layer deposition. Methoxysilanes chlorosilane and poly(trimethylsilylstyrene) self-assembled monolayers are utilized to prevent wetting of water and cobalt bis(N-tert butyl, N'-ethylpropionamidinate) from the substrate, thereby controlling nucleation on the substrate and providing a pathway to enable selective deposition of cobalt oxide. Sr and Al are deposited atop the oxide films to scavenge oxygen and yield carbon-free cobalt metal films. Thermal reduction of the oxide layer in the presence of CO and H 2 was also investigated as an alternative. Finally, we demonstrate control over the tunability of the coercivity of the resultant films by controlling the reduction conditions.

Η τεχνολογία φωτοβολταϊκών λεπτών φιλμ πυριτίου συνδυάζει χαμηλό κόστος παραγωγής, μικρό χρόνο ενεργειακής απόσβεσης και χαμηλές απαιτήσεις σε πρώτες ύλες. Ωστόσο, μειονεκτήματα όπως η χαμηλή απόδοση και η φωτοεπαγόμενη υποβάθμιση του άμορφου πυριτίου καθιστουν την τεχνολογία αυτή λιγότερο ανταγωνιστική σε σχέση με τα φωτοβολταϊκά κρυσταλλικού πυριτίου. Για να αυξηθεί η απόδοση χρησιμοποιούνται περισσσότερα ενεργά στρώματα οδηγώντας σε φωτοβολταϊκά πολυεπαφών. Συνδυάζοντας άμορφο και μικροκρυσταλλικό πυρίτιο, με ενεργειακό χάσμα περίπου 1.7eV και 1.1eV αντίστοιχα προκύπτει η διάταξη a-Si/μc-Si. Στην παρούσα εργασία παρουσιάζεται εκτενώς το φωτοβολταϊκό a-Si/μc-Si, το οποίο αναφέρεται και ως micromorph. Μελετώνται τα χαρακτηριστικά των ενεργών υλικών από τα οποία αποτελείται και οι ιδιότητες εκείνες που απαιτούνται για υψηλής ποιότητας επιστρώσεις. Παρουσιάζονται τα ιδιαίτερα χαρακτηριστικά της τεχνολογίας φωτοφολταϊκών λεπτών φιλμ πυριτίου και οι διαφορές της με τις υπόλοιπες τεχνολογίες. Μελετάται επίσης η δομή της διάταξης a-Si/μc-Si και η έρευνα που αφορά τις τεχνικές βελτιστοποίησής της και την αύξηση της απόδοσης. Στη συνέχεια γίνεται πειραματική μελέτη για τις επιδόσεις ενός φωτοβολταϊκού πλαισίου a-Si/μc-Si σε συνθήκες εξωτερικού χώρου, σε σύγκριση με φωτοβολταϊκά πλαίσια άλλων τεχνολογιών πυριτίου, ενός μονοκρυσταλλικού και ενός άμορφου. Το πλαίσιο a-Si/μc-Si της εταιρείας Heliosphera που μελετήθηκε έχει υποστεί την αναμενόμενη φωτοεπαγόμενη υποβάθμιση και η απόδοσή του σε πρότυπες συνθήκες βρέθηκε ίση με 8.14% με μια μείωση 8.5% από την αρχική απόδοση. Μελετήθηκε η εξάρτηση της επίδοσης των φωτοβολταϊκών πλαισίων από την μεταβολή της γωνίας πρόσπτωσης, τη θερμοκρασία και την ένταση της ηλιακής ακτινοβολίας. Επιβεβαιώθηκε πειραματικά η μείωση της απόδοσης του πλαισίου a-Si/μc-Si με την αύξηση της αέριας μάζας, κάτι που παρατηρήθηκε και για το πλαίσιο αμόρφου πυριτίου. Η μελέτη φωτοβολταϊκών πλαισίων σε συνθήκες εξωτερικού χώρου θα οδηγήσει στην κατανόηση των διαφορών μεταξύ διαφορετικών τεχνολογιών και στη σημασία των κλιματολογικών συνθηκών ενός τόπου στην επιλογή των φωτοβολταϊκών πλαισίων για κάποια εγκατάσταση. / Thin film silicon photovoltaic technology combines low production cost, short energy payback time and low demands of raw materials. However, drawbacks as low efficiency and light induced degradation make this technology less competitive in regard to crystalline silicon solar cells. In order to increase the efficiency, more active layers are used leading to multijuction photo voltaics. Combining amorphous and microcrystalline silicon with energy bandgap of 1.7eV and 1.1eV correspondingly, results in the device a-Si/μc-Si.. In this work a-Si/μc-Si, which is also referred as micromorph, is thoroughly presented. The characteristics of its active materials and the properties required for device quality layers are studied. The specific properties of thin film silicon photovoltaics are presented along with the differences with other technologies. The structure of the a-Si/μc-Si device and the research for its optimization techniques and efficiency increase are also studied. An experimental study takes place for the performance of an a-Si/μc-Si photovoltaic module in outdoor conditions, in comparison with other silicon photovoltaic technologies, as monocrystalline and amorphous silicon. The module a-Si/μc-Si of the company “Heliosphera” that was studied has undertaken the prospective light induced degragation and its efficiency in standard conditions was 8.14% with a reduction of 8.5% from the initial efficiency. The performance of the photovoltaic modules was studied under the effect of shifts in the angle of incidence, temperature changes and changes in the solar irradiation intensity. The reduction in the efficiency of the a-Si/μc-Si module with the increase of the air mass was experimentally confirmed and was also verified for the amorphous silicon module. The study of photovoltaic modules in outdoor conditions will lead in better understanding the differences among various technologies and the effect of the climate conditions of a location on the choice of the photovoltaic modules for an installation.

Membrane technology has been used in water purification for decades. However, membrane fouling remains a limiting factor. One way to control fouling is through surface modification. Several studies report that increasing surface hydrophilicity can reduce membrane fouling. Surface modification via physical coating (i.e., thin-film composite membrane) was explored in this research to prevent membrane fouling. Before making thin-film composite membranes, it was important to study structure/property relations in a series of potential coating materials. This research aims to contribute to a better fundamental understanding of the structure/property relations which govern water transport, rejection of model foulants (i.e., emulsified oil droplet or protein), and fouling characteristics in hydrogels based on poly(ethylene glycol) diacrylate (PEGDA) and N-vinyl-2-pyrrolidone (NVP). Crosslinked poly(ethylene glycol) (PEG) free-standing films were prepared by UV-induced photopolymerization of PEGDA crosslinker in the presence of varying amounts of water or monofunctional poly(ethylene glycol) acrylate (PEGA). The crosslinked PEGDA films exhibited polymerization induced phase separation (PIPS) when the water content of the prepolymerization mixture was greater than 60 wt%. Visible light absorbance measurements, water uptake, water permeability, and salt kinetic desorption experiments were used to characterize the structure of these phase-separated, crosslinked hydrogels. The films with PIPS exhibited a porous morphology in cryogenic scanning electron microscope (CryoSEM) studies. Dead-end filtration experiments using deionized water and bovine serum albumin (BSA) solutions were performed to explore the fundamental transport and fouling properties of these materials. The total flux of pure water through the films after prior exposure to BSA solution was nearly equal to that of the as-prepared material, indicating that these PEGDA films resist fouling by BSA under the conditions studied. Crosslinked NVP free-standing films were prepared by UV-induced photopolymerization in the presence of water, with NVP as the monomer and N,N’-methylenebisacrylamide (MBAA) as the crosslinker. A series of crosslinked films were polymerized at various prepolymerization water contents, NVP/MBAA ratios and at various levels of UV light intensity in the polymerization. Like PEGDA, the NVP films also underwent phase-separation during polymerization. The influence of monomer/ crosslinker ratio, prepolymerization water content, and UV intensities on membrane morphology and water transport was characterized with CryoSEM, bio-atomic force microscope (Bio-AFM) and dead-end filtration. Molecular weight cutoff (MWCO) measurements were used to characterize the sieving property of crosslinked NVP films polymerized at different UV intensities. UV intensity was found to have an impact on the interconnectivity of crosslinked membranes. Finally, tests of fouling resistance to protein solution (bovine serum albumin) and oily water emulsion were performed. The NVP crosslinked films had good protein and oily water fouling resistance. Overall, both crosslinked PEGDA and NVP films exhibit fouling resistance to oily water emulsions or protein solution. NVP films had more porous structure and higher water permeability than did PEGDA films, while the more compact structure of PEGDA films led to better rejection of model foulants (e.g., protein) than in NVP films. Based on different applications (e.g., oil/water separation, protein filtration), different coating materials must be chosen according to the membrane morphology, transport property, and rejection of model foulants to achieve the highest water flux and foulant rejection in membranes used for water purification. / text

Low-k dielectrics with porosity are being introduced to reduce the RC delay of Cu/low-k interconnect. However, during the O2 plasma ashing process, the porous low-k dielectrics tend to degrade due to methyl depletion, moisture uptake, and densification, increasing the dielectric constant and leakage current. This dissertation presents a study of the mechanisms of plasma damage and dielectric recovery. The kinetics of plasma interaction with low-k dielectrics was investigated both experimentally and theoretically. By using a gap structure, the roles of ion, photon, and radical in producing damage on low-k dielectrics were differentiated. Oxidative plasma induced damage was proportional to the oxygen radical density, enhanced by VUV photon, and increased with substrate temperature. Ion bombardment induced surface densification, blocking radical diffusion. Two analytical models were derived to quantify the plasma damage. Based on the radical diffusion, reaction, and recombination inside porous low-k dielectrics, a plasma altered layer model was derived to interpret the chemical effect in the low ion energy region. It predicted that oxidative plasma induced damage can be reduced by decreasing pore radius, substrate temperature, and oxygen radical density and increasing carbon concentration and surface recombination rate inside low-k dielectrics. The model validity was verified by experiments and Monte-Carlo simulations. This model was also extended to the patterned low-k structure. Based on the ion collision cascade process, a sputtering yield model was introduced to interpret the physical effect in the high ion energy region. The model validity was verified by checking the ion angular and energy dependences of sputtering yield using O2/He/Ar plasma, low-k dielectrics with different k values, and a Faraday cage. Low-k dielectrics and plasma process were optimized to reduce plasma damage, including increasing carbon concentration in low-k dielectrics, switching plasma generator from ICP to RIE, increasing hard mask thickness, replacing O2 by CO2 plasma, increasing CO addition in CO/O2 plasma, and increasing N2 addition in CO2/N2 plasma. By combining analytical techniques with the Kramers-Kronig dispersion relation and quantum chemistry calculation, the origin of dielectric loss was ascribed to the physisorbed water molecules. Post-ash CH4 plasma treatment, vapor silylation process, and UV radiation were developed to repair plasma damage. / text

Organic semiconductors are widely studied as potential active components for consumer electronics due largely to their easily tuned properties and the promise of lower-cost solution-based processing technology. Imide-functionalized organic small molecule compounds have been one of the more important and studied organic semiconductors. However, very few imide-functionalized conjugated polymers have been reported in the literature. The body of this dissertation focuses on the synthesis, structure-property and device studies of imide-functionalized conjugated polymers. Reasons for choosing arylene imides as polymer building blocks include: a) they impart low-lying LUMOs to polymers, allowing band-gap engineering through choice of comonomers with variable electron-donating ability; b) imide-nitrogens provide points to attach side chains to manipulate solubility and solid-state packing; c) they are easily prepared. Structure-property studies include electrochemical measurements, UV-Vis absorption spectroscopy, differential scanning calorimetry (DSC), x-ray diffraction, and in some cases evaluation as active components in field-effect transistors (OFETs) and photovoltaic devices (PVDs). The published method to synthesize 3,6-dibromo-pyromellitic bisimides (PMBI) was streamlined and poly(phenylene ethynylene)s (PPEs) with variable band gaps were prepared from them (Chapter 2). As noted in all the chapters, electrochemical and optical measurements reveal that the LUMO of the polymers is indeed dictated by the arylene imide, while the HOMO, and therefore the optical energy gap is controlled through varying the electron donor monomer. Intramolecular hydrogen bonding was employed for increasing backbone coplanarity and therefore the polymer could have higher conjugation. One of these polymers demonstrated the narrowest band gap (1.50 eV) for any published PPE. Chapter 3 describes the first published conjugated copolymers from naphthalene bisimides (NBI), here using thiophene-based comonomers as donor units. Polymers with high molecular weight and decent solubility were obtained by choosing appropriate side chains. The optical energy gaps could be tuned across the visible and into the near IR. Preliminary OFET studies revealed electron mobility as high as ~0.01 cm2/Vs. One low band gap polymer provided OFETs with electron mobility of ~0.04 cm2/Vs and hole mobility of ~0.003 cm2/Vs, which is also among the highest mobilities of ambipolar polymeric semiconductors. Using the same approach as in Chapter 3, phthalimide-based monomers were incorporated into polymer backbones for developing new high performance p-type polymer semiconductors for OFETs and PVDs (Chapter 4). Some analogues based on benzothiadiazole, PMBI, and thiophene imides as acceptors were prepared for comparison. Again, high molecular weight, soluble polymers with band gaps spanning the visible and into the near IR were obtained. OFETs from one of the polymers yielded hole mobility ~0.3 cm2/Vs under ambient atmosphere without post-processing thermal annealing, which places it squarely within the state-of-the-art for conjugated polymers. Due to the high mobility and low band gap, this polymer also leads to PVDs with moderately good power conversion efficiency (PCE: ~2%).

Donor-acceptor copolymers have received a great deal of attention for application as organic semiconductors, in particular as the active layers in low-cost consumer electronics. The functional groups grafted to the polymer backbones generally dictate the molecular orbital energies of the final materials as well as aid in self-assembly. Additionally, the side chains attached to these functional groups not only dictate the solubility of the final materials, but also their morphological characteristics. The bulk of the research presented in this dissertation focuses on the synthesis and structure-property relationships of polymers containing novel acceptor motifs. Chapter 2 focuses on the synthesis of 1,2-disubstituted cyanoarene monomers as the acceptor motif for copolymerization with known donors. It was found that cyanation of both benzene and thiophene aromatic cores resulted in a decrease of the molecular orbital energy levels. Additionally, the small size of this functional group allowed favorable self-assembly and close π-stacking to occur relative to related acceptor cores carrying alkyl side chains as evidenced by UV-Vis and WAXD data. Chapter 3 describes the systematic variation of side chain branching length and position within a series of phthalimide-based polymers. Branching of the side chains on bithiophene donor units resulted in the expected increase in solubility for these materials. Furthermore, a correlation was found between the branching position, size, and the HOMO energy levels for the polymers. Additionally, it was demonstrated that branching the alkyl side chains in close proximity to polymer backbones does not disrupt conjugation in these systems. A novel acceptor motif based on the 1,3-indanedione unit is presented in Chapter 4. Despite the stronger electron withdrawing capability of this functional group relativeto phthalimide, it was found that polymers based on this unit have the same HOMO molecular orbital energy levels as those presented in Chapter 3. It was found, however, the presence of orthogonal side chains greatly enhanced the solubility of the final polymers. Additionally, UV-Vis and WAXD measurements revealed that thermal annealing had a profound effect on the ordering of these polymers. Despite the presence of orthogonal side chains, long range order and close π-stacking distances were still achieved with these materials. Finally, alkynyl “spacers” were used in Chapter 5 to separate the solubilizing alkyl side chains from the polymer backbones on bithiophene donor monomers. The alkynyl groups allowed for conjugated polymer backbones to be achieved as well as low HOMO energy levels. A correlation between the side chain size, π-stacking distances and HOMO-LUMO energy levels was measured in this polymer series.

High deposition rates on large areas are industrial needs for mass production of microcrystalline silicon (μc-Si:H) solar cells. This doctoral work aims at exploring the usefulness of Matrix Distributed Electron Cyclotron Resonance (MDECR) plasmas to process the intrinsic layer of μc-Si:H p-i-n solar cells at high rates. With the high dissociation of silane achieved in MDECR plasmas, deposition rates as high as 6nm/s and 2.8nm/s have been demonstrated in our lab for amorphous and microcrystalline silicon respectively, without hydrogen dilution. This technique is also promising because it can be easily scaled up on large areas, just by extending the matrix of elementary microwave applicators. This subject was a unique opportunity to cover the whole chain of this field of research : A new MDECR reactor has been specially designed and assembled during this project. Its maintenance and its improvement have been important technical challenges : for example, the addition of a load-lock enabled us to lower the oxygen concentration in our films by a factor of 10. The impact of the deposition parameters (e.g. the ion energy, the substrate temperature, different gas mixtures, the microwave power) has been explored in extensive parametric studies in order to optimize the material quality. Great efforts have been invested in the characterization of the films. Our strategy has been to develop a wide range of diagnostics (ellipsometry, Raman spectroscopy, SIMS, FTIR, XRD, electrical characterizations etc.). Finally, p-i-n cells have been processed with the selected interesting materials. The successive successful improvements in the material quality (e.g. diffusion lengths of holes parallel to the substrate as high as 250 nm) did unfortunately not result in high efficiency solar cells. Their limited performance is in particular due to a very poor response in the red part of the spectrum resulting in low current densities. Consequently, the potential sources of limitation of the reactor, the material and the device have been studied : e.g. the presence of “cracks” prone to post-oxidation in the highly crystallized materials and the risk of deterioration of the ZnO substrate or of the p-doped layer by a too high process temperature or by hydrogen diffusing from the plasma.