Two identified setbacks for CIGS based devices in order to obtain higher efficiency are parasitic absorption in the window layer structure and losses in open-circuit voltage due to bad interfaces. This study investigated how the performance of the solar cell is affected by depositing intrinsic ZnO (i-ZnO) and ZnMgO with atomic layer deposition (ALD) instead of the conventional sputtering. No significant improvement in fill factor was obtained by the use of ALD compared to sputtering, leading to the conclusion that pinholes in the sputtered film are not a detrimental factor for the cell. As the thickness of the i-layer increased, an increase in FF was observed for the ALD-deposited i-layer, whereas a decrease was observed for the sputtered i-layer. The open-circuit voltage was considered constant between the two series with only small fluctuations, indicating that the defect chemistry of the i-ZnO/CdS interface was not improved with the use of ALD. In this study it is shown that a gain in short-circuit current can be obtained for CIGS solar cells in the high energy region of the spectrum by reducing the thickness of the i-ZnO, as well as alloying the ZnO with Mg. When compared with a baseline layer sample with a sputtered i-layer thickness of around 90 nm, the estimated gain in short-circuit current density without a loss in fill factor was 0.14 and 0.20 mA/cm2 for ALD and sputtering, respectively. For the series with a ZnMgO i-layer, the highest estimated gain was 0.17 mA/cm2. This was observed for the sample with a 4:1 (Zn:Mg) pulse ratio, whereas higher Mg contents yielded a too high band gap that resulted in an electron blocking barrier.

Nas últimas décadas, sistemas de suprimento de energia que utilizam recursos renováveis têm sido estudados e empregados como opção para o fornecimento de energia elétrica. Devido aos avanços da tecnologia fotovoltaica, associada à diminuição de custos e maior conhecimento de seu desempenho, os sistemas fotovoltaicos apresentam-se como uma opção tecnicamente promissora. Neste contexto, a energia solar fotovoltaica, que, além de gerar eletricidade de forma distribuída também vem ganhando cada vez mais espaço no mercado mundial. Esta tecnologia evita as emissões de gases poluentes e é uma fonte alternativa que diversifica a matriz energética. Para complemento da energia hidrelétrica é necessária uma fonte energética com várias características ecologicamente corretas, a energia solar fotovoltaica é uma dessas fontes, pois é limpa (não poluente), inesgotável, silenciosa, estática, distributiva, simples em sua operação, possui características modulares podendo-se integrar as edificações. Para viabilizar sua implantação nas edificações, vários países, inclusive o Brasil, também buscam soluções para o futuro, elaborando estudos para avaliar a eficácia dessa tecnologia. Adicionalmente, como a energia é cada vez mais necessária para o desenvolvimento humano, utilizar a fonte de geração próxima ao ponto de consumo é uma maneira eficaz de reduzir as perdas por transmissão e distribuição. Esta dissertação tem por objetivo apresentar os conceitos, aspectos e aplicações das células solares de filmes finos na inserção como gerador fotovoltaico de energia elétrica integrada a estrutura das edificações. O foco principal do tema da dissertação é o estudo de área disponível na edificação, estimando o potencial fotovoltaico de geração existente no envoltório. Através desta análise, pode-se quantificar a contribuição energética de uma unidade geradora fotovoltaica para a redução de consumo energético na rede em que a edificação estiver conectada. / In recent decades, energy supply systems that use renewable resources have been studied and used as an option for the supply of electricity. Due to advances in photovoltaic technology, coupled with lower costs and greater knowledge of its performance, photovoltaic systems are presented as an option technically promising. In this context, photovoltaic solar energy, this, besides generating electricity in distributed also gaining more and more space in the world market. This technology avoids the emissions of greenhouse gases and is an alternative source to diversify the energy matrix. To complement the hydropower energy supply is needed with various features eco-friendly, photovoltaic solar energy is one of those sources, because it is clean (clean) endless, silent, static, distributive, simple in its operation, has modular features can to integrate the buildings. To enable its deployment in buildings, several countries, including Brazil, also look for solutions for the future, preparing studies to evaluate the effectiveness of this technology. Additionally, energy is increasingly necessary for human development, using the power generation near the point of consumption is an effective way to reduce transmission and distribution losses. This paper aims to present the concepts, issues and applications of thin film solar cells in photovoltaic generator insertion as power integrated structure of buildings. The main focus of the dissertation topic is the study of the available area in the building, estimating the potential of photovoltaic generation in existing wrap. Through this analysis, one can quantify the energy contribution of a photovoltaic generating unit to reduce energy consumption in the network in which the building is connected.

My dissertation work integrates the techniques of microfabrication, micro/nanofluidics, and bioanalytical chemistry to develop miniaturized devices for healthcare applications. Semiconductor processing techniques including photolithography, physical and chemical vapor deposition, and wet etching are used to build these devices in silicon and polymeric materials. On-chip micro-/nanochannels, pumps, and valves are used to manipulate the flow of fluid in these devices. Analytical techniques such as size-based filtration, solid-phase extraction (SPE), sample enrichment, on-chip labeling, microchip electrophoresis (µCE), and laser induced fluorescence (LIF) are utilized to analyze biomolecules. Such miniaturized devices offer the advantages of rapid analysis, low cost, and lab-on-a-chip scale integration that can potentially be used for point-of-care applications.The first project involves construction of sieving devices on a silicon substrate, which can separate sub-100-nm biostructures based on their size. Devices consist of an array of 200 parallel nanochannels with a height step in each channel, an injection reservoir, and a waste reservoir. Height steps are used to sieve the protein mixture based on size as the protein solution flows through channels via capillary action. Proteins smaller than the height step reach the end of the channels while larger proteins stop at the height step, resulting in separation. A process is optimized to fabricate 10-100 nm tall channels with improved reliability and shorter fabrication time. Furthermore, a protocol is developed to reduce the electrostatic interaction between proteins and channel walls, which allows the study of size-selective trapping of five proteins in this system. The effects of protein size and concentration on protein trapping behavior are evaluated. A model is also developed to predict the trapping behavior of different size proteins in these devices. Additionally, the influence of buffer ionic strength, which can change the effective cross-sectional area of nanochannels and trapping of proteins at height steps, is explored in nanochannels. The ionic strength inversely correlates with electric double layer thickness. Overall, this work lays a foundation for developing nanofluidic-based sieving systems with potential applications in lipoprotein fractionation, protein aggregate studies in biopharmaceuticals, and protein preconcentration. The second project focuses on designing and developing a microfluidic-based platform for preterm birth (PTB) diagnosis. PTB is a pregnancy complication that involves delivery before 37 weeks of gestation, and causes many newborn deaths and illnesses worldwide. Several serum PTB biomarkers have recently been identified, including three peptides and six proteins. To provide rapid analysis of these PTB biomarkers, an integrated SPE and µCE device is assembled that provides sample enrichment, on-chip labeling, and separation. The integrated device is a multi-layer structure consisting of polydimethylsiloxane valves with a peristaltic pump, and a porous polymer monolith in a thermoplastic layer. The valves and pump are fabricated using soft lithography to enable pressure-based sample actuation, as an alternative to electrokinetic operation. Porous monolithic columns are synthesized in the SPE unit using UV photopolymerization of a mixture consisting of monomer, cross-linker, photoinitiator, and various porogens. The hydrophobic surface and porous structure of the monolith allow both protein retention and easy flow. I have optimized the conditions for ferritin retention, on-chip labelling, elution, and µCE in a pressure-actuated device. Overall functionality of the integrated device in terms of pressure-controlled flow, protein retention/elution, and on-chip labelling and separation is demonstrated using a PTB biomarker (ferritin). Moreover, I have developed a µCE protocol to separate four PTB biomarkers, including three peptides and one protein. In the future, an immunoaffinity extraction unit will be integrated with SPE and µCE to enable rapid, on-chip analysis of PTB biomarkers. This integrated system can be used to analyze other disease biomarkers as well.

The aluminum oxide growth rate for aluminum protected with 2.4 nm of aluminum fluoride has been determined. We show that a 2.4 nm aluminum fluoride layer does not prevent aluminum from oxidation but does significantly retard the oxide growth – decreasing the oxide layer thickness from 1 nm in less than an hour to 0.9 nm over 116 hours. Additionally, the optical constants for aluminum oxide growing under an aluminum fluoride barrier layer have been determined – showing an increase in absorption at high energies for Al2O3 forming at room temperature as compared to highly ordered Al2O3 formed at high temperatures.

La lumière polarisée est généralement considérée comme une valeur ajoutée et est souvent utilisée pour améliorer l'observation de scènes et d’échantillons, grâce à différents processus d'optimisation. Cependant, il existe un certain nombre de situations où la polarisation de la lumière est pénalisante, et pour lesquelles il est majeur que la lumière polarisée soit transformée en lumière non polarisée. Pour illustration, de nombreuses applications spatiales nécessitent des détecteurs embarqués pour analyser les flux optiques provenant de la Terre ou de l’environnement. Ces flux sont collectés après avoir été diffusés et réfléchis par les différents éléments rencontrés, qui peuvent partiellement polariser la lumière étudiée. Cette dépolarisation n’est pas prédictible car elle dépend fortement des milieux traversés alors qu’elle influe fortement sur l’étalonnage des instruments. Bien que l'on puisse facilement transformer l'état de polarisation de la lumière en un autre état arbitraire, ou passer d’une lumière non polarisée à une lumière polarisée, la situation inverse qui consiste à dépolariser une lumière est moins fréquente et s'accompagne souvent de pertes optiques et d'une réduction de la cohérence spatiale ou temporelle. Dans cette thèse, nous proposons une technique alternative originale s’appuyant sur le principe de dépolarisation spatiale. Elle requiert un composant de type multicouche optique présentant un gradient transverse de propriétés optiques. Nous montrons dans quelles conditions ce gradient vient satisfaire à une condition de dépolarisation spatiale, sans créer de perte d’énergie / Polarized light is generally considered as an added value and is often used to improve the viewing of scenes and samples through various optimization processes. However, there are a number of situations where the polarization of the light is penalizing, and for which it is important that the polarized light is transformed into unpolarized light. For example, many space applications require embedded sensors to analyze optical flux from the Earth or the environment. These fluxes are collected after being scattered and reflected by the different elements encountered, which can partially polarize the light studied. This depolarization is not predictable because it strongly depends on the environments encountered whereas it strongly influences the calibration of the instruments. Although the polarization state of light can be easily transformed into another arbitrary state, or from unpolarized light to polarized light, the reverse situation of depolarizing light is less common and is often accompanied by optical losses and a reduction in spatial or temporal coherence. In this thesis, we propose an original alternative technique based on the principle of spatial depolarization. It requires an optical multilayer type component having a transverse gradient of optical properties. We show under which conditions this gradient satisfies a spatial depolarization condition, without creating energy losses. This synthesis step simultaneously takes into account the spatial and spectral variations of the optical properties of the filter

Millimeter wave imaging systems are the next generation imaging systems being developed for security and surveillance purposes. In this work, thin film metal-insulator-metal (MIM) tunnel junction based detector using Ni-NiO-Cr has been developed for the first time for millimeter wave detection operating at 94 GHz. Extensive process development has been carried out to fabricate the MIM junctions. Arrays of MIM junctions with 1 µm² contact area and ultra-thin insulator layer of ~3 nanometer have been developed using e-beam lithography and reactive sputtering, respectively. MIM diodes were also fabricated in a bulk-micromachined diaphragm configuration to minimize surface wave loss. DC and millimeter wave measurements were carried out on the fabricated diodes to determine the device characteristics and performance. The current-voltage (I-V) measurements yielded current in the range of few µA with significant non-linearity and asymmetry. A maximum sensitivity of 7 V-1 was also obtained from the fabricated diode. These tunnel junctions showed a positive response to millimeter wave signal, with output current in the range of few µA. By controlling the input power of the millimeter wave signal, the output current from the device could be varied. Additionally, MIM diodes with 100 µm² contact area were developed using optical lithography technique. The I-V characteristics of diode demonstrated a uniform behavior, with a sensitivity value of 15 V-1. Furthermore, the diodes were utilized to observe the effects of post-deposition annealing on the diode I-V behavior. The I-V measurement provided evidence of diode operation up to 350°C, with optimal operation at 250°C. Finally, the feasibility of using an organic insulator was also investigated. MIM junctions were fabricated with a thin layer of polyaniline using Langmuir-Blodgett deposition process. The electrical characteristics of the polyaniline based MIM junction was determined by evaluating its I-V response. The use of an alternate dielectric proved successful, yielding a significant non-linearity and asymmetry. However, the output current obtained from these junctions was in the order of nano-Amperes. By optimizing the deposition process, the organic MIM junctions can be developed to yield better device characteristics.

Gold monolayer-protected nanoclusters (MPCs) with average diameters of 1-5 nm protected by alkane- and arenethiolates were synthesized. Mixed-monolayer protected nanoparticles (MMPCs) were prepared by functionalizing hexanethiolate-protected MPCs with either 11-mercaptoundecanoic acid (MUA-MMPC), 11-mercaptoundecanol (MUO-MMPC), or 4-aminothiophenol (ATP-MMPC) using ligand place exchange. Presentation of various chemical reagents such as nucleophile, acid, or base and change in physical environment through ultrasonic and thermal irradiation resulted in changes to particles and their physical properties. Thermogravimetric analysis (TGA) was used to measure maximum temperature of the derivated thermogravimetric peaks (Tmax,DTG) as a means of comparing temperature dependence of mass loss. The absorption spectrum within the surface plasmon resonance (SPR) band was monitored over time throughout chemical and ultrasonic treatments to assess stability of these particles in solution. MUA-MMPCs and ATP-MMPCs were self-assembled with Cu2+, poly(sodium 4- styrenesufonate), poly(allylamine hydrochloride), generation 2 polyamidoamine dendrimer, and C60 fullerene as linking molecules on functionalized glass substrates using a layer-by-layer approach resulting in nanoparticle multi-layer films. The thin films were characterized using UV-vis spectroscopy during deposition, and then before and after chemical treatment, and thermal and ultrasonic irradiation to assess stability of nanocomposites. Finally, an in-situ cross-linking approach was used to deposit gold MPC-C60 thin film nanocomposite on functionalized glass substrate. UV-vis spectroscopy was used to monitor deposition rates of the resulting film in comparison with the MPC-C60 multilayer film assembled layer-by-layer. These MPC-C60 nanocomposites were also characterized using conductive atomic force microscopy (C-AFM).

The 5d transition metal oxides have drawn substantial interest for predictions of being suitable candidates for hosting exotic electronic and magnetic states, including unconventional superconductors, magnetic skyrmions, topological insulators, and Weyl semimetals. In addition to the electron-electron correlation notable in high-temperature 3d transition metal superconductors, the 5d oxides contain a large spin-orbit interaction term in their ground state, which is largely responsible for the intricate phase diagram of these materials. Iridates, or compounds containing 5d iridium bonded with oxygen, are of particular interest for their spin-orbit split Jeff = 1/2 state, which is partially filled without the presence of any additional electron correlation. However, the comparable energetics between a small, finite electron correlation energy and the spin-orbit interaction make the band structure of iridates amenable to small perturbations of the crystalline lattice and ideal for exploring the interplay between these two interactions. While altering the spin-orbit interaction strength of iridium is tenably not feasible, the electron correlation energy can be tuned using a variety of experimental techniques. In this dissertation, the electronic and magnetic properties of iridates at various electron correlation energies are studied by altering the epitaxial lattice strain, dimensionality, and the radius size of the A-site cation. These parameters tune the effective electronic bandwidth of the system, which is inversely proportional to the effective electron correlation energy. The lattice strain and the cationic radius size achieve this by altering the Ir-O-Ir bond angle between nearest neighbor Ir ions. In the case of dimensionality tuning, the effective bandwidth is controlled via the coordination number of each Ir ion. In the first study, a metal-to-insulator transition is observed in thin films of the semi-metallic SrIrO3 as in-plane compressive lattice strain is increased. This observation is consistent with the expectation of compressive lattice strain increasing the effective correlation energy; however, optical spectroscopy spectra reveal the increase is not sufficient for opening an insulating Mott gap. In the second part, the effective correlation energy is adjusted using a dimensional confinement of the layered iridate Sr2IrO4. Here, the coordination number of each Ir ion is reduced using an a-axis oriented superlattice of one-dimensional IrO2 quantum stripes, where several emergent features are revealed in its insulating Jeff = 1/2 state. In the final study, the effective correlation is tuned in a series of mixed-phase pyrochlore iridate thin films, where the Ir atoms take a corner-shared tetrahedral configuration. Here, a transition between conducting to insulating magnetic domain walls is revealed as the correlation energy is increased via A-site chemical doping. Each of these studies sheds light on the pronounced role the effective correlation energy plays in determining the local subset of phases predicted for iridates and related systems featuring strong spin-orbit interactions.

Hydrogen exposure of insulating d0-titanates, such as SrTiO3 (STO), has displayed the formation of intriguing conducting states. These conducting states form through the use of forming gas (N2/H2) annealing or hydrogen plasma exposure, where hydrogen gas is exposed to high energy microwaves. The exposure of STO to hydrogen causes metallic conductivity due to the introduction of hydrogen cations on some of the oxygen sites. However, the optical properties of this hydrogen-exposed STO have not been well-studied. Further, Ba0.5Sr0.5TiO3 (BST), an insulating dielectric, also shows changes in its conductivity upon hydrogen exposure. Unlike STO where the conductivity of the hydrogen-exposed material has been characterized, the optical, electronic, and transport properties of hydrogen exposed BST have not been studied. Thus, by studying hydrogen-exposed BST and STO, our understanding of the effects of hydrogen on insulators can be enhanced. In the first study, the effects of the exposure of insulating dielectric BST thin films to a hydrogen plasma is presented. These BST thin films are deposited on GdScO3 (GSO) substrates via Pulsed Laser Deposition (PLD). After deposition, the thin films are exposed to a hydrogen plasma. Just five minutes of hydrogen plasma exposure is enough to induce conductivity in the BST thin film. This conducting state is dominated by the interplay of disorder and strong electron correlations introduced during hydrogen exposure. Further, the optical properties indicate the formation of a transparent conductor, as the introduction of disorder and strong correlations has not changed the optical properties of the BST thin film in the visible spectrum. BST demonstrates an example of a new type of transparent conductor that utilizes large effective mass carriers to generate conductivity. In the second study, the effects of hydrogen doping on the surface of STO is explored. The conducting heterointerface that forms between PLD-deposited thin films of LaAlO3 (LAO) on STO is used as the standard to explore this hydrogen surface doping. The optical, electronic, and transport properties of water-leached and buffered hydrofluoric acid (BHF) etched heterointerfaces are characterized and compared. The recently developed water-leaching method is compared with the well-known BHF etching method, which has been shown to unintentionally dope the STO surface with fluorine and hydrogen. Both methods generate single-terminated atomically flat STO substrate surfaces that are ideal for heterointerface formation. After deposition, the optical, electronic, and transport properties of both the water-leached and BHF-etched heterointerfaces show no meaningful difference, demonstrating that water-leaching may also unintentionally dope the STO substrate surface with hydrogen. However, these results confirm that water-leaching generates a high-quality conducting heterointerface without the safety concerns of BHF.

Thin film arrays of molecules or supramolecules are active subjects of investigation because of their potential value in electronics, chemical sensing, catalysis, and other areas. Scanning probe microscopes (SPMs), including scanning tunneling microscopes (STMs) and atomic force microscopes (AFMs) are commonly used for the characterization and metrology of thin film arrays. As opposed to transmission electron microscopy (TEM), SPMs have the advantage that they can often make observations of thin films in air or liquid, while TEM requires highly specialized techniques if the sample is to be in anything but vacuum. SPM is a surface imaging technique, while TEM typically images a 2D projection of a thin 3D sample. Additionally, variants of SPM can make observations of more than just topography; for instance, magnetic force microscopy measures nanoscale magnetic properties. Thin film arrays are typically two-dimensionally periodic. A perfect, infinite two-dimensionally periodic array is mathematically constrained to belong to one of only 17 possible 2D plane symmetry groups. Any real image is both finite and imperfect. Crystallographic Image Processing (CIP) is an algorithm that Fourier transforms a real image into a 2D array of complex numbers, the Fourier coefficients of the image intensity, and then uses the relationship between those coefficients to first ascertain the 2D plane symmetry group that the imperfect, finite image is most likely to possess, and then adjust those coefficients that are symmetry-related so as to perfect the symmetry. A Fourier synthesis of the symmetrized coefficients leads to a perfectly symmetric image in direct space (when accumulated rounding and calculation errors are ignored). The technique is, thus, an averaging technique over the direct space experimental data that were selected from the thin film array. The image must have periodicity in two dimensions in order for this technique to be applicable. CIP has been developed over the past 40 years by the electron crystallography community, which works with 2D projections from 3D samples. Any periodic sample, whether it is 2D or 3D has an "ideal structure" which is the structure absent any crystal defects. The ideal structure can be considered one average unit cell, propagated by translation into the whole sample. The "real structure" is an actual sample containing vacancies, dislocations, and other defects. Typically the goal of electron and other types of microscopy is examination of the real structure, as the ideal structure of a crystal is already known from X-ray crystallography. High resolution transmission electron microscope image based electron crystallography, on the other hand, reveals the ideal crystal structure by crystallographic averaging. The ideal structure of a 2D thin film cannot be easily in a spatially selective fashion examined by grazing incidence X-ray or low energy electron diffraction based crystallography. SPMs straightforwardly observe thin films in direct space, but SPM accuracy is hampered by blunt or multiple tips and other unavoidable instrument errors. Especially since the film is often of a supramolecular system whose molecules are weakly bonded (via pi bonds, hydrogen bonds, etc.) both to the substrate and to each other, it is relatively easy for a molecule from the film to adhere to the scanning tip during the scan and become part of the tip during subsequent observation. If the thin film array has two-dimensional periodicity, CIP is a unique and effective tool both for image enhancement (determination of ideal structure) and for the quantification of overall instrument error. In addition, if a sample of known 2D periodicity is scanned, CIP can return information about the contribution of the instrument itself to the image. In this thesis we show how the technique is applied to images of two dimensionally periodic samples taken by SPMs. To the best of our knowledge, this has never been done before. Since 2D periodic thin film arrays have an ideal structure that is mathematically constrained to belong to one of the 17 plane symmetry groups, we can use CIP to determine that group and use it for a particularly effective averaging algorithm. We demonstrate that the use of this averaging algorithm removes noise and random error from images more effectively than translational averaging, also known as "lattice averaging" or "Fourier filtering". We also demonstrate the ability to correct systematic errors caused by hysteresis in the scanning process. These results have the effect of obtaining the ideal structure of the sample, averaging out the defects crystallographically, by providing an average unit cell which, when translated, represents the ideal structure. In addition, if one has recorded a scanning probe image of a 2D periodic sample of known symmetry, we demonstrate that it is possible to use the Fourier coefficients of the image transform to solve the inverse problem and calculate the point spread function (PSF) of the instrument. Any real scanning probe instrument departs from the ideal PSF of a Dirac delta function, and CIP allows us to quantify this departure as far as point symmetries are concerned. The result is a deconvolution of the "effective tip", which includes any blunt or multiple tip effects, as well as the effects caused by adhesion of a sample molecule to the scanning tip, or scanning irregularities unrelated to the physical tip. We also demonstrate that the PSF, once known, can be used on a second image taken by the same instrument under approximately the same experimental conditions to remove errors introduced during that second imaging process. The preponderance of two-dimensionally periodic samples as subjects of SPM observation makes the application of CIP to SPM images a valuable technique to extract a maximum amount of information from these images. The improved resolution of current SPMs creates images with more higher-order Fourier coefficients than earlier, "softer" images; these higher-order coefficients are especially amenable to CIP, which can then effectively magnify the resolution improvement created by better hardware. The improved resolution combined with the current interest in supramolecular structures (which although 3D usually start building on a 2D periodic surface) appears to provide an opportunity for CIP to significantly contribute to SPM image processing.