Nos últimos anos, um conjunto de fatores tem colaborado para expansão da energia fotovoltaica no Brasil. No entanto, ainda não se oferecem políticas públicas ou incentivos regulatórios para que as distribuidoras contribuam com a geração fotovoltaica sem prejuízo ao equilíbrio de suas operações. Diante disso, este trabalho buscou investigar a viabilidade de novos papéis para as distribuidoras brasileiras frente aos desafios de modernização do setor elétrico. Para isso, buscou nos EUA, país que apresenta crescente participação de energia FV em sua matriz elétrica, exemplos de incentivos financeiros e regulatórios e novos modelos de negócios para operação das distribuidoras. Através da metodologia de análise SWOT, três modelos de negócio do mercado fotovoltaico norte-americano são avaliados para o setor de distribuição brasileiro. Os resultados evidenciam as forças e fraquezas das distribuidoras em relação a outros atores do mercado e as oportunidade e ameaças de cada modelo. / In recent years, a combination of events have contributed for solar photovoltaics raising adoption in Brazil. However, there are yet no available regulatory incentives or public policies to enable utilities participation without harming their financial equilibrium. As a result, the current study aims to identify new roles for Brazilian utilities that comply with smart grid emerging challenges. In an effort to identify examples of financial and regulatory incentives as well as new business models, North American solar photovoltaic experiences were evaluated. The effectiveness of three American business models for the Brazilian energy sector were discussed through SWOT analysis. The results indicate utilities main strengths and weaknesses compared to other energy market actors and also the opportunities and threats of each business model.

To design an efficient solar energy conversion device, theoretical input is extremely important to provide the basic guideline for experimental scientists, to fabricate the most efficient, cheap, and stable device with less efforts. This desire can be made possible if computational scientist use a proper theoretical protocol, design an energy material, then the experimentalist will only invest weeks or months on the synthetic effort. This thesis highlights my recent efforts in this direction. Monoclinic BiVO4 is has been using as a photocatalyst due to its stability, cheap, easily synthesizable, narrow band gap and ideal VB (-6.80 eV vs vacuum) but inappropriate CB (-4.56 eV vs vacuum) edge position, responsible for its low efficiency. We have carried out a comprehensive experimental and periodic density functional theory (DFT) simulations of the pristine, Oxygen defective (Ov), Se doped monoclinic BiVO4 and heterojunction with Selenium (Se-BiVO4), to improve not only its CB edge position but photocatalytic and charge carrier properties. It is found that Ov (1% Oxygen vacancy) and mild doped BiVO4 (1 to 2% Se) are thermodynamically stable, have ideal band edges ~ -4.30 eV), band gaps (~1.96 eV), and small effective masses of electrons and holes. We have also investigated the contribution of Se to higher performance by effecting morphology, light absorption and charge transfer properties in heterojunction. Finally, it is found that Se makes a direct Z-scheme (band alignments) with BiVO4 where the photoexcited electron of BiVO4 recombine with the VB of Se, consequences electron-hole separation at Se and BiVO4, respectively, as a result, enhanced photocurrent is obtained. Theoretical study of β-TaON in the form of primitive unit cell, supercell and its N, Ta, and O terminated surfaces are carried out with the help of periodic DFT. Optical and electronic properties of all these different species are simulated, which predict TaON as the best candidate for photocatalytic water splitting contrast to their Ta2O5 and Ta3N5 counterparts. The calculated bandgap, valence band, and conduction band edge positions predict that β-TaON should be an efficient photoanodic material. The valence band is made up of N 2p orbitals with a minor contribution from O 2p, while the conduction band is made up of Ta 5d. Turning to thin films, the valence band maximum; VBM (−6.4 eV vs. vacuum) and the conduction band minimum; CBM (−3.3 eV vs. vacuum) of (010)-O terminated surface are respectively well below and above the redox potentials of water as required for photocatalysis. Charge carriers have smaller effective masses than in the (001)-N terminated film (VBM −5.8 and CBM −3.7 eV vs. vacuum). However, due to wide band gap (3.0 eV) of (010)-O terminated surface, it cannot absorb visible wavelengths. On the other hand, the (001)-N terminated TaON thin film has a smaller band gap in the visible region (2.1 eV) but the bands are not aligned to the redox potential of water. Possibly a mixed phase material would produce an efficient photoanode for solar water splitting, where one phase performs the oxidation and the other reduction. Computational study of an optically transparent, near-infrared-absorbing low energy gap conjugated polymer, donor−acceptor−donor (D-A-D) with promising attributes for photovoltaic application is reported herein. The D and A moiety on the polymeric backbone have been found to be responsible for tuning the band gap, optical gap, open circuit (Voc) and short-circuit current density (Jsc) in the polymers solar cells (PSC). Reduction in the band gap, high charge transformation, and enhanced visible light absorption in the D-A-D system is because of strong overlapping of molecular orbitals of D and A. In addition, the enhanced planarity and weak steric hindrance between adjacent units of D-A-D, resulted in red-shifting of its onset of absorption. Finally, PSC properties of the designed D-A-D was modeled in the bulk heterojunction solar cell, which gives theoretical Voc of about 1.02 eV. DFT study has been carried out to design a new All-Solid-State dye-sensitized solar cell (SDSC), by applying a donor-acceptor conjugated polymer instead of liquid electrolyte. The typical redox mediator (I1−/I3−) is replaced with a narrow band gap, hole transporting material (HTM). A unique “upstairs” like band energy diagram is created by packing N3 between HTM and TiO2. Our theoretical simulations prove that the proposed configuration will be highly efficient as the HOMO level of HTM is 1.19 eV above the HOMO of sanitizer (dye); providing an efficient pathway for charge transfer. High short-circuit current density and power conversion efficiency is promised from the strong overlapping of molecular orbitals of HTM and sensitizer. A low reorganization energy of 0.21 eV and exciton binding energy of 0.55 eV, confirm the high efficiency of HTM. Theoretical and experimental studies of a series of four porphyrin-furan dyads were designed and synthesized, having anchoring groups, either at meso-phenyl or pyrrole-β position of a zinc porphyrin based on donor–π–acceptor (D–π–A) approach. The porphyrin macrocycle acts as donor, furan hetero cycle acts as π-spacer and either cyanoacetic acid or malonic acid group acts as acceptor. Optical bandgap, natural bonding, and molecular bonding orbital (HOMO–LUMO) analysis confirm the high efficiency pyrrole-β substituted zinc porphyrins contrast to meso-phenyl dyads. DFT study of polypyrrole-TiO2 composites has been carried out to explore their optical, electronic and charge transfer properties for the development of an efficient photocatalyst. Titanium dioxide (Ti16O32) was interacted with a range of pyrrole (Py) oligomers to predict the optimum composition of nPy-TiO2 composite with suitable band structure for efficient photocatalytic properties. The study has revealed that Py-Ti16O32 composites have narrow band gap and better visible light absorption capability compared to individual constituents. A red-shifting in λmax, narrowing band gap, and strong intermolecular interaction energy (-41 to −72 kcal/mol) of nPy-Ti16O32 composites confirm the existence of strong covalent type interactions. Electron−hole transferring phenomena are simulated with natural bonding orbital analysis where Py oligomers found as donor and Ti16O32 as an acceptor in nPy-Ti16O32 composites. Sensitivity and selectivity of polypyrrole (PPy) towards NH3, CO2 and CO have been studied at DFT. PPy oligomers are used both, in the doped (PPy+) and neutral (PPy) form, for their sensing abilities to realize the best state for gas sensing. Interaction energies and amount of charges (NBO and Mulliken charge analysis) are simulated which reveal the sensing ability of PPy towards these gases. PPy, both in doped and neutral state, is more sensitive to NH3 compared to CO2 and CO. More interestingly, NH3 causes doping of PPy and de-doping of PPy+, providing evidence that PPy/PPy+ is an excellent sensor for NH3 gas. UV-vis and UV-vis-near-IR spectra of nPy, nPy+, and nPy/nPy+-X complexes demonstrate strong interaction of PPy/PPy+ with these atmospheric gases. The applications of graphene (GR) and its derivatives in the field of composite materials for solar energy conversion, energy storage, environment purification and biosensor applications have been reviewed. The vast coverage of advancements in environmental applications of GR-based materials for photocatalytic degradation of organic pollutants, gas sensing and removal of heavy metal ions is presented. Additionally, the presences of graphene composites in the bio-sensing field have been also discussed in this review.

Organic solar cells show great potential to become a commercially available technology for renewable clean energy production due to their attractive properties. Inexpensive materials and manufacturing processes, including classical roll-to-roll fabrication, as well as the ability to produce flexible, low weight, semitransparent devices are some of the advantages organic photovoltaics provide. Addressing the most common issues in these new technologies, i.e., the low efficiencies of devices and rapid degradation of materials, could bring a realistic alternative for the photovoltaic industry. In this work, the performance of P3HT:PCBM based bulk heterojunction solar cells modified through low energy gold ion implantation in the hole transporting layer, the PEDOT:PSS, is studied. Reference solar cells without gold were also fabricated and characterized for comparison. Through field emission scanning electron microscopy (FESEM) micrographs, the formation of gold nanoparticles (AuNPs) in the PEDOT:PSS has been shown layer for the highest implantation doses used. Absorbance measurements of PEDOT:PSS films before and after gold implantation further confirmed this result. TRIDYN and SRIM simulation programs estimated shallow gold implantations of ~3 nm underneath the PEDOT:PSS films surface. Current-voltage (JxV) characteristics of reference solar cells under AM 1.5 illumination presented the uncommon S-shaped curves, an abnormal deviation from typical JxV curves. This was attributed to PEDOT:PSS degradation due to oxygen and water exposure, which reduced its work function significantly. As a result, deteriorated parallel and series resistances were obtained in reference devices, which ultimately reduced their field factors and power conversion efficiencies. This abnormal behavior was consistently eliminated with the introduction of AuNPs near the PEDOT:PSS/Active-layer interface, leading to the rectification of the illuminated JxV curves of modified solar cells and the reestablishment of cell parameters. Consequently, outstanding improvements in the field factors and power conversion efficiencies were observed in these devices. This was attributed to enhancement (and prevention from the reduction) of the PEDOT:PSS work function layer due to the presence of AuNPs, which rearranged the energy levels at the interface to a more favorable state: higher electron blocking and lower hole extraction barriers. / Células solares orgânicas têm mostrado grande potencial para se tornar uma alternativa tecnológica na produção de energia limpa e renovável. Baixo custo dos materiais e dos processos de manufatura, e a possibilidade de fabricar dispositivos com baixo peso, flexibilidade e semitransparência, inclusive pelo método clássico de roll-to-roll, são algumas das vantagens oferecidas pela fotovoltaica orgânica. Resolver os problemas mais comuns destes dispositivos, como a baixa eficiência na conversão de energia e a rápida degradação dos materiais, é necessário para sua disponibilização no mercado fotovoltaico atual. Neste trabalho, células solares de heterojunção volumétrica baseadas no polímero P3HT e modificadas através da implantação de íons de ouro de baixa energia na camada de PEDOT:PSS são estudadas. Dispositivos equivalentes sem modificação de ouro também foram fabricados e caracterizados como referência. Imagens obtidas através de um microscópio eletrônico de varredura por emissão de campo (FESEM Field Emission Scannig Electron Microscopy) mostraram a formação de nanopartículas de ouro (AuNPs) na camada de PEDOT:PSS para as doses de implantação mais elevadas. Medidas do espectro de absorbância dos filmes de PEDOT:PSS antes e depois da implantação de ouro confirmam este resultado. Simulações feitas com os softwares TRIDYN e SRIM estimaram o ouro implantado em u ma profundidade de ~3 nm abaixo da superfície do PEDOT:PSS. As curvas de corrente-tensão (JxV) características das células solares de referência sob iluminação AM 1.5 mostraram um comportamento de forma S, que corresponde a um desvio da forma típica das curvas JxV. Isto foi atribuído à degradação dos filmes de PEDOT:PSS devido à exposição ao oxigênio e à água, que reduz sua função trabalho significativamente. Como resultado, deterioraram-se as resistências em paralelo e em série destes dispositivos, o que em última instância, reduziu o Field Factor (FF) e a eficiência na conversão de energia. Este comportamento anormal foi eliminado de forma consistente após a introdução de AuNPs perto da interface PEDOT:PSS/Camada-Ativa. As curvas JxV das células solares modificadas sob iluminação foram retificadas e os valores dos seus parâmetros restabelecidos. Melhorias notáveis no FF e eficiência de conversão de energia foram obtidas para todas as células solares modificadas. Isto foi atribuído ao aumento da função trabalho da camada de PEDOT:PSS pela presença das AuNPs, que reorganizou os níveis de energia na interface para um estado mais favorável: com barreiras de potencial otimizadas para bloquear a extração de elétrons e favorecer a de buracos.

Cette thèse est axée sur la fabrication et l’optimisation d’une nouvelle structure permettant théoriquement d’améliorer les performances des cellules à base de silicium cristallin. Cette nouvelle architecture de cellule utilise la technologie des hétérojonctions de silicium a-Si:H/ c-Si (Si-HJ) appliquée sur des structures à contacts interdigités en face arrière (IBC). Le potentiel de rendement des cellules IBC Si-HJ est supérieur à 25%, mais leur fabrication nécessite une localisation des couches de a-Si:H de dopage différent et de leurs métallisations. L’intégration de ces étapes dans un procédé simplifié utilisant des techniques industrielles (PECVD, pulvérisation, sérigraphie et laser) a été étudiée. De plus, une structure obtenue sans séparation entre le BSF et l’émetteur est présentée, permettant de réduire le nombre d’étapes de fabrication. Les avantages ainsi que les limites liés à cette architecture simplifiée ont été illustrés du point de vue expérimental et par simulation. Dans le cadre de ces travaux, le rendement maximum atteint sur les dispositifs IBC Si-HJ simplifiés de 25cm² est de 19% (substrats de type n), ce qui constitue le 3e meilleur résultat au niveau mondial. Les performances des cellules restent encore limitées par l’absorption des couches de a-Si:H utilisées pour la passivation de la face avant, et par la conductivité des couches dopées en face arrière. De nombreuses pistes d’amélioration sont explorées dans cette étude. Un procédé de métallisation innovant a également été élaboré pour le passage sur des substrats de grande taille (150cm²). Il permet de limiter les pertes résistives tout en offrant de la flexibilité au niveau de la géométrie des contacts. La mise en module de cellules ayant ce design de métallisation a ensuite été étudiée, et un module de 4 cellules IBC Si-HJ a pu être fabriqué. / This thesis studies the fabrication and the optimization of a new structure to enhance the efficiency of crystalline silicon based solar cells. This new cell design uses a-Si:H/c-Si heterojunction (Si-HJ) technology applied on interdigitated back contact structures (IBC). With IBC Si-HJ solar cells, the efficiency potential is theoretically higher than 25%. Their fabrication requires to pattern doped a-Si:H and the associated metallization on the same side. The implementation of those process steps has been carefully studied. All processes used in this study are potentially industrial (PECVD, sputtering, screen-printing, and laser) and the obtained structure without buffer layer between the BSF and the emitter allows to reduce fabrication steps. Issues linked to this design have been investigated. Within the frame of this work, the maximum efficiency reached on reduced size devices (25cm²) with n-type substrate and is 19% which is the 3rd best result worldwide. The cell performances are still limited by the absorption of front surface passivating layer (a-Si:H) and by the low doped layer conductivity. Several optimization ways are explored in this study. An innovative metallization process is then elaborated to allow large area solar cell fabrication while limiting resistive losses and offering more flexibility on metallized pattern. The interconnection and the encapsulation of cells with this metallization design have been illustrated and a module with 4 cells has been fabricated.

This thesis examines the development of DC-DC converters that are suitable for Module Integrated Converters, (MICs), in grid interactive photovoltaic (PV) systems, and especially concentrates on the study of the half bridge dual converter, which was previously developed from the conventional half bridge converter. Both hard-switched and soft-switched half bridge dual converters are constructed, which are rated at 88W each and transform a nominal 17.6Vdc input to an output in the range from 340V to 360Vdc. An initial prototype converter operated at 100kHz and is used as a base line device to establish the operational behaviours of the converter. The second hard-switched converter operated at 250kHz and included a coaxial matrix transformer that significantly reduced the power losses related to the transformer leakage inductance. The soft-switched converter operated at 1MHz and is capable of absorbing the parasitic elements into the resonant tank. Extensive theoretical analysis, simulation and experimental results are provided for each converter. All three converters achieved conversion efficiencies around 90%. The progressive increases in the operation frequency, while maintaining the conversion efficiency, will translate into the reduced converter size and weight. Finally different operation modes for the soft-switched converter are established and the techniques for predicting the occurrence of those modes are developed. The analysis of the effects of the transformer winding capacitance also shows that soft switching condition applies for both the primary side mosfets and the output rectifier diodes.

<p>The interactions between the molecular constituents in dye-sensitized solar cells were studied with UV-VIS and IR spectroscopy, Raman scattering, conductivity and electron accumulation measurements.</p><p>From stability studies of the dye, bis(tetrabutylammonium)cis-bis(thiocyanato) bis(2,2’-bipyridine-4-carboxylic acid, 4’-carboxylate) ruthenium(II), in the complete solar cell, the thiocyanate ion ligand was found to be lost from the dye. A method was developed to study mechanisms in a sealed dye-sensitized solar cell using resonance Raman scattering (RRS). RRS studies of a complete dye-sensitized solar cell including iodine and lithium iodide in the electrolyte indicate that triiodide exchange the SCN^- ligand of the dye. It was proposed that an ion pair Li⁺…I₃^- formation occurred, which, by a reduced electrostatic repulsion between I₃^- and SCN^- facilitated the exchange of these anions at Ru(II) of the dye. The additive 1-methylbenzimidazole suppressed the SCN^-/I₃^- ligand exchange by forming a complex with Li⁺.</p><p>In order to study charge transport in nanostructured TiO₂ films permeated with electrolyte, a technique was developed for determining activation energies of conduction, electron accumulation and effective mobility. Two regions were distinguished from the relation between conductivity and electron concentration. In the first region (~1-20 electrons per TiO₂ particle), which resembles best the region where the nanostructured dye-sensitized solar cell operates, the results can be fitted to some extent with a trapping/detrapping or a hopping model for charge transport, but not with a conduction band model. For the second region (> 20 electrons per TiO₂ particle), charge transport by electrons in the conduction band seems to be the most applicable model.</p><p>Through this work many effects from the interplay between the solar cell components were observed. These observations emphasize the importance of well-balanced interactions in dye-sensitized solar cells.</p>

The interactions between the molecular constituents in dye-sensitized solar cells were studied with UV-VIS and IR spectroscopy, Raman scattering, conductivity and electron accumulation measurements. From stability studies of the dye, bis(tetrabutylammonium)cis-bis(thiocyanato) bis(2,2’-bipyridine-4-carboxylic acid, 4’-carboxylate) ruthenium(II), in the complete solar cell, the thiocyanate ion ligand was found to be lost from the dye. A method was developed to study mechanisms in a sealed dye-sensitized solar cell using resonance Raman scattering (RRS). RRS studies of a complete dye-sensitized solar cell including iodine and lithium iodide in the electrolyte indicate that triiodide exchange the SCN- ligand of the dye. It was proposed that an ion pair Li+…I3- formation occurred, which, by a reduced electrostatic repulsion between I3- and SCN- facilitated the exchange of these anions at Ru(II) of the dye. The additive 1-methylbenzimidazole suppressed the SCN-/I3- ligand exchange by forming a complex with Li+. In order to study charge transport in nanostructured TiO2 films permeated with electrolyte, a technique was developed for determining activation energies of conduction, electron accumulation and effective mobility. Two regions were distinguished from the relation between conductivity and electron concentration. In the first region (~1-20 electrons per TiO2 particle), which resembles best the region where the nanostructured dye-sensitized solar cell operates, the results can be fitted to some extent with a trapping/detrapping or a hopping model for charge transport, but not with a conduction band model. For the second region (&gt; 20 electrons per TiO2 particle), charge transport by electrons in the conduction band seems to be the most applicable model. Through this work many effects from the interplay between the solar cell components were observed. These observations emphasize the importance of well-balanced interactions in dye-sensitized solar cells.

Organic solar cells have the potential to be portable power sources that are light-weight, flexible, and inexpensive. However, the highest power conversion efficiency for organic solar cells to date is ~8%, and most high-efficiency solar cells have an area of less than 1 cm². This thesis advances the field of organic solar cells by studying the physics and engineering of the devices to understand the reverse saturation current, which is related to efficiency, and the effects of area scaling. The most commonly accepted models to describe the physics of organic photovoltaic devices are reviewed and applied to planar heterojunction solar cells based on pentacene / C60 as a model system. The equivalent circuit model developed for inorganic solar cells is shown to work well to describe the behavior of organic devices and parameterize their current-voltage characteristics with five parameters. Changes in the parameters with different material combinations or device structures are analyzed to better understand the operation of the presented organic solar cells. A one-dimensional diffusion model for the behavior of excitons and treatment of the organic layers as planes is demonstrated to adequately model the external quantum efficiency and photocurrent in pentacene / C60 solar cells. The origin of the open-circuit voltage is studied using cells with different electrodes and different donor materials. While changing the electrodes does not affect open-circuit voltage, it is greatly modified by changes in the donor. Tests with additional semiconductors show the change in open-circuit voltage is not consistent from donor to donor as the acceptor is varied, suggesting a more complex relation than just the difference in energy levels. Study of the temperature dependence of the equivalent circuit parameters shows that the reverse saturation current, which has a significant role in determining the open-circuit voltage, has a thermally activated behavior. From this behavior, the reverse saturation current is related back to charge transfer at the donor / acceptor heterojunction to suggest that both the effective energy barrier presented by the energy levels and the electronic coupling are important in determining the reverse saturation current and open-circuit voltage. This marks a shift from just considering a built-in voltage or the energy levels to also considering the electronic coupling of the donor and acceptor materials. Temperature-dependent performance characteristics are also used to show key differences between organic and inorganic devices. Finally, the effect of area scaling is explored with pentacene / C60 solar cells having areas of 0.11, 7, and 36.4 cm². Analysis with the equivalent circuit model shows that performance decreases as area increases because of an increasing series resistance presented by the transparent electrode. A metal grid, to provide low resistance pathways for current, fabricated on top of the transparent electrode is proposed to reduce the effective resistance. The grid is unique in that it is placed between the electrode and the semiconductor layer and must be passivated to prevent shorts through the thin semiconductor to the back metal electrode. Analysis of the grid predicts greatly reduced series resistance, and experimental results show reduced resistance and improved performance for the 7 cm² and 36.4 cm² devices when including the grid.

In the crystalline Si solar cell industry, there is a push to reduce module cost through a combination of thinner substrates and increased cell efficiency. Achieving solar cells with sub-100 µm substrates cost-effectively is a formidable task because such thin substrates impose stringent handling requirements and thermal budget due to their flexibility, ease of breakage, and low yield. Moreover, as the substrate thickness decreases the surface passivation quality dictates the performance of the cells. Crystalline Si heterojunction (HJ) solar cells based on hydrogenated amorphous silicon (a-Si:H) have attracted significant interest in recent years due to their excellent surface passivation properties, potential for high efficiency, low thermal budget and low cost. HJ cells with ultra-passivated surfaces showing > 700 mV open-circuit voltages (Voc) and > 20% conversion efficiency have been demonstrated. In these cells, it has been identified that high-quality a-Si:H films deposited by a low-damage plasma process is key to achieving such high cell performance. However, the options for low-damage plasma deposition process are limited. The main objectives of this work are to develop a low-plasma damage a-Si:H thin film deposition process based on remote plasma chemical vapor deposition (RPCVD) and to demonstrate high efficiency HJ solar cells on bulk substrates as well as on ultra-thin silicon and germanium substrates obtained by a novel, low-cost semiconductor-on-metal (SOM) technology. This manuscript presents a detailed description of the RPCVD system and the process leading to the realization of high quality a-Si:H thin films and high efficiency HJ solar cells. First, p-type a-Si:H thin films are developed and optimized, then HJ solar cells are subsequently fabricated on bulk and ultra-thin Si and Ge SOM substrates without intrinsic a-Si:H passivation. Single HJ cells on ~ 500 µm bulk Si and ~25 µm ultra-thin substrates exhibited conversion efficiencies of η = 16% (Voc = 615 mV, Jsc = 34 mA/cm2, and FF = 77%) and η = 11.2% (Voc = 605 mV, Jsc = 29.6 mA/cm2, and FF = 62.8%), respectively. The performance of the ~25 µm cell was further improved to η = 13.4% (Voc = 645 mV, Jsc = 31.4 mA/cm2, and FF = 66.2%) by implementing the dual HJ architecture without front side i-layer passivation. For single HJ cells based on Ge substrates, the results were η = 1.78 % (Voc = 148 mV, Jsc = 35.1 mA/cm2, and FF = 1.78%) on ~500 µm bulk Ge, compared to η =5.3% (Voc = 203 mV, Jsc = 44.7 mA/cm2, and FF = 5.28%) on ~ 50 µm Ge SOM substrates. Respectively, the results obtained on ultra-thin SOM substrates are among the highest reported in literature for based on comparable architecture and substrate thickness. In order to achieve improved cell performance, dual HJ cells with i-layer passivation of both surfaces were fabricated. First, optimized RPCVD-based i-layer films were developed by varying the deposition temperature and H2 dilution ratio (R). It was found that excellent surface passivation on planar substrates with as-deposited minority carrier lifetimes > 1 ms is achievable by using deposition temperature of 200 ºC and moderate dilution ratio 0.5 ≤ R ≤ 1, even without the more rigorous RCA pre-cleaning process typically used in literature for achieving comparable results. Subsequently, dual HJ solar cells with i-layer films were demonstrated on planar and textured bulk Si substrates showing improved conversion efficiencies of η = 17.3% (Voc = 664 mV, Jsc = 34.34 mA/cm2 and FF = 76%) and η = 19.4% (Voc = 643 mV, Jsc = 38.99 mA/cm2, and FF = 77.5%), respectively. / text

The understanding of molecular effects in nanoscale environments is becoming increasingly relevant for various emerging fields. These include spectroscopy for molecular identification as well as in finding molecules for energy harvesting. Theoretical quantum chemistry has been increasingly useful to address these phenomena to yield an understanding of these effects. In the first part of this dissertation, we study the chemical effect of surface-enhanced Raman scattering (SERS). We use quantum chemistry simulations to study the metal-molecule interactions present in these systems. We find that the excitations that provide a chemical enhancement contain a mixed contribution from the metal and the molecule. Moreover, using atomistic studies we propose an additional source of enhancement, where a transition metal dopant surface could provide an additional enhancement. We also develop methods to study the electrostatic effects of molecules in metallic environments. We study the importance of image-charge effects, as well as field-bias to molecules interacting with perfect conductors. The atomistic modeling and the electrostatic approximation enable us to study the effects of the metal interacting with the molecule in a complementary fashion, which provides a better understanding of the complex effects present in SERS. In the second part of this dissertation, we present the Harvard Clean Energy project, a high-throughput approach for a large-scale computational screening and design of organic photovoltaic materials. We create molecular libraries to search for candidates structures and use quantum chemistry, machine learning and cheminformatics methods to characterize these systems and find structure-property relations. The scale of this study requires an equally large computational resource. We rely on distributed volunteer computing to obtain these properties. In the third part of this dissertation we present our work related to the acceleration of electronic structure methods using graphics processing units. This hardware represents a change of paradigm with respect to the typical CPU device architectures. We accelerate the resolution-of-the-identity Moller-Plesset second-order perturbation theory algorithm using graphics cards. We also provide detailed tools to address memory and single-precision issues that these cards often present.