abstract: Natural photosynthesis dedicates specific proteins to achieve the modular division of the essential roles of solar energy harvesting, charge separation and carrier transport within natural photosynthesis. The modern understanding of the fundamental photochemistry by which natural photosynthesis operates is well advanced and solution state mimics of the key photochemical processes have been reported previously. All of the early events in natural photosynthesis responsible for the conversion of solar energy to electric potential energy occur within proteins and phospholipid membranes that act as scaffolds for arranging the active chromophores. Accordingly, for creating artificial photovoltaic (PV) systems, scaffolds are required to imbue structure to the systems. An approach to incorporating modular design into solid-state organic mimics of the natural system is presented together with how conductive scaffolds can be utilized in organic PV systems. To support the chromophore arrays present within this design and to extract separated charges from within the structure, linear pyrazine-containing molecular ribbons were chosen as candidates for forming conductive linear scaffolds that could be functionalized orthogonally to the linear axis. A series of donor-wire-acceptor (D-W-A) compounds employing porphyrins as the donors and a C60 fullerene adduct as the acceptors have been synthesized for studying the ability of the pyrazine-containing hetero-aromatic wires to mediate photoinduced electron transfer between the porphyrin donor and fullerene acceptor. Appropriate substitutions were made and the necessary model compounds useful for dissecting the complex photochemistry that the series is expected to display were also synthesized. A dye was synthesized using a pyrazine-containing heteroaromatic spacer that features two porphyrin chromophores. The dye dramatically outperforms the control dye featuring the same porphyrin and a simple benzoic acid linker. A novel, highly soluble 6+kDa extended phthalocyanine was also synthesized and exhibits absorption out to 900nm. The extensive functionalization of the extended phthalocyanine core with dodecyl groups enabled purification and characterization of an otherwise insoluble entity. Finally, in the interest of incorporating modular design into plastic solar cells, a series of porphyrin-containing monomers have been synthesized that are intended to form dyadic and triadic molecular-heterojunction polymers with dedicated hole and electron transport pathways during electrochemical polymerization. / Dissertation/Thesis / Ph.D. Chemistry 2013

Orientador: Ana Flávia Nogueira / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-17T19:59:01Z (GMT). No. of bitstreams: 1 Benedetti_JoaoEduardo_D.pdf: 8810025 bytes, checksum: 02324ef0185baef0d7794ea229fb5cda (MD5) Previous issue date: 2010 / Resumo: Este trabalho consistiu na preparação, caracterização e posterior aplicação de eletrólitos poliméricos gel em celulas solares de TiO2/corante. No Capítulo I, e apresentado uma introdução geral sobre células solares e eletrólitos poliméricos. O Capítulo II contém os objetivos deste trabalho. No Capítulo III, são preparados os eletrólitos polimérico gel utilizando a matriz polimérica de poli(oxido de etileno-co-2-(2-metoxietoxi) etil glicidil eter) (P(EO/EM)) contendo I2 e várias concentrações de g-butirolactona (GBL) e LiI. Esses eletrólitos foram caracterizados por medidas de calorimetria exploratória diferencial (DSC), ressonância magnética de Li (RMN), termogravimetria (TGA), difração de raios-X (DRX), condutividade e voltametria cíclica (VC). O eletrólito polimérico gel P(EO/EM)/GBL/LiI/I2 apresentou excelentes propriedades químicas e eletroquímicas. Esses eletrólitos foram aplicados nas células solares de TiO2/corante, conforme e apresentado no Capítulo IV. As células solares foram caracterizadas por meio das curvas de corrente-potencial (J-V), estimativa do tempo de vida do eletron e espectroscopia de absorção transiente (TAS). De modo geral, os dispositivos montados com o eletrólito polimérico (P(EO/EM)/GBL/LiI/I2 apresentaram um aumento da fotocorrente com a incorporação de GBL no eletrólito. Esse resultado e influência da maior difusão das especies redox no meio. Em contrapartida, o aumento da concentração de GBL no eletrólito também provocou uma acentuada perda no potencial de circuito aberto, o que foi relacionado ao aumento dos processos de recombinação na interfaces, contribuindo para a perda da eficiência das células solares. Para minimizar esses efeitos, no Capítulo V, e apresentada a caracterização por meio das curvas de corrente-potencial da célula solar de TiO2/corante montadas com o eletrólito P(EO/EM)/GBL/LiI/I2 preparado com terc-butilpiridina e éter coroa. A incorporação desses aditivos proporcionou um aumento de Voc das células solares e, consequentemente, da eficiência dos dispositivos. O Capítulo VI apresenta os testes de estabilidade das células solares de TiO2/corante preparadas com o eletrólito polimérico gel, no qual apresentou estabilidade apropriada durante 30 dias de teste. O Capítulo VII contém as principais conclusões deste trabalho e perspectiva de continuação para esta linha de pesquisa / Abstract: This thesis consisted in the preparation, characterization and application of gel polymer electrolytes in dye-sensitized TiO2 solar cells. A general introduction to solar cells and to polymer electrolytes will be presented in Chapter I. Chapter II describes the aims of this work. Chapter III deals with the preparation of gel polymer electrolytes based on the poly(ethylene oxide-co-2-(2-methoxyethoxy) ethyl glycidyl ether) (P(EO/EM)) polymer matrix containing I2 and different concentrations of g-butyrolactone (GBL) and LiI. These electrolyte samples were characterized by differential scanning calorimetry (DSC), Li nuclear magnetic resonance (Li RMN), thermogravimetry (TGA), X-ray diffraction (RDX), conductivity measurements and cyclic voltammetry (VC). The gel polymer electrolyte P(EO/EM)/GBL/LiI/I2 provided excellent chemical and electrochemical properties. The electrolytes were applied in dye-sensitized TiO2 solar cells, as discussed in Chapter IV. Solar cells were characterized by current-voltage (IV) curves, electron lifetime measurements and transient absorption spectroscopy (TAS). Most of the solar cells based on the polymer electrolyte P(EO/EM)/GBL/LiI/I2 presented an increase in photocurrent with the addition of GBL to the electrolyte composition. This result may be explained by the enhanced diffusion of redox species in the medium. However, a significant decrease in open-circuit voltage was observed after increasing the GBL concentration in the electrolyte composition. The decrease in open-circuit voltage was assigned to an increase in recombination losses taking place at the interfaces, which resulted in solar cells with lower performance. In order to minimize these drawbacks, dye-sensitized TiO2 solar cells were assembled with the electrolyte P(EO/EM)/GBL/LiI/I2 containing 4-tert-butylpyridine and crown ether molecules. The addition of these additives provided an increase in Voc and, consequently, improved device performance. The characterization of these solar cells based on gel polymer electrolyte containing additives was carried out by means of current-voltage (I-V) curves, as discussed in Chapter V. Dye-sensitized TiO2 solar cells based on gel polymer electrolyte were subjected to durability tests. Good durability results were achieved during a 30-day test, which are discussed in Chapter VI. Chapter VII deals with the main conclusions of this work and outlines some perspectives for the next steps of this research / Doutorado / Quimica Inorganica / Doutor em Ciências

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Orientadores: Francisco das Chagas Marques, Ana Flávia Nogueira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-26T08:45:20Z (GMT). No. of bitstreams: 1 Coutinho_NataliadeFaria_M.pdf: 12394800 bytes, checksum: 1d28bb92259a5c9eb6848a0fe678b6b3 (MD5) Previous issue date: 2014 / Resumo: A demanda mundial de energia elétrica tem crescido muito nas últimas décadas, o que tem levado a uma busca mais expressiva por fontes de energia renováveis e sustentáveis. Deste modo, as células solares, que através do efeito fotovoltaico convertem a energia proveniente do sol em energia elétrica, tem ganhado atenção. Dentre os vários tipos de células solares, se encontram as células solares sensibilizadas por corante, DSSC, que têm ganhado interesse de estudiosos da área por apresentarem uma possibilidade de geração de energia elétrica a baixo custo. Para que essas células ganhem competitividade no mercado, é necessário que suas eficiências aumentem, e é nesse ramo de pesquisa que o presente trabalho se coloca. Este trabalho foi baseado no estudo e otimização da eficiência de células solares sensibilizadas por corante, onde verificamos a influência de vários fatores na eficiência das células. Dentre eles, se encontram o processo de manufatura das células, o pós-tratamento de TiCl4 sobre o filme nanoestruturado de TiO2, a composição da pasta de TiO2 e do eletrólito líquido, o método de deposição da Pt no contra-eletrodo, e a utilização de uma camada espalhadora de luz com nanopartículas de TiO2 da ordem de 200nm. Além disso, um estudo a respeito do efeito de uma blocking layer de TiO2 entre o FTO e o filme nanoestruturado de TiO2, depositada pela técnica conhecida como atomic layer deposition, ALD, também foi realizado, o que levou a um aumento na eficiência das células. Através desses estudos, conseguimos aumentar a eficiência das células em até 90% se comparado às primeiras células que produzimos (de 3,9% a 7,4%), atingindo valores de tensão de circuito aberto Voc, densidade de corrente de curto-circuito Jsc, fator de preenchimento FF e eficiência ? de até 0,71V, 14,38mA/cm2, 0,67 e 7,4%, respectivamente. Deste modo, uma melhora significativa na performance das células foi observada, chegando a resultados comparáveis aos obtidos por diversos grupos de pesquisa em todo o mundo / Abstract: World demand for electricity has grown in the last decades, which has led to a more expressive search for renewable and sustainable energy sources. Consequently, solar cells have been getting attention because of their capacity to convert energy from the sun into electrical energy through the photovoltaic effect. Among the various types of solar cells, there are the dye-sensitized solar cells, DSSC, which have gained interest of the solar cell community for having a possibility of power generation at low cost. In order to these cells get market competitiveness, it is necessary to increase their efficiency, and this is the research field that the present work is placed into. This thesis was based on the study and optimization of dye-sensitized solar cells efficiency, where we could see the influence of various factors in cells efficiency. Among these, there are the cells manufacturing process, the post-treatment on nanostructured TiO2 films using a TiCl4 solution, the composition of the TiO2 paste and the liquid electrolyte, the method of Pt deposition at the counter electrode, and the use of a reflecting layer with 200nm TiO2 nanoparticles. In addition, a study of the effect of a TiO2 blocking layer between the FTO and the nanostructured TiO2 film deposited by the technique known as atomic layer deposition, ALD, was also performed, which led to an increase in cells efficiency. Through these studies, we could increase cells efficiency by up to 90% compared to the first cells we produced (from 3,9% to 7,4%), reaching values of open circuit voltage Voc, short circuit current density Jsc, fill factor FF and efficiency _ of up to 0,71V, 14,38mA/cm2, 0,67 and 7,4%. Thus, a significant improvement in cells performance was observed, reaching results comparable to that obtained by many research groups around the world / Mestrado / Física / Mestra em Física

Dye sensitized solar cells (DSSCs) are an attractive way to convert light into electricity. Its development requires a detailed understanding and kinetic optimization of various electronic processes, especially those occurring at the mesoporous TiO2/dye/electrolyte interface. This dissertation work is focused on the exploration of the various electronic processes at the sensitized-electrode/electrolyte interface by using various electrochemical and photochemical methods. Firstly, an alternative redox couple—TEMPO/TEMPO·+ with a relatively high positive redox potential—is explored, aiming to reduce the energy loss during the dye regeneration process. Despite the fast dye regeneration, the charge recombination between the electrons in the conduction band of mesoporous TiO2 and the oxidized redox species is found to be the limiting factor of the device. Further, a more efficient tandem-electrolyte system is developed, leading to DSSCs with the power conversion efficiency of 10.5 % and 11.7 % at 1 sun and 0.5-sun illumination, respectively. An electron-transfer cascade process during dye regeneration by the redox mediators is discovered to be beneficial. Further stability studies on the device suggest the crucial role of TiO2/dye/electrolyte interfaces in the long-term stability of cobalt bipyridyl electrolyte-based DSSCs. On the fundamental level, the local electric field and Stark effects at the TiO2/dye/electrolyte interface are investigated in various aspects—including the charge compensation mechanism, the factors affecting the electric field strength, as well as its impact on charge transfer kinetics. These results give further insights about the TiO2/dye/electrolyte interface, and contribute to the further development and understanding of DSSCs.

No description available.

Metal and semiconducting nanocrystals have received a great deal of attention from fundamental scientists and application-oriented researchers due to their physical and chemical properties, which differ from those of bulk materials. Nanocrystals are essential building blocks in the development of nanostructured devices for energy conversion. Colloidal metals and metal chalcogenides have been developed for use as nanocrystal inks to produce efficient solar cells with lower costs. All high-performing photovoltaic nanocrystals contain toxic elements, such as Pb, or scarce elements, such as In; thus, the production of solution-processable nanocrystals from earth-abundant materials using environmentally benign synthesis and processing methods has become a major challenge for the inorganic semiconductor-based solar field. This dissertation, divided into two parts, addresses several aspects of these emerging challenges. The first portion of the thesis describes the synthesis and characterization of nanocrystals of antimony sulfide, which is composed of non-scarce and non-toxic elements, and examines their performance in photovoltaic devices. The effect of various synthetic parameters on the final morphology is explored. The structural, optical and morphological properties of the nanocrystals were investigated, and Sb2S3 nanocrystal-based solid-state semiconductor-sensitized solar cells were fabricated using different deposition processes. We achieved promising power conversion efficiencies of 1.48%. The second part of the thesis demonstrates a novel method for the in situ synthesis and patterning of nanocrystals via reactive inkjet printing. The use of low-cost manufacturing approaches for the synthesis of nanocrystals is critical for many applications, including photonics and electronics. In this work, a simple, low-cost method for the synthesis of nanocrystals with minimum size variation and waste using reactive inkjet printing is introduced. As a proof of concept, the method was used for the in situ synthesis of gold nanoparticles as a model system. Relatively monodisperse gold nanoparticles were produced. The size and shape of gold nanoparticles can be controlled by the gold precursor and surfactant concentration in the ‘ink.’ This approach can be extended to the synthesis of other nanocrystals and is thus a truly impactful process for the low-cost synthesis of materials and devices incorporating nanocrystals.

Dye-sensitized solar cells (DSSCs) or Grätzel cells are electrochemical devices in where physicochemical properties of different materials are combined to obtain electric energy. These photoconversion devices have evolved from a pioneering concept of molecular photovoltaics to industrial development with confirmed record efficiencies of 14.3%. Their efficiency combined with low-cost production methods and a high aesthetic interest enables the production of DSSC products for consumer electronics market. The strengths of this technology and the fact that its drawbacks are not limiting for this application makes consumer electronics and DSSC a perfect match for the development of self-powered devices. Some companies have already spot a potential market and are currently launching different consumer electronics and other devices with embedded DSSC. This thesis provides an overview of the operation principles of DSSC and the possible routes to improve the efficiency of these devices to emerge and thrive. Additionally, improvements in efficiency, stability and manufacturing needed to be addressed in the near future for this technology are discussed and its suitability to represent a breakthrough in the market of consumer electronics. An overview of the main companies developing DSSC and current prototypes and products is included.

This work studies the subject of perovskite solar cells. The structure of perovskites is described along with a portion of photovoltaics history that led to the employment of perovskites as absorpsion layers. Further, methods of measurement for solar cells such as impedance spectroscopy, photospectroscopy and load characteristics are summarized. Lastly there is a description of already done analytics of perovskite solar cells with the summary of the results. In the practical part, there are measurements made to find out any effect of cell topology or light source wavelength on the cell performance.

MSc (Physics) / Department of Physics / Currently the dye sensitized solar cells have attracted more attention due to their low cost, transparency and flexibility. These types of solar cells use the dye molecule adsorbed on TiO2 semiconductor in Nano architecture with the role of absorbing photons, in recent research attempts are being made to shifts the absorption spectral of TiO2 to visible and near infrared–region of solar spectrum to achieve maximum photo absorption which yields to an increase in the efficiency of the dye sensitized solar cells. In the current study, density functional theory (DFT) was used to model two croconate dyes (CR1 and CR2), one with an electron donating methyl group (CR1) and the other with an electron –withdrawing caboxyl group (CR2). The geometric, electronic and optical properties of these dyes were compared. The adsorption behaviour of the two dyes on (010 and 100) anatase TiO2 surfaces were investigated in this study by employing first principle calculation based on DFT using a plane-wave pseudo potential method. The generalized gradient approximation (GGA) was used in the scheme of Perdew-Burke Ernzerhof to describe the exchange -correlation function as implemented in the CASTEP package in Material Studio of BIOVIA. The adsorption results shows a spontaneous electron injection followed by efficient regeneration of the oxidized dye molecules by the electrolyte and strong binding ability of CR2 to the TiO2 surface, but also shows a comparable binding strength of CR1. The results of this study will help in the design of high efficient dye for DSSCs. / NRF