The diploma thesis deals with the study of perovskite solar cells with a regular n-i-p architecture. The theoretical part of this work is mainly focused on the stability of perovskite solar cells, i.e. thermal stability and the influence of UV radiation on final perovskite solar cell stability. Furthermore, the deposition methods, the architecture of solar cells and the materials used for the preparation of electron and hole transport layers were described in more detail. The experimental part deals with the optimization of the preparation of perovskite solar cells (especially in terms of resulting photovoltaic conversion efficiency), with a description of the structure preparation process of the final photovoltaic cell and the interpretation of the measured results.

[pt] Esta dissertação foi desenvolvida com o objetivo de criar e validar uma metodologia para identificação e classificação do potencial dos grandes clientes de uma concessionária local ao uso da tecnologia de conversão fotovoltaica como alternativa estratégica de racionalização do consumo. O estudo faz uso de dados oficiais de radiação global incidente no Rio de Janeiro, fornecidos pelo Instituto Nacional de Meteorologia do Brasil, e de dados de consumo de grandes clientes fornecidos pela Light. A motivação consiste em oferecer uma ferramenta, à concessionária e ao Regulador, a ser utilizada como subsídio ao planejamento estratégico da empresa, visando ao deslocamento de carga para horários fora da ponta. A metodologia proposta consiste em comparar a curva de energia elétrica consumida pelo cliente com a curva de radiação global incidente no Rio de Janeiro. Assim, utiliza-se uma metodologia fuzzy para identificar e categorizar os usuários de energia elétrica. Os resultados enquadraram os consumidores em cinco diferentes categorias que indicam o nível de potencial para fazer uso da conversão fotovoltaica. Dentre as conclusões, a metodologia desenvolvida mostrou-se eficaz como ferramenta de auxílio e a conversão fotovoltaica uma alternativa interessante, quando se trata da análise do consumo e da radiação global, para pelo menos 85 porcento dos grandes clientes analisados. / [en] This work was developed with the goal of creating and validating a methodology for identification and classification of potential major customers of a local electricity utility to the use of photovoltaic conversion technology as a strategic alternative to rationalize consumption. The study makes use of official data of global radiation incident in Rio de Janeiro, provided by the National Meteorology Institute of Brazil, and consumption data of major customers provided by Light. The motivation is to provide a tool to the electricity utility and the regulator, to be used as input to the strategic planning of the firm seeking to shift load of off-peak times. The proposed methodology consists in comparing the curve of electrical energy consumed by the customer with the curve of global radiation incident in Rio de Janeiro. Thus, the fuzzy methodology is used to identify and categorize the users of electricity. Results framed consumers in five different categories that indicate the level of potential to make use of photovoltaic conversion. Among the conclusions, the methodology was effective as an aid tool and photovoltaic conversion an attractive alternative when it comes to the analysis of consumption and global radiation for at least 85 percent of large customers analyzed.

Ce travail porte sur la synthèse et l’évaluation de systèmes pi-conjugués en tant matériaux actifs pour des dispositifs opto(électroniques). Un premier chapitre décrit une série d’oligothiophènes cruciformes et leur évaluation dans des dispositifs électrochromes. Le second chapitre décrit la synthèse d’accepteurs moléculaires à base de benzodithiophène et l’analyse de leur potentialités comme matériaux accepteurs dans des cellules solaires organiques. La plus large part du travail porte sur l’analyse des relations structure-propriétés d’une série de petites molécules push-pull comportant un groupe donneur triphénylamine (TPA) relié à un groupe accepteur par un espaceur thiényl. Une première étape a consisté à remplacer l’un des cycles phényles de la TPA par des groupes aromatiques tels que p-fluorophényle, anthryle et naphtyle. Ces modifications ont peu d’influence sur les propriétés électroniques de la molécule mais induisent de large variations des propriétés de transport de charge et de conversion photovoltaïque des matériaux correspondants. Au cours d’une seconde étape l’un des groupes phényles de la TPA a été remplacé par des chaînes alkyle, perfluoroalkyle et oligo(oxyethylene). Les résultats de diffraction X, spectroscopie d’absorption et de fluorescence, génération de second harmonique et électrochimie démontrent que certaines de ces molécules présentent des propriétés d’émission contrôlées par agrégation tandis que les matériaux correspondants se réorganisent spontanément à l’état solide sous forme d’agrégats H ou J dotés de propriétés de transport de charges et de conversion photovoltaïque fortement améliorées et de propriétés d’absorption, d’émission et de génération de second harmonique mécaniquement modulables. / This work deals with the design, synthesis and evaluation of molecular pi-conjugated systems as active materials for (opto)electronics devices. A short first chapter describes three X-shaped oligothiophenes, thecharacterization of their structure and properties and a first evaluation of their performances in electrochromic devices. The second chapter describes the synthesis of molecular acceptors based on a benzodithiophene and the analysis of their potentialities when combined with molecular donors in organic solar cells.The major part of the work is focused on the analysis of structure-properties relationships of a series of smallpush-pull molecules involving di- or tri-arylamine donorblocks linked to an acceptor group by a thienyl bridge. In a first step, a phenyl ring of triphenylamine (TPA) is replaced by p-fluorophenyl, anthryl and naphtyl groups.Optical and electrochemical results show that substitution has little effect at the molecular level but can markedly affect solid-state properties with in particular an improvement of charge-transport and short-circuit current density of solar cells based on these donor materials.In a second step, a phenyl ring of TPA is replaced by alkyl, perfluoroalkyl and oligo(oxyethylene) chains. Results of X-ray diffraction, absorption and photoluminescence spectroscopies, second harmonic generation, and electrochemistry demonstrate that some of these molecules under go aggregation controlled photoluminescence emission wave length while the corresponding materials spontaneous lyre organize in the solid-state to form either H or Jaggregates with enhanced charge mobility, photovoltaic conversion efficiency and mechanically-induced chromism, fluorochromism and NLO-chromism.

This diploma thesis concentrates on the properties characterization of new organic materials for solar cells. In the theoretical part, there is a solar cells themed literature search, there is described a mechanism of conversion of solar energy, factors influencing photovoltaic conversion efficiency and materials using for preparation of organic solar cells. The practical part includes the preparation of solar cells and characterization of optical and electrical properties of the studied materials in thin layers and solutions. Used materials were conjugated polymers and derivatives of fullerenes.

La production durable d’énergie et la recherche d’alternatives aux sources non renouvelables font l’objet d’un grand intérêt à l’heure actuelle. Le principal objectif de cette thèse était de synthétiser et étudier de nouveaux complexes organométalliques à base de Ru-acétylure, puis évaluer leurs propriétés photovoltaïques dans des cellules solaires hybrides à colorant et organique à hétérojonction volumique. Des complexes bimétalliques dissymétriques ont été développés afin d’obtenir des chromophores à absorption panchromatique, en bénéficiant d’une structure « push-pull » et du motif [Ru(dppe)2] comme excellent relai d’électron. En parallèle des complexes symétriques à un ou deux centres métalliques ont été développés, ceux-ci ont ensuite été intégrés à des cellules solaires organiques à hétérojonction volumique. Lors de cette étude, chaque dispositif a fait l’objet de différentes étapes d’optimisations dans le but d’améliorer les transferts de charges en améliorant la morphologie de la couche active. Les principales méthodes d’optimisations appliquées ont consisté à réaliser des traitements par « solvent vapor annealing », ajouter des additifs structurants et utiliser le colorant dans une matrice polymère dans un dispositif à mélange ternaire. / Today the sustainable energy production and research for alternatives to non-renewable sources attract a lot of interest. The aim of this PhD research was to synthetize and study new organometallic complexes Ru-diacetylide based, then to characterize their photovoltaic properties in hybrid dye-sensitized and organic bulk-heterojunction solar cells. To obtain panchromatic chromophores, asymmetric bimetallic complexes have been designed using [Ru(dppe)2] unit as excellent electron relay in a “push-pull” structure. In parallel, symmetric complexes have been developed with one or two metallic centres, and then they have been integrated to organic bulk-heterojunction solar cells. For this study, each device has been optimized through different steps, in order to improve charges transfers by improving morphology of the active layer. The main methods of optimization applied consisted of application of “solvent vapor annealing” treatment, addition of structure additives and addition of the dye in polymer matrix, in ternary molecules blend device.

Le sujet de cette thèse porte sur l’élaboration du nouveau nanomatériau par la gravure électrochimique bipolaire (BEE) — le Ge mésoporeux et sur l’analyse de ses propriétés physico-chimiques en vue de son utilisation dans des applications photovoltaïques. La formation du Ge mésoporeux par gravure électrochimique a été précédemment rapportée dans la littérature. Cependant, le verrou technologique important des procédés de fabrication existants consistait à obtenir des couches épaisses (supérieure à 500 nm) du Ge mésoporeux à la morphologie parfaitement contrôlée. En effet, la caractérisation physico-chimique des couches minces est beaucoup plus compliquée et le nombre de leurs applications possibles est fortement limité. Nous avons développé un modèle électrochimique qui décrit les mécanismes principaux de formation des pores ce qui nous a permis de réaliser des structures épaisses du Ge mésoporeux (jusqu’au 10 um) ayant la porosité ajustable dans une large gamme de 15% à 60%. En plus, la formation des nanostructures poreuses aux morphologies variables et bien contrôlées est désormais devenue possible. Enfin, la maitrise de tous ces paramètres a ouvert la voie extrêmement prometteuse vers la réalisation des structures poreuses à multi-couches à base de Ge pour des nombreuses applications innovantes et multidisciplinaires grâce à la flexibilité technologique actuelle atteinte. En particulier, dans le cadre de cette thèse, les couches du Ge mesoporeux ont été optimisées dans le but de réaliser le procédé de transfert de couches minces d’une cellule solaire à triple jonctions via une couche sacrificielle en Ge poreux. / The subject of this thesis is the development of the new nanomaterial by bipolar electrochemical etching (BEE) - the mesoporous Ge and analysis of its physico-chemical properties for use in photovoltaic applications. The formation of mesoporous Ge by electrochemical etching has been previously reported in the literature. However, the important technological barrier of existing manufacturing processes was to obtain thick layers (above 500 nm) of the mesoporous Ge with perfectly controlled morphology. Indeed, the physico-chemical characterization of thin layers is much more complicated and the number of possible applications is very limited. We have developed an electrochemical model that describes the main mechanisms of formation of pores which allowed us to produce thick mesoporous structures of Ge (up to 10 um) with adjustable porosity in a range of 15% to 60% . In addition, the formation of porous nanostructures with well-controlled variable morphologies has now become possible. Finally, the mastery of these parametres has opened the extremely promising path towards the realization of porous multilayer structures based on Ge for many innovative and multidisciplinary applications. In particular, in the context of this thesis, the mesoporous layers of Ge were optimized for the purpose of performing a layer transfer process of a triple-junction solar cell via a sacrificial layer of porous Ge.

[pt] O tema das mudanças climáticas é um dos maiores desafios globais por parte de governos nacionais e articulações internacionais, visando estabilizar as concentrações de Gases do Efeito Estufa (GEE) e evitar interferências antropogênicas perigosas sobre a atmosfera e o sistema climático global. De acordo com o Painel Intergovernamental para a Mudança de Clima (IPCC), as principais causas das mudanças climáticas estão relacionadas as emissões liberadas pela queima dos combustíveis fósseis que compõem a matriz energética de muitos países industrializados, tornando-se necessária a limpeza do componente fóssil, particularmente do carbono. O Brasil está entre os dez países que mais emite GEE, apesar de possuir uma das matrizes energéticas com mais energias renováveis do mundo, assumiu em 2015 na convenção do clima em Paris o compromisso global de descarbonização da economia e de aumentar a participação de fontes de energia renováveis, como a eólica e a solar, na sua matriz energética. Valendo-se do alto potencial de irradiação solar no território brasileiro, o presente estudo aponta a geração distribuída de energia fotovoltaica como um dos caminhos para acelerar o ingresso do Brasil na economia de baixo carbono honrando o compromisso de mitigação dos GEE. Simulando cenários com base no ano de 2010 e usando o recurso de geoprocessamento, concluiu-se que com a instalação massiva de sistema fotovoltaico nos telhados dos domicílios brasileiros, é possível antecipar metas de mitigação dos GEE e gerar excedentes de emissões evitadas posicionando o Brasil como um importante protagonista na descarbonização da economia global até o final do século. / [en] Since the last decades of the twentieth century, human society has been facing economic and environmental crisis, influencing each other, drawing attention of national governments, international and non-governmental organizations together with several sectors of civil society. The economic crisis recently experienced by several countries and aggravated by various pressures of a global population that reached 7.3 billion in 2015 with a projected growth for 2030 of 8.5 billion people, will require an increase of employment, food production, water supply, energy production and industry development. As far as the environment is concerned, there is sufficient agreement by the scientific community, attributing to industrial processes, the use of fossil fuels, deforestation and land use throughout the 19th and 20th centuries, several environmental impacts such as: cumulative discharge of waste contaminating the soil, rivers and oceans; overexploitation of natural resources often leading to the risk of their depletion; emission of polluting gases (particularly CO2) causing global temperature rise, warming the atmosphere and oceans reducing snow and melting ice from the glacial regions, acidifying and raising the level of the oceans; use of agrochemicals and pesticides in agricultural activities contaminating soil and food; deforestation leading to severe ecological imbalances, biodiversity loss and changes in climate patterns. From this global context, several countries have been restructuring their laws and economies to stop the predatory exploitation of natural resources and implementing actions to clean up their energy matrix and decarbonize the economy reducing carbon emissions of fossil fuels sources responsible for the environment contamination.

Objective of master’s thesis theoretical part is especially to illustrate influence of operation conditions, such as solar radiation, temperature or pollution of photovoltaic generator active area, on load and power characteristics of photovoltaic generator, or more precisely on photovoltaic conversion efficiency. Possible variants of increasing effectivity of using photovoltaic generator are explored, such as solar radiation concentration, photovoltaic generator active area cooling or aplication of optimalization circuit. Pivotal part of master‘s thesis is focused on experimental device practical realisation, concretely type MSQ36-10 photovoltaic generator with oriented concentrators of solar radiation. Practical realisation includes design of master‘s thesis experimental part construction with subsequent design of photovoltaic generator motion cycle necessary for adequate simulation of configuration variants solved using single testing photovoltaic generator. Description of own experimental device construction with list of measuring places used in task takes up. It is used automatic monitoring system working as independent measurement task for required values measuring and consecutive data collecting. It is done in two phases. First phase is measurement of all required values, in second phase measurement with attached optimalization circuit is made. Optimalization circuit sets best working point of photovoltaic generator according to actual working conditions. Master‘s thesis intention is experimental verification of solar radiation concentrators application convenience, orientation of photovoltaic generator or its mutual combination, namely using type MSQ36-10 photovoltaic generator. Objective is evaluation of reached energetic gain for all experimental device layouts in variable operating conditions.