Nous avons synthétisé différentes dyades donneurs-accepteurs (D-A) π-conjuguées à base de fullerène pour des applications photovoltaïques dans lesquelles les unités D étaient soit des oligophenylenevinylenes (OPV) soit des oligophenyleneethynylene (OPE) et les unités A étaient le C60 ou un endofullerène du type Y3N@C80. Il y avait une exigence supplémentaire pour nos matériaux, à savoir qu’ils devaient s’auto-organiser en phases liquides-cristallines. Pour ce faire, toutes les unités D contenaient un promoteur mésogène afin d'induire le mésomorphisme de la dyade D- et donc de contrôler la morphologie des couches minces nécessaires à l’élaboraiton des cellules photovoltaïques grâce à une organisation supramoléculaire. En dehors de cela, nous avons étudié l’influence de la nature chimique du donneur (par exemple lyophile ou amphiphile), de la longueur des oligomères et de la multiaddition sur les propriétés photophysiques et sur l'auto-assemblage. Nous avons synthétisé une dyade OPE-Y3N@C80 qui est le premier dérive mésomorphe et photosensible de ce type de métallofullerène endohédral. / We have synthesized different π-conjugated system-fullerene dyads for photovoltaic applications, where the donor units were either oligophenylenevinylene (OPV) or oligophenyleneethynylene (OPE) derivatives and for the acceptor, C60 or Y3N@C80 was used. There was an additional requirement for our materials: liquid crystallinity. All the donor units contained a mesogenic promoter in order to induce mesomorphism in the D-A dyad and to control the morphology of the prepared film through supramolecular organization. Apart from that, we investigated the effect of the chemical nature of the donor moiety (ie. lyophilic or amphiphilic), the oligomeric length and multiaddition on the photophysical properties and on the self-assembly. We have synthesized an OPE-Y3N@C80 dyad which is the first trimetallic nitride template endohedral metallofullerene derivative with mesomorphic and photoactive properties.

abstract: This is a two part thesis: Part – I This part of the thesis involves automation of statistical risk analysis of photovoltaic (PV) power plants. Statistical risk analysis on the field observed defects/failures in the PV power plants is usually carried out using a combination of several manual methods which are often laborious, time consuming and prone to human errors. In order to mitigate these issues, an automated statistical risk analysis (FMECA) is necessary. The automation developed and presented in this project generates about 20 different reliability risk plots in about 3-4 minutes without the need of several manual labor hours traditionally spent for these analyses. The primary focus of this project is to automatically generate Risk Priority Number (RPN) for each defect/failure based on two Excel spreadsheets: Defect spreadsheet; Degradation rate spreadsheet. Automation involves two major programs – one to calculate Global RPN (Sum of Performance RPN and Safety RPN) and the other to find the correlation of defects with I-V parameters’ degradations. Based on the generated RPN and other reliability plots, warranty claims for material defect and degradation rate may be made by the system owners. Part – II This part of the thesis involves the evaluation of Module Level Power Electronics (MLPE) which are commercially available and used by the industry. Reliability evaluations of any product typically involve pre-characterizations, many different accelerated stress tests and post-characterizations. Due to time constraints, this part of the project was limited to only pre-characterizations of about 100 MLPE units commercially available from 5 different manufacturers. Pre-characterizations involve testing MLPE units for rated efficiency, CEC efficiency, power factor and Harmonics (Vthd (%) and Ithd (%)). The pre-characterization test results can be used to validate manufacturer claims and to evaluate the product for compliance certification test standards. Pre-characterization results were compared for all MLPE units individually for all tested parameters listed above. The accelerated stress tests are ongoing and are not presented in this thesis. Based on the pre-characterizations presented in this report and post-characterizations performed after the stress tests, the pass/fail and time-to-failure analyses can be carried out by future researchers. / Dissertation/Thesis / Masters Thesis Engineering 2015

Les nanofils de silicium présentent un fort potentiel d'intégration, et leur utilisation dans des dispositifs électroniques tels que des cellules solaires photovoltaïques ne peut se faire que si leur élaboration et leurs propriétés structurales sont maitrisées. Nous présentons dans cette thèse une méthode de fabrication de matrices de nanofils de silicium par croissance catalysée par l'or ou le cuivre en dépôt chimique en phase vapeur et faisant appel à des matrices de guidage de la croissance en alumine nanoporeuse. Cette technique permet notamment la croissance d'assemblées de nanofils ultra-denses (1.10^{10} nanofils/cm²) sur substrat non préférentiel ou d'hétérostructures comme des nanofils de germanium sur substrat de silicium. Grâce à la diffraction des rayons X nous montrons ensuite que les nanofils produits sont de très bonne qualité structurale malgré leur substrat non préférentiel et la présence d'une légère déformation de leur maille cristalline. Le contrôle de la déformation cristalline de nanofils de germanium est par ailleurs démontré en encapsulant les nanofils dans une coquille de nitrure de silicium. De nouveaux éléments de réflexion sont également rapportés concernant la contamination des nanofils de silicium par le catalyseur de leur croissance. Enfin l'intégration des nanofils de silicium dans des dispositifs solaires photovoltaïques est démontré en faisant appel à des jonctions PN radiales entre le coeur et la coquille des nanofils. / Silicon nanowires are promising objects but their integration in electronic devices such as photvoltaic solar cells relies on the ability to control their production and tailor their structural properties. In this thesis we present a method to produce nanowire matrices using a gold or copper catalysed growth process by chemical vapor deposition and using a nanoporous alumina growth template. This method enables the fabrication of ultra-dense nanowire arrays (1.10^{10} nanowires/cm²) on non preferential substrate or heterostructures such as germanium nanowires on silicon substrate. Using X-ray diffraction we also show that the structural quality of the template grown nanowires is very good in spite of their non preferential substrate and the presence of a small cristalline lattice strain. The control of germanium nanowires strain is also demonstrated by embeding them in a silicon nitride shell. Besides, new results are presented concerning the catalyst contamination of silicon nanowires. Silicon nanowires integration in photovoltaic devices is eventually demonstrated using a radial geometry for the PN junction between the core and the shell of the nanowires.

L'extraction du bore du silicium liquide est une étape d'une chaîne de procédés de purification de silicium de qualité suffisante pour les applications photovoltaïques. Cette thèse étudie en priorité le procédé dit "gaz froid" qui consiste en l'injection d'un mélange de gaz Ar-H2-H2O sur du silicium liquide chauffé électromagnétiquement. Une deuxième méthode similaire ("procédé plasma") où on injecte un plasma thermique issu d'un mélange Ar-H2-O2 a également été étudiée. Un modèle est nécessaire afin d'optimiser le procédé pour économiser de l'énergie.Les trois objectifs du modèle sont la prédiction du flux de silicium issu de la surface (vitesse d'oxydation), du flux de bore issu de la surface (pour avoir la vitesse de purification), et du seuil de passivation. Le seuil de passivation est la limite de concentration d'oxydant au-delà de laquelleil apparait une couche de silice passivante qui empêche la purification. Afin de minimiser la consommation d'énergie en accélérant le procédé, on cherche à injecter une concentration d'oxydant juste en dessous du seuil de passivation.De précédentes études ont montré que le facteur limitant pour les flux de bore et de silicium est le transport d'oxydant dans la phase gaz. Ainsi, nous avons fait un modèle monodimensionnel réactif-diffusif à l'équilibre thermodynamique de la couche limite gazeuse. Selon ce modèle, l'effet de la formation d'aérosols de silice est de diviser par deux le flux d'oxydant vers la surface, ce qui sert aux simulations CFD. Cet effet des aérosols de silice sur les flux d'oxydant peut aussi se retrouver si on enlève l'hypothèse d'équilibre thermodynamique des aérosols de silice avec la phase gaz, ce qui est confirmé par des simulations CFD et des expériences.Pour ce qui concerne l'estimation de la vitesse de purification, les données les plus réalistes concernant l'enthalpie de formation de HBO(g) et le coefficient d'activité du bore dans le silicium liquide ont été sélectionnées. Nous obtenons une bonne prédiction de la vitesse de purification à différentes températures et concentrations d'oxydant, y compris pour le cas plasma que nous avons étudié, en utilisant ces données thermodynamiques et en supposant que les produits de réaction de surface SiO(g) et HBO(g) diffusent de manière similaire. Ces coefficients de transfert identiques pour HBO(g) et SiO(g) peuvent s'expliquer par une précipitation simultanée et commune de HBO(g) et SiO(g), selon des mécanismes de germination et croissance restant à déterminer.Un dispositif expérimental de lévitation électromagnétique de silicium sous un jet oxydant a été monté. La mesure et le contrôle de température d'une bille de silicium ont été mis en oeuvre ce qui permettra la mesure sans contaminations de données thermodynamiques concernant les impuretés .Le seuil de passivation mesuré sur quelques expériences disponibles peut être prédit par notre modèle d'oxydation (associé au facteur deux représentant les aérosols de silice), si on l'associe à un critère proposé dans la littérature, qui couple la fraction du flux d'oxydant arrivant à la surface à une loi d'équilibre entre SiO(g), Si(l) et SiO2(s/l). Nous montrons dans cette thèse que la couche passivante n'est compatible avec des aérosols de silice que si ces aérosols ne sont pas en équilibre avec la phase gaz. La cinétique de formation des aérosols de silice doit donc être étudiée plus en détails. / Boron extraction from liquid silicon is a step within a new chain of processes aimed to purify silicon that meets purity requirements specific to photovoltaic applications. This thesis focuses mostly on cold gas processes that involve the injection of a mixture of Ar-H2-H2O gases onto electromagnetically stirred liquid silicon. A second similar method ("plasma processes") that involves the injection of thermal plasma made from an Ar-H2-H2O mixture has also been studied. A model is needed to minimize energy consumption by optimizing the process.We want to be able to predict the flow of silicon from the reactive surface (oxidation speed), the flow of boron from the surface (to have the purification speed) and the passivation threshold. For a given setting, the passivation threshold is the limit oxydant partial pressure at injection beyond which a passivating silica layer appears on the surface of the liquid silicon, which interrupts the purification. In order to minimize the energy consumption, and for that matter , in order to speed up the process, we want to inject oxydant in a quantity just below the passivation threshold.Previous studies have shown that the limiting factor for the oxidation and purification speed is the transport of oxidant in the gas phase. That's why we have made a 1D reactive-diffusive model at thermodynamical equilibrium of the gaseous boundary layer. According to this model the effect of the formation of silica aerosols is to divide by two the flow of oxydant towards the surface, which is useful for the simplification of CFD simulations. This effect of the formation of silica aerosols on oxidant flows can also be found without the hypothesis of thermodynamical equilibrium of silica aerosols with the gas phase, as confirmed by simulations and experiments.Regarding the estimation of the purification speed, we have selected the most realistic values of the enthalpy of formation of HBO(g) and of the activity coefficient of boron in liquid silicon.We could get good estimates of the purification speed at different temperatures and levels of oxidant concentrations at injection, by using the selected thermodynamical values and by supposing that the surface reaction products HBO(g) and SiO(g) diffuse similarly. A reason for this similar diffusion of SiO(g) and HBO(g) might be a common and simultaneous precipitation , due to specific dynamics of nucleation and growth that need to be investigated further. Those results for cold gas processed could also be obtained for a plasma experiment.However for the plasma experiment, silica aerosols can be formed only in a very thin layer near the surface and this result needs confirmation from other experiments.Temperature measurement and control for electromagnetically levitating liquid silicon under a flow of oxidant were achieved. With more time, quantitative results could be achieved to measure thermodynamical data on impurities without contaminations.Regarding the prediction of the passivation threshold, we justified a thermodynamical equilibrium at surface of SiO(g) with Si(l) and SiO2(s/l) at passivation threshold with the spreading of silica particles over the liquid silicon surface with the stirring. We show that the passivation layer is compatible with silica aerosols only if those aerosols are not in equilibrium with the gas phase. Therefore the kinetics of formation of silica aerosols should be studied further. A previous empirical formula on the prediction of the passivation threshold for experiments where H2O is the oxidant has been confirmed using our CFD model. A passivation experiment has shown the absence of impact of silica aerosols on oxidant transport when the oxidant is O2.

Battery energy storage systems are a key factor for enabling a continuous increase of the fraction of photovoltaics in the Swedish electricity grid. One big challenge is to utilise all potential services of such a storage system. The aim of this study was to improve the supervisory controller for an existing battery storage and photovoltaic solution marketed by the Swedish company Ferroamp AB. This has been done by developing a combined peak reduction and time-of-use bill management algorithm, together with a simulation and evaluation software for optimisation of algorithm parameters. The algorithms and tools were evaluated using an installation made by Ferroamp AB and Vattenfall Eldistribution AB as a case study. Sensitivity analyses has been performed on economic parameters and length of the algorithm training data set. Improvement of economic profit, in this case study, were 300 % compared to the currently used algorithm and 32 % compared to a conventional threshold peak reduction algorithm. Despite this improvement, the battery energy storage system is shown to be non-profitable, with the economic profit only covering 36 % of the investment costs, not taking interest rate into account. Like in many other studies, power storage was found more profitable than energy storage. An increase of the grid power tariff and the grid energy fee of 30 % to 40 % is found to make the system viable. One interesting finding is that by using the proposed optimal algorithm, 55 % of the cycle life of the battery storage is still accessible for other services when considering 10 years of economic depreciation time for the system.

Orientador: Odivaldo José Seraphim / Banca: Luiz Francisco da Cruz / Banca: Eduardo Antonio Sleiman / Resumo: O uso de energias alternativas e renováveis tem sido cada vez mais discutido em todos os setores da sociedade. O interesse nessas fontes de energias, alternativas e renováveis, é de fundamental importância, tanto no que se refere à escassez, quanto ao preço do petróleo, além das questões ambientais envolvidas no uso dessas energias. Sistemas de geração eólica e fotovoltaica com armazenamento de energia em baterias tem-se apresentado como uma forma de geração alternativa de energia. A variabilidade na intensidade da energia eólica e solar pode ser contornada pela complementação entre uma fonte e outra, ou pela maior estabilidade configurada à geração do sistema. O objetivo desta dissertação é criar uma metodologia fuzzy e simular seu uso no controle inteligente de um sistema híbrido de geração de energia elétrica, utilizando as energias solar-fotovoltaica e eólica. Quando utilizamos um sistema de controle baseado na lógica fuzzy, é atingido o ponto de máxima geração de energia, desta forma transferindo toda a energia gerada à partir das fontes alternativas, solar-fotovoltaica e eólica, à carga e/ou as baterias quando seu uso não imediato. O modelo utilizado adota três variáveis de entrada, que são: velocidade do vento, radiação solar e carga do banco de baterias.Serão utilizados para as simulações alguns softwares como o MATLAB e outros, que serão citados ao longo do trabalho. Nestes ambientes serão analisadas e simuladas todas as modelagens matemáticas, regras e demais variáveis descritas no sistema fuzzy. Este modelo foi utilizado para a implementação de um sistema de controle de sistemas híbridos de geração de energia, proporcionando o melhor aproveitamento das fontes de energia, sol e vento, de modo que possamos extrair o máximo de energia possível dessas fontes alternativas sem nenhum prejuízo ao meio ambiente...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The use of alternative and renewable energy has been increasingly discussed in all sectors of society. The interest in these sources of energy, alternative and renewable, it is of fundamental importance, both in terms of shortage, as the price of oil, in addition to the environmental issues involved in the use of these energies. Systems with photovoltaic and wind generation storage of energy in batteries has been presented as a form of alternative energy generation. The variability in the intensity of solar and wind energy can be circumvented by complementation between a source and another, or the more stable set to the generation of the system. The objective of this dissertation is to create a methodology fuzzy and simulate their use in intelligent control of a hybrid system of generating power, using the energy solar-photovoltaic and wind.When you use a system of control based on fuzzy logic, is reached the point of maximum generation of energy, thus transferring all the energy generated on the basis of alternative sources, solar, photovoltaic and wind, to the load and / or batteries when its use not immediately. The model takes three variables of entry, which are: wind speed, solar radiation and loading the bank of batteries. The simulations will be used for some software such as MATLAB and others, that will be cited during the work. In these environments will be analyzed and simulated all mathematical modeling, rules and other variables in the system described fuzzy. This model could be used in the implementation of a system of control of hybrid systems to generate energy, providing the best use of energy sources, sun and wind, so we can extract the maximum energy possible these alternative sources without any prejudice to the environment. The work was developed in the Laboratory of Energização Rural, of the Department of Rural Engineering of UNESP - FCA...(Complete abstract, click electronic access below) / Mestre

Este documento mostra uma interpretação do comportamento do consumo de energia elétrica baseada nos dados numéricos que foram coletados com o uso de contadores de Ah em 38 instalações fotovoltaicas domiciliares. A pesquisa envolveu igual número de famílias de 10 comunidades rurais com diferentes características sócioculturais localizadas nos Estados de São Paulo, Pernambuco e Amazonas, no Brasil, e adicionalmente na região Puno, no Peru. Também se discute diversas questões acerca do consumo de energia elétrica em sistemas fotovoltaicos domiciliares e sua relação com o desenvolvimento socioeconômico. O objetivo principal é propor um procedimento para dimensionar esses sistemas que inclua os múltiplos fatores que foram identificados e que exercem forte influência no comportamento do consumo. Estes foram denominados fatores técnicos, gerenciais, psicológicos, geográficos, demográficos, socioculturais e econômicos. O procedimento proposto leva em conta a constatação resultante da análise estatística dos dados por meio da qual a função de distribuição Gama é a que melhor caracteriza o comportamento desse consumo. Em sua essência, esta função indica que “muitas pessoas consomem pouco e poucas pessoas consomem muito”. / This document shows an interpretation of the behavior of the electric energy consumption based on the numerical data collected with the use of Ah meter in 38 solar home systems. The research involved an equal number of families of 10 rural communities with different sociocultural characteristics located in the Brazilian States of São Paulo, Pernambuco and Amazonas, and additionally in the Puno region, in Peru. It also raises several points concerning the electric energy consumption in SHS´s and its relationship with the socioeconomic development. The main objective is to suggest a procedure for the sizing of SHS´s that includes the several factors that were identified and that exert strong influence in the behavior of the consumption. These were called technical, administrative, psychological, geographical, demographical, sociocultural and economic factors. This procedure takes into account the evidence resultant of the statistic analysis of the data by means of which the Gamma distribution function is the one which better characterizes the behavior of this consumption. Essentially, this function indicates that “many people consume little and few people consume much”.

Face à la problématique énergétique, les solutions envisagées dans le domaine du bâtiment s’orientent sur un mix énergétique favorisant la production locale ainsi que l’autoconsommation. Concernant l’électricité, les systèmes photovoltaïques intégrés au bâtiment (BiPV) représentent l’une des rares technologies capables de produire de l’électricité localement et sans émettre de gaz à effet de serre. Cependant, le niveau de température auquel fonctionnent ces composants, influence sensiblement leur efficacité ainsi que leur durée de vie. Ces deux constats mettent en lumière l’importance du refroidissement passif par convection naturelle de ces modules. La configuration privilégiée est une configuration d’intégration au sein d’une enveloppe ventilée qualifiée de double-peau photovoltaïque. La présente étude expérimentale porte sur les transferts de chaleur et les caractéristiques de l’écoulement en convection naturelle dans des canaux chauffés verticaux ou inclinés. Deux bancs d’essais existants ont été complétés afin d’obtenir des données. Ils sont composés de deux plaques planes parallèles séparées par une lame d’air. Les parois sont soumises à des conditions aux limites de type densité de flux imposée. Les températures moyennes à la paroi ont été mesurées par thermocouples. Un système de vélocimétrie par image de particules a permis d’obtenir des profils de vitesse moyenne ainsi que les distributions d’intensité turbulente dans l’écoulement. Les champs de vitesse instantanée ont également été examinés. Trois configurations ont été étudiées avec un nombre de Rayleigh variant entre 3,86 x 105 et 6,22 x 106. La première est un canal vertical avec une des deux parois chauffée uniformément. La seconde est un canal vertical dans lequel les deux parois sont chauffées de façon non-uniforme et alternée. La troisième est de type canal incliné chauffé uniformément sur la paroi supérieure. Le rapport de forme du canal (largeur/hauteur) est de 1/15 pour le deux premières configurations et de 1/16 pour la troisième. Une attention particulière a été portée sur l’identification de la zone de transition laminaire-turbulent. L’étude a permis de mettre en évidence la sensibilité de l’écoulement aux perturbations extérieures. Pour un chauffage uniforme et asymétrique, à partir d’un nombre de Rayleigh Ra* de 3.5 x 106 et pour θ = 60° et 90°, il a été constaté que la propagation de structures cohérentes dans le canal a lieu à partir de la mi-hauteur de ce canal. Ces instabilités favorisent alors les transferts thermiques. Dans le cas d’un chauffage non-uniforme sur les deux parois du canal, l’écoulement est fortement perturbé ce qui conduit à l’augmentation du brassage et de la contrainte de Reynolds sur la majorité de la largeur du canal. Enfin, pour chacune des configurations, des corrélations permettant de quantifier les transferts de chaleur à la paroi et au sein de la lame d’air (nombre de Nusselt moyen en fonction du nombre de Rayleigh) ont été établies. / Among technologies capable to produce electricity locally without contributing to GHG releases, building integrated PV systems (BIPV) could be major contributor. However, when exposed to intense solar radiation, the temperature of PV modules increase significantly, leading to a reduction in efficiency so that only about 14% of the incident radiation is converted into electrical energy. The high temperature also decrease the life of the modules, thereby making passive cooling of the PV components through natural convection a desirable and cost-effective means of overcoming both difficulties. An experimental investigation of heat transfer and fluid flow characteristics of natural convection of air in vertical and inclined open-ended heated channels is therefore undertaken so as provide reliable information for the design of BIPV. Two experimental set ups were developed and used during the present investigations; one located at the CETHIL laboratory in Lyon, the F-device and the other located at the University of New South Wales in Sydney, the R-device. Both channels consisted of two wide parallel plates each of which could be subjected to controlled uniform or non-uniform heat fluxes. The investigation has been conducted by analyzing the mean wall temperatures, measured by thermocouples and mean velocity profiles and turbulent quantity distributions of the flow, measured with a PIV system. Flow patterns close to the heated faces were also investigated. The study is particularly focused on the transition region from laminar to turbulent flow. Three different heating geometric arrangements are examined in the modified Rayleigh number range from 3.86 x 105 to 6.22 x 106. The first is a vertical channel with one wall uniformly heated while the other was unheated, the second was a vertical channel in which both walls were non-uniformly heated and the third is an inclined channel uniformly heated from above. In the vertical configurations the width-to-height channel aspect ratio was fixed at 1:15 and in the inclined ones at 1:16. It is shown that the flow is very sensitivity to disturbances emanating from the ambient conditions. Moreover, the propagation of vortical structures and unsteadiness in the flow channel which are necessary to enhance heat transfer, occurred downstream of the mid-channel section at Ra* = 3.5 x 106 for uniformly and asymmetrically heated channels inclined between 60° and 90° to the horizontal. Indeed, these unsteady flow phenomena appears upstream the location of the inflexion point observed in the temperature excess distribution of the heated wall. In the case of non-uniform heating on both sides of the channel, a stronger ‘disruption mechanism’ exists, which leads to enhanced mixing and increased Reynolds stresses over most of the width of the channel. Empirical correlations of average Nusselt number as a function of modified Rayleigh number were obtained for each configuration.

L’objectif final de la thèse est l'impression de la couche photo-active ternaire d'une cellule solaire organique en utilisant deux approches: l'une concerne l'apport de nanotubes de carbone (SWCNT) pour améliorer les propriétés de transport, l'autre concerne la préparation de mélanges ternaires de matériaux pour contrôler la couleur des cellules. Les encres pour la couche active incluant des SWCNT fonctionnalisés sont composées d’un donneur d'électron (polymère) (poly(3-hexylthiophène), [P3HT]) et d’un accepteur d'électron ( [6,6]-phényl C61-butyrique ester méthylique d'acide [PCBM]) et ont été développées pour la fabrication de cellules inversées. Ces cellules sont réalisées sur substrats de verre pour l'optimisation de leurs performances, puis sur substrats plastiques pour les applications. Diverses couches d'interfaces ont été testées, qui incluent l'oxyde de zinc (ZnO, couches obtenues par pulvérisation ionique (IBS) ou à partir de solutions de nanoparticules) pour la couche de transport d'électrons et le PEDOT:PSS, le P3MEET, le V2O5 et le MoO3 pour la couche de transport de trous. Des essais ont été effectués avec et sans CNT afin d’étudier leur impact sur les performances. Des résultats similaires sont obtenus dans les deux cas. Il était attendu que les CNT améliorent les performances, ce qui n’a pas été observé pour le moment. Des travaux supplémentaires sont donc nécessaires au niveau de la formulation de la couche active.Avec trois polymères de couleur rouge (P3HT), bleu (B1) et vert (G1), nous avons préparé des mélanges ternaires efficaces permettant l'obtention de couleurs jusque là indisponibles . Nous avons fait une étude sur le piégeage et les mécanismes de diodes parallèles associés aux mélanges. En général, nous avons constaté que les mélanges ternaires de polymères bleu et vert peuvent être décrits par une mécanisme de diodes parallèles, sans entrainer de perte de performances, ce qui n'est pas possible pour les systèmes P3HT:B1 :PCBM et P3HT:G1:PCBM qui se piègent mutuellement. L’objectif final du projet est l'impression de la couche photo-active ternaire d'une cellule solaire organique, composites ternaires (polymère:polymères:acceptor) ou dopés avec les SWCNT. Cette étape nécessite encore des développements futurs. / Two approaches were followed to achieve increased control over properties of the photo-active layer (PAL) in solution processed polymer solar cells. This was accomplished by either (1) the addition of functionalized single-walled carbon nanotubes (SWCNTs) to improve the charge transport properties of the device or (2) the realization of dual donor polymer ternary blends to achieve colour-tuned devices.In the first component of the study, P3HT:PC61BM blends were doped with SWCNTs with the ambition to improve the morphology and charge transport within the PAL. The SWCNTs were functionalized with alkyl chains to increase their dispersive properties in solution, increase their interaction with the P3HT polymer matrix, and to disrupt the metallic characteristic of the tubes, which ensures that the incorporated SWCNTs are primarily semi-conducting. P3HT:PCBM:CNT composite films were characterized and prepared for use as the photoactive layer within the inverted solar cell. The CNT doping acts to increase order within the active layer and improve the active layer’s charge transport properties (conductivity) as well as showed some promise to increase the stability of the device. The goal is that improved charge transport will allow high level PSC performance as the active layer thickness and area is increased, which is an important consideration for large-area inkjet printing. The use of ternary blends (two donor polymers with a fullerene acceptor) in bulk-heterojunction (BHJ) photovoltaic devices was investigated as a future means to colour-tune ink-jet printed PSCs. The study involved the blending of two of the three chosen donor polymers [red (P3HT), blue (B1), and green (G1)] with PC61BM. Through EQE measurements, it was shown that even devices with blends exhibiting poor efficiencies, caused by traps, both polymers contributed to the PV effect. However, traps were avoided to create a parallel-like BHJ when two polymers were chosen with suitable physical compatibility (harmonious solid state mixing), and appropriate HOMO-HOMO energy band alignment. The parallel diode model was used to describe the PV circuit of devices with the B1:G1:PC61BM ternary blend.

Au cours des dernières années, le développement des cellules organiques à réseaux interpénétrés a permis d’améliorer les rendements de conversion photovoltaïque (PV). Ces dispositifs incorporent une couche active constituée d’un mélange d’un matériau donneur d’électron (D) et d’un matériau accepteur d’électron (A). La réalisation de ces cellules requiert une optimisation minutieuse de ce mélange et de la morphologie de cette couche photo-active qui en résulte. Cette dernière peut cependant évoluer spontanément vers une ségrégation de phase, généralement délétère pour les performances PV. Une solution possible, et relativement peu étudiée, consiste à lier chimiquement le donneur D et l’accepteur A par un espaceur non-conjugué. Les travaux décrits dans ce manuscrit portent sur la synthèse et la caractérisation d’assemblages moléculaires de type D-σ-A ainsi que leur utilisation comme matériau dit « unique » pour la fabrication de cellules solaires organiques mono composant. Une première famille de dyades et triades à base d’un bloc donneur de type quaterthiophène a été étudiée. Cette partie décrit la méthodologie générale d’assemblage des blocs D et A via une réaction de cycloaddition de type Huisgen. Au cours des chapitres suivant, plusieurs dyades basées sur un bloc donneur « push-pull » ont été synthétisées puis caractérisées. Les performances PV de ces composés ont été évaluées au sein de cellules solaires mono-composant et les meilleurs rendements de conversion, atteignant 1.4 %, rivalisent avec l’état de l’art. / Over the last few years, the development of bulk heterojunction organic solar cells (BHJ OSCs) led to significant increase in photovoltaic (PV) efficiency. Such devices are based on interpenetrated networks of an electron-donor material (D) and an electron-acceptor material (A) constituting the active layer. Nevertheless a careful optimization of the morphology is required to reach high power conversion efficiency. Furthermore, this optimized morphology can evolve towards spontaneous phase segregation which can be detrimental for the PV performances. To circumvent these limitations, a relatively unexplored approach relies on the use of a material where the donor and the acceptor moieties are covalently linked to each other through a nonconjugated π-connector. In this context, the work reported herein describes the synthesis and characterization of various molecular D-σ-A assemblies, as well as their preliminary evaluation as “unique” material for the realisation of single component organic solar cells (SC-OSCs). A first family of dyads and triads, based on quaterthiophene moieties as donor block, was studied. A general methodology to assemble the two D and A blocks via a Huisgen-type click-chemistry is described. Then, in the next chapters, several dyads based on a “push-pull” donor block have been synthesized and characterized. The PV performances of these compounds have been evaluated in SC-OSCs leading to power conversion efficiency up to 1.4 %, a value close to the state of the art.