Organic solar cells have shown great promise of becoming a cheaper alternative to inorganic solar cells. Additionally, they can also be made semitransparent. To avoid using expensive indium tin oxide electrodes in organic solar cells the electrodes can be made from conductive polymer, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). However, these so-called PEDOT-PEDOT solar cells are prone to short-circuiting. The work behind this thesis thus aimed to find the cause of these short circuits. The initial working hypothesis assumed the hygroscopic PSS in the bottom electrode could attract water across the active layer when the top electrode layer was applied. This would then swell the bottom electrode and cause the active layer to crack leading to short circuits. Accordingly, swelling was investigated as it was suspected to be the main cause of the shorts. This was achieved by coating reflective substrates with different layers from the solar cell, dropping water on top of the stack and then filming the thin film interference effects. SEM, AFM and IR were also used for further analysis. Although the bottom electrode swells, it was found that water does not cause permanent cracking. Instead, the research unveiled that water causes a formation of blisters, which are suspected to be made of PSS. The exact mechanism for the formation of the shorts remains unclear however.

<p>Nanomaterials have been heavily studied in the past two decades. Previous findings have demonstrated that the characteristics of nanocomposites and the performance of nanomaterial-based devices are both determined by the interfacial characteristics of the nanomaterials. However, there are still some remaining challenges from interfacial characteristics to device applications, which are specified as follows: the difficulty in identifying the interfacial contacts of nanostructured surfaces, the instability of nanocomposite surfaces, and the under-researched mechanism of the correlation between interfacial characteristics and the performance of devices.</p> <p>Therefore, the main theme of this thesis is to investigate the interfacial contacts of nanostructured solid-liquid interfaces by direct observation, and to develop a stable nanocomposite based on which the direct observation of the interfacial contact can be better conducted, and to eventually investigate the effect of interfacial contacts on the performance of organic solar cells.</p> <p>As the previous identification of the solid-liquid interface is limited to a microscale range, a direct method of tracing the different wetting states of water was developed, on nanostructured surfaces. This method provided an answer to a long standing question of, whether there is a transition from Wenzel to Cassie states in the sliding angle drop on nanocomposite thin films. In order to complete the observation of the wetting states of water, a stable superhydrophobic nanocomposite thin film with hierarchical structure was developed.</p> <p>Furthermore, with the knowledge of identifying the wetting states and the preparing procedures of the nanocomposites, a surfactant-free small-molecule nanoparticle organic solar cell with a much improved fill factor was developed by spin coating. The inverse correlation of series resistance and parallel resistance was discovered, due to the morphology change and the variation of the charge carrier concentration near the donor-acceptor interface in small-molecule organic solar cells.</p> / Doctor of Philosophy (PhD)

This thesis explores the evaporation kinetics of various polymer-solvent and binary solvent mixtures to explore possible connections between the solutions properties and their evaporation process. By looking at the evaporation of polymer-solutions and binary-solvent solutions, through the change in weight as the solvent evaporates and the evaporation rate of the evaporation process, potential connections could be found. The results indicate that the presence of polymers influence the solvent evaporation, with polystyrene (PS) generally accelerating and polymethyl methacrylate (PMMA) either decelerating or having minimal impact on evaporation rates. Binary solvent mixtures exhibited non-proportional increases in evaporation rates, suggesting complex intermolecular interactions, but no apparent patterns between their properties and deviation in the evaporation process. This would need further research to find possible connections to be able to predict the evaporation process. But these findings highlight the importance of understanding polymer-solvent compatibility and evaporation dynamics to enhance performance and to identify environmentally friendly solvents for organic photovoltaic (OPV) cell fabrication. / Detta examensarbete undersöker avdunstningskinetiken hos olika polymer-lösningsmedel och binära lösningsmedelsblandningar för att utforska möjliga samband mellan lösningarnas egenskaper och deras avdunstningsprocess. Genom att studera avdunstningen av polymer-lösningar och binära lösningsmedelslösningar, genom förändringen i vikt när lösningsmedlet avdunstar och avdunstningshastigheten, kan potentiella samband identifieras. Resultaten indikerar att närvaron av polymerer påverkar lösningsmedlets avdunstning, där polystyren (PS) generellt accelererar och polymetylmetakrylat (PMMA) antingen decelererar eller har minimal inverkan på avdunstningshastigheterna. Binära lösningsmedelsblandningar visade icke-proportionella ökningar i avdunstningstider, vilket tyder på komplexa intermolekylära interaktioner, men inga tydliga mönster mellan deras egenskaper och avvikelser i avdunstningsprocessen kunde identifieras. Ytterligare forskning behövs för att finna möjliga samband för att kunna förutsäga avdunstningsprocessen. Dessa fynd understryker vikten av att förstå polymer-lösningsmedelskompatibilitet och avdunstningsdynamik för att förbättra effektiviteten och kunna identifiera miljövänliga lösningsmedel för tillverkning av organiska solceller (OPV).

The aim of this work was to investigate silver nanowire as well as carbon nanotube networks as transparent conducting electrodes for small molecule organic solar cells. In the framework of the nanowire investigations, a low-temperature method at less than 80 °C is developed to obtain highly conductive networks directly after the deposition and without post-processing. In detail, specific non-conductive organic materials act as a matrix where the nanowires are embedded in such that a mutual attraction based on capillary forces and hydrophobic interaction is created. This process is mediated by the ethanol contained in the nanowire dispersion and works only for sublayer materials which exhibit hydrophobic and hydrophilic groups at the same time. In contrast to high-temperature processed reference electrodes (210 °C for 90 min) without matrix, a slightly lower sheet resistance of 10.8 Ohm/sq at a transparency of 80.4 % (including substrate) is obtained by using polyvinylpyrrolidone as the sublayer material. In comparison to annealed silver nanowire networks, the novel approach yields a performance enhancement in corresponding organic solar cells which can compete with ITO-based devices. Furthermore, a novel approach for scalable, highly conductive, and transparent silver nanowire top-electrodes for organic optoelectronic devices is introduced. By utilizing a perfluorinated methacrylate as stabilizer, silver nanowires with high aspect ratio can be transferred into inert solvents which do not dissolve most organic compounds making this modified dispersion compatible with small molecule and polymer-based organic optoelectronic devices. The inert silver nanowire dispersion yields highly performing top-electrodes with a sheet resistance of 10.0 Ohm/sq at 80.0 % transparency (including substrate) directly after low-temperature deposition at 30 °C and without further post-processing. In comparison to similarly prepared reference devices comprising a thin-metal film as transparent top-electrode, reasonable power conversion efficiencies are demonstrated by spray-coating this dispersion directly on simple, air-exposed small molecule-based organic solar cells. Moreover, a deeper understanding of the percolation behavior of silver nanowire networks has been achieved. Herein, direct measurements of the basic network parameters, including the wire-to-wire junction resistance and the resistance of a single nanowire of pristine and annealed networks have been carried out for the first time. By putting the values into a simulation routine, a good accordance between measurement and simulation is achieved. Thus, an examination of the electrical limit of the nanowire system used in this work can be realized by extrapolating the junction resistance down to zero. The annealed silver nanowires are fairly close to the limit with a theoretical enhancement range of only 20 % (common absolute sheet resistance of approximately 10 Ohm/sq) such that a significant performance improvement is only expected by an enlargement of the nanowire length or by the implementation of new network geometries. In addition, carbon nanotube networks are investigated as alternative network-type, transparent bottom-electrode for organic small molecule solar cells. For that purpose, cleaning and structuring as well as planarization procedures are developed and optimized which maintain the optoelectronic performance of the carbon nanotube electrodes. Furthermore, a hybrid electrode consisting of silver nanowires covered with carbon nanotubes is fabricated yielding organic solar cells with only 0.47 % power conversion efficiency. In contrast, optimized electrodes comprising only carbon nanotubes show significantly higher efficiency. In comparison to identically prepared ITO devices, comparable or lower power conversion efficiencies of 3.96 % (in p-i-n stack), 4.83 % (in cascade cell) as well as 4.81 % (in p-n-i-p architecture) are demonstrated. For an inverted n-i-p stack design, the highest power conversion efficiency of 5.42 % is achieved.

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The demand for renewable energy sources has grown out of the humanity’s increasing need for electricity as well as depleting fossil fuel reserves. Organic-dye sensitised solar cells were developed as a green, cost-effective alternative to the market-dominating silicon solar cell technology. The field of photovoltaic devices and organic-DSSCs is interesting because we want to develop better, more efficient cells at lower costs using environmentally friendly materials. By studying the fundamental physics and chemistry processes occurring during and after the interaction of light with these devices, we create a window into the mechanism of photosynthesis. Our DSSCs were prepared by sensitisation of highly porous ZnO with different indoline dyes containing the same chromophore, but different alkyl chain lengths bonded to one of two carboxyl anchors as: DN91 (1 C) < DN216 (5 C) < DN285 (10 C). The role of the dye molecules is to absorb photons and donate electrons to the ZnO which acts as the charge acceptor, at the dye|ZnO interface. Through photoelectrochemical characterisation it was found that the structure of the dyes has an effect on the maximum current (JSC) produced by the cells: the shorter the alkyl chain, the higher the JSC. This macroscopic investigation was complimented by microscopic measurements in the form of transient absorption spectroscopy. This allows us to follow, in real time, the photoinduced oxidation of the dye and its regeneration occurring through desired and undesired pathways. It was found that the injection efficiencies of the dye molecules were directly responsible for the trend in the short circuit currents. / AFRIKAANSE OPSOMMING: Die aanvraag na die ontwikkeling van herwinbare energie bronne spruit voort uit die voorsienbare uitputting van fossiel brandstof bronne sowel as die groeiende behoefte om aan die mensdom se elektrisiteit behoeftes te voldoen. Kleurstof gesensitiseerde sonselle is ontwikkel as ’n groen, koste-effektiewe alternatief tot die silikon sonsel tegnologie wat die mark domineer. Die fotovoltaïse toestel veld, spesifiek organiese kleurstof gesensitiseerde sonselle is interessant omdat daar ruimte bestaan vir die ontwikkeling van beter meer effektiewe selle in terme van vervaardigings koste en prosesse wat omgewingsvriendelik is. Deur die fundamentele fisika en chemiese prosesse wat plaas vind tydens en na lig interaksie met hierdie selle te bestudeer gee dit insig oor die werkingsmeganisme van fotosintese. Ons kleurstof gesensitiseerde sonselle is voorberei deur sensitasie van hoogs poreuse ZnO met verskillende indolien kleurstowwe wat dieselfde kromofoor bevat wat met verskillende alkiel ketting lengtes verbind is aan een van twee karboksiel ankers as: DN91 (1 C) < DN216 (5 C) < DN285 (10 C). Die rol van die kleurstof molekules is om fotone te absorbeer en elektrone te doneer aan die ZnO wat as die lading akseptor dien by die kleurstof|ZnO intervlak. Deur fotoelektrochemiese karakterisasie is bevind dat die struktuur van die kleurstof ’n effek het op die maksimum stroom (JSC) wat die selle produseer: hoe korter die die akiel ketting, hoe hoër die JSC. Hierdie makroskopiese ondersoek is voltooi deur mikroskopiese metings in die vorm van tydopgelosde absorpsiespektroskopie. Dit laat ons toe om die fotogeinduseerde oksidasie asook regenerasie van die kleurstof te volg soos wat dit plaas vind deur gewenste sowel as ongewenste roetes. Dit is bevind dat die inspuitings effektiwiteit van die kleurstof molekules direk verantwoordelik is vir die waarneembare trajek in die kortsluitings stroom.

This thesis describes studies on nanohybrid systems consisting of single-walled carbon nanotubes (SWNTs) with monolayer coatings of semiconducting polymers. Steady-state and time-resolved optical and high-resolution microscopy experiments were used to investigate the blends. These materials show promise for use in organic photovoltaics (OPVs) owing to the high carrier mobilities and large aspect ratios of SWNTs, the controllable solubilisation of tubes with various polymers and the broad light-harvesting abilities of organic polymers. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising carbon nanotubes in OPV devices, revealing poor performances to date. The experimental methods used during the thesis are detailed in Chapter 3 and the solution processing techniques used to prepare the polymer–nanotube blend samples are described in Chapter 4. Chapter 5 describes a study on a nanotube blend with a thiophene polymer, a system previously unsuccessfully implemented into OPV devices. Ultrafast spectroscopic measurements showed that electrons can transfer on a 400 fs time scale from the polymer to nanotubes and the conditions to allow long-lived free charges to be produced were found. The study is extended in Chapter 6 to show that nanostructures consisting of a nanotube coated in one polymer can then be coated by a second polymer and that these nano-engineered structures could be implemented into OPV devices. The use of a competition binding process to isolate purely semiconducting nanotubes dispersed with any desired polymer is then described in Chapter 7. Finally, Chapter 8 introduces systems consisting of chains of porphyrin units, nature’s light-harvesting systems, bound to nanotubes and the blends were found to exhibit the required electronic alignment for use in OPVs. The work described in this thesis provides an explanation for the poor device behaviour of nanotube–polymer blends to date and, in particular, demonstrates several nanohybrid systems that show particular promise for improved OPV applications.

As células solares orgânicas, ou dispositivos fotovoltaicos orgânicos (OPVs), vêm se consolidando como uma tecnologia promissora para a geração de energia limpa e renovável devido aos progressos observados nos últimos anos em termos de eficiência e, sobretudo, ao seu baixo custo e facilidade de processamento, e à sua adaptabilidade à eletrônica flexível. Entretanto, ainda se faz necessário aumentar sua eficiência, sua estabilidade e seu tempo de vida de operação. Esses desafios só serão superados por meio de uma melhor compreensão dos processos de geração e de recombinação dos portadores fotogerados, e dos fenômenos de transporte eletrônico ao longo do dispositivo, desde a geração dos portadores até sua coleta pelos eletrodos. A perda de propriedades quando em operação sob condições ambientais é outro obstáculo a ser vencido, e para isso, é necessário conhecer as razões que provocam a degradação do dispositivo. Neste contexto, esta tese tem por objetivo o estudo de propriedades fundamentais que governam a geração, recombinação, transporte e coleta de cargas pelos eletrodos de células solares orgânicas com estrutura ITO/PEDOT:PSS/PTB7-Th:PC71BM/Ca/Al em diferentes condições de funcionamento. Em específico, em atmosfera inerte de nitrogênio e em atmosfera ambiente. O primeiro passo nesse sentido foi a fabricação e otimização dos dispositivos através de diferentes métodos experimentais. Conseguimos progredir muito na parte de confecção, produzindo células OPVs com eficiência de 7,85 %. Posteriormente, realizamos um estudo comparativo entre dois dispositivos com essa estrutura, sendo a diferença entre eles a adição de um aditivo durante a preparação da camada ativa (PTB7-Th:PC71BM): a molécula de 1,8-diiodooctano (DIO). Os dispositivos foram então caracterizados por técnicas de absorção de UVVis e Microscopia de Força Atômica (AFM). Os estudos elétricos dos dispositivos foram realizados por medidas de J-V no escuro e sob iluminação (1 sol), em diferentes temperaturas (150 a 300 K). Com o auxílio da equação de Mott-Gurney obtivemos os valores de mobilidade eletrônica (&mu;) dos portadores de cargas, para diferentes temperaturas, em ajustando-se as curvas de retificação no escuro. Os ajustes das respostas J-V (fotocorrente) sob iluminação foram ajustadas por uma equação derivada da cinética das taxas de geração e extração, em considerando-se cinética de segunda ordem para a recombinação bimolecular, de onde extraímos a razão &mu;2k (k é o coeficiente de recombinação) também para diferentes temperaturas. Deste estudo, foi possível concluir que o efeito do DIO na morfologia da camada ativa melhora o processo de condução por hopping e diminui o coeficiente de recombinação, o que possibilita um melhor desempenho fotovoltaico do dispositivo. Esse estudo permitiu obter o fator de redução (&zeta;) do coeficiente de recombinação, e sua variação com a temperatura. O nosso último estudo foi investigar os mecanismos de degradação de um dispositivo com DIO exposto em condições ambientais, sobretudo devido à ação do oxigênio. Nesse estudo foram realizadas medidas de Foto-CELIV (Extração da Corrente pelo Aumento Linear da Tensão -CELIV) e os ajustes das curvas de J-V sob iluminação foram feitos pela equação de circuito equivalente de uma célula solar dos quais obteve-se a variação das resistências série e paralelo em função do tempo de exposição ao ambiente. / Organic solar cells, or organic photovoltaics devices (OPVs), have been consolidating as a promising technology for the generation of clean and renewable energy due to the progress observed in recent years in terms of efficiency, and above all by its low cost and ease of processing, and their adaptability to flexible electronics. However, it is still required to increase its efficiency, its stability and its operating life. These challenges will only be overcome through a better understanding of the processes of generation and recombination of the photogenerated carriers, and of the phenomena of electronic transport throughout the device, from the generation of the carriers to their collection by the electrodes. The loss of properties when operating under environmental conditions is another obstacle to be overcome, and for this, is mandatory to well known the reasons of degradation effects. In this context, this thesis aims at the study of fundamental properties that govern the generation, recombination, transport and collection of charges by the electrodes, at different operating conditions, having ITO/PEDOT:PSS/PTB7-Th:PC71BM/Ca/Al as structure. Specifically, in an inert atmosphere of nitrogen, and in an ambient atmosphere. The first step in this direction was the manufacturing and optimization of the devices through different experimental methods. We achieved a great of progress in the manufacturing process, producing OPV cells with 7.85% efficiency. Afterward, we performed a comparative study between two devices of this structure, the difference between them being the addition of an additive during the preparation of the active layer (PTB7-Th: PC71BM): the 1,8-diiodooctane (DIO) molecule. The devices were then characterized by UV-Vis absorption techniques and Atomic Force Microscopy (AFM).The electrical studies of the devices were performed by J-V measurements, in the dark and under illumination (1 sol), at different temperatures (150 to 300 K). With the aid of the Mott-Gurney equation we obtained the values of electronic mobility (&mu;) of the charge carriers, for different temperatures, by adjusting the rectification curves in the dark. The adjustments of the JV responses under illumination were obtained by an equation that was derived from the kinetics of the generation and extraction rates, considering second-order kinetics for bimolecular recombination. From such fitting, it was extracted the &mu;2k ratio (k is the coefficient of recombination) also for different temperatures. From this study, it was possible to conclude that the effect of DIO on the active layer morphology improves the hopping conduction and decreases the recombination coefficient, leading to a better photovoltaic performance of the device. This study allowed to obtain the reduction factor (&zeta;) of the recombination coefficient, and its variation with temperature. Our last study was to investigate the mechanisms of degradation of a device with DIO exposed in environmental conditions, mainly due to the action of oxygen. In this study, photo-CELIV (Current Extraction by Linear Increasing Voltage - CELIV).technique was performed and the adjustments of the J-V curves under illumination were made by the equivalent circuit equation of a solar cell, from which the variation of the series and parallel resistances was obtained as a function of the exposure time to the environment.

L’objectif de la thèse consiste à développer une série des molécules d’architecture en haltère à base de phtalocyanine et à caractère donneur, pour l’élaboration de cellules solaires organiques. Plus particulièrement, les molécules sont des triades entièrement conjuguées, constituées de deux phtalocyanines de zinc séparés par un chromophore rigide de nature variable (un dérivé de benzothiadiazole, d’isoindigo ou de dikétopyrrolopyrrole). Dans ce travail, nous avons cherché à optimiser les modes de synthèse en utilisant différentes réactions de couplages catalysées. Nous avons également cherché à faire varier la nature du cœur et le nombre de chaînes ramifiées périphériques, afin d’étudier leur impact sur les niveaux d’énergie et les propriétés optiques, structurales, de transport de charge et enfin photovoltaïques. / This work reports a series of dumbbell-shaped molecules based on phthalocyanine with an electro-donating character, to be used in organic solar cells. More particularly, the molecules are fully-conjugated triads, made of two zinc phthalocyanine fragments separated by a rigid central dye of different nature (derivative of benzothiadiazole, isoindigo or diketopyrrolopyrrole). The synthesis of the materials was optimized by varying the type of the cross-coupling reactions. The properties of the molecules (absorption, energy levels, structure, charge transport and photovoltaic) were investigated as function of the nature of the central dye and the peripheral ramified chains on the phthalocyanine fragments.

La faible durée de vie des cellules solaires organiques constitue un frein à leur développement commercial. Dans ce contexte, ce travail de thèse a été consacré à l’amélioration de la résistance mécanique des cellules d’une part, et d’autre part à l’étude de leur stabilité chimique sous l’impact de la lumière. Concernant le premier axe de recherche, nous avons proposé la synthèse de nouveaux copolymères à blocs (P3HT-b-P(R)SS) susceptibles d’améliorer l’adhésion entre la couche active (P3HT:PCBM) et la couche qui transporte les trous (PEDOT:PSS) dans des dispositifs inverses. Puis, concernant le second axe de recherche, à savoir l’amélioration de la résistance à la lumière de la couche active des cellules, nous avons élucidé les mécanismes de dégradation des polymères et identifié celles de leurs propriétés physico-chimiques impactant leur stabilité. En combinant techniques analytiques et modélisation, il a tout d’abord été possible d’identifier les points faibles d’un polymère modèle, le Si-PCPDTBT. Puis, dans l’objectif d’établir une relation structure-stabilité, l’effet de la variation systématique du squelette conjugué et de la chaîne latérale du polymère a été étudié. Finalement, une analyse multi-échelle a été mise en oeuvre, allant de la stabilité de la couche active jusqu’à celle de la cellule solaire correspondante. Il a alors été montré qu’en choisissant judicieusement les matériaux de la couche active, les couches interfaciales, l’architecture et l’encapsulation des cellules, il était tout à fait possible d’atteindre des durées de vie supérieures à trois ans sans perte significative de performance électrique des dispositifs. / The commercial application of Organic Solar Cells is limited by their short operational lifetimes. In this context, this work has been devoted to the improvement of both the mechanical resistance of these devices and their chemical stability when exposed to light. Concerning the former, the synthesis of P3HT-b-P(R)SS block copolymers as adhesive materials has been proposed to improve adhesion between the active layer (P3HT:PCBM) and the hole transport layer (PEDOT:PSS) in inverted devices. In order to improve the photochemical resistance of the active layer, the second main objective of this project was to identify both polymer degradation pathways and the properties determining polymer stability. Firstly, analytical techniques and modelling have been employed to identify the weak structural points in model low bandgap polymer, Si-PCPDTBT. Then, a series of polymers with systematically modified backbones and/or alkyl side chains has been studied with the aim of establishing a relationship between chemical structure and stability. Finally, multiscale analysis was undertaken on the degradation of solar cells, going from the stability of separate active layers to that of complete devices. It was shown that judicious selection of device layers, architectures, and encapsulation materials, can lead to operational lifetimes over three years with no efficiency losses.

Une alternative aux énergies fossiles est le domaine du photovoltaïque organique qui a récemment commencé son transfert technologique des laboratoires de recherche vers l’industrie. De nombreux efforts de recherche sont réalisés sur les matériaux et les procédés pour augmenter les performances des cellules solaires organiques. Dans ce contexte, ce travail présente une étude complète allant de la conception de nouveaux polymères donneurs d’électrons à grande largeur de bande interdite à leur caractérisation en dispositifs photovoltaïques. La principale caractéristique recherchée a été de diminuer le niveau énergétique HOMO des polymères pour augmenter la tension en circuit ouvert des dispositifs photovoltaïques. L’approche « donneur-accepteur » a été utilisée pour obtenir les propriétés désirées. Des polymères comportant des unités pauvres en électrons, quinoxaline ou dithienoquinoxaline, et des unités riches en électrons, dibenzosilole ou carbazole, ont été synthétisés par couplage de Suzuki ou par hétéroarylation directe. Des masses molaires allant jusqu’à 56 kg.mol-1 ont été obtenues. Le motif quinoxaline a été décliné sous forme de plusieurs molécules substituées par des atomes de fluor sur le benzène ou par des groupements thiophènes, bithiophènes et terthiophènes sur la partie pyrazine. Des espaceurs thiophènes ou thiazoles ont été utilisés pour relier l’unité riche en électrons et l’unité pauvre en électrons. Les relations entre les modifications structurales et les propriétés structurales et optoélectroniques des polymères ont été analysées. Les propriétés optiques ont été étudiées par spectroscopie UV-visible et par spectroscopie de fluorescence et ont montré une absorption allant jusqu’à 550 nm pour les polymères à motifs dithienoquinoxaline-dibenzosilole, 650 nm pour les polymères à motifs quinoxaline-dibenzosilole et 700 nm pour la famille quinoxaline-carbazole. Ces valeurs correspondent à des largeurs de bande interdite comprises entre 1,8 eV et 2,3 eV. Les niveaux énergétiques HOMO et LUMO des polymères ont été déterminés par électrochimie. Tous les polymères possèdent des niveaux énergétiques HOMO inférieurs à -5,0 eV. Les atomes de fluor et les espaceurs thiazoles ont permis d’abaisser les niveaux énergétiques HOMO des polymères jusqu’à -5,69 eV. Les structures des polymères ont été modélisées par DFT et étudiées par diffraction des rayons X. Les mobilités des trous des polymères ont été mesurées en transistor organique à effet de champ, des valeurs atteignant 9,0. 10 3 cm.V 1.s 1 ont été atteintes. Les polymères ont été testés en dispositifs photovoltaïques selon une architecture standard à hétérojonction volumique en mélange binaire et en mélange ternaire. En mélange avec le PC71BM ou l’IC61BA, ces polymères ont permis d’atteindre des tensions en circuit ouvert entre 0,65 V et 1,05 V et des rendements de conversion photovoltaïque jusqu’à 5,14 % sur une surface active de 0,28 cm2. Les morphologies des couches actives ont été étudiées par AFM afin de comprendre en détail les paramètres de fonctionnement des cellules obtenues. Les polymères présentés dans cette étude ont été utilisés dans des cellules solaires à mélange ternaire présentant de bonnes performances. Certains polymères ont été testés dans des photocathodes pour la production d’hydrogène et ont permis d’obtenir une amélioration du potentiel de réduction par rapport à celui obtenu avec les photocathodes à base de P3HT. Enfin, compte tenu de leurs propriétés optoélectroniques et de leurs performances photovoltaïques certains de ces polymères devraient pouvoir être employés de manière avantageuse en sous cellules de dispositifs tandem en remplacement du P3HT par exemple. / An alternative to fossil fuels are the organic photovoltaic cells which have recently started their technological transfer from research laboratories to industry. Many research efforts have been made on the modification of materials and processes to increase the performance of organic solar cells. In this context, this work presents a comprehensive study from the design of new electron-donor high band gap polymers to their characterisation in photovoltaic devices. The main requirement was to decrease the HOMO energy level of the polymers in order to increase the open circuit voltage of the solar cells. The "push-pull" approach was used to obtain the desired properties. Polymers with quinoxaline or dithienoquinoxaline as electron-deficient units and dibenzosilole or carbazole as electron-rich units were synthesized by Suzuki coupling or by direct heteroarylation. Molecular weights up to 56 kg.mol 1 were obtained. The electron-withdrawing unit quinoxaline was substituted by fluorine atoms on the benzene moiety and by thiophene, bithiophene and terthiophene group on the pyrazine moiety. Thiophenes or thiazoles were used as spacers to link the electron-donating and the electron-withdrawing units. The relationship between the structural modification of the polymers and their optoelectronic properties were analysed. The optical properties were studied by UV-visible spectroscopy and fluorescence spectroscopy. Whereby it appears that polymers with dithienoquinoxaline-dibenzosilole units showed an absorption up to 550 nm and polymers with both quinoxaline-dibenzosilole units and quinoxaline-carbazole units showed an absorption up to 650-700 nm respectively. The corresponding optical band gaps were found to range from 1.8 eV to 2.3 eV. The HOMO and LUMO energy levels of the polymers were determined by electrochemistry. All polymers exhibited HOMO energy levels below -5.0 eV. Fluorine atoms and thiazole spacers significantly lowered the HOMO energy levels of the polymers up to -5.69 eV. DFT was used to model the polymer structures. X-ray diffraction was used to analyse the distances between the polymer chains. Hole mobilities were measured in organic field effect transistors and values of up to 9.0 x 10 3 cm2.V-1.s-1 were obtained. The polymers were tested in organic photovoltaic devices according to a standard bulk heterojunction structure in binary and ternary mixtures. In a blend with PC71BM or IC61BA, these polymers have led to open circuit voltages ranging from 0.65 V to 1.05 V and to power conversion efficiencies of up to 5.14 % on a surface area of 0.28 cm2. The active layer morphologies were studied by AFM. The polymers presented in this work were used in ternary blend solar cells. Some polymers were tested in photocathodes for hydrogen evolution and showed an improvement of the reduction potential compared to that of the photocathodes based on P3HT. Owing to their optoelectronic properties and their photovoltaic properties in standard device configurations, some of the materials developed in this study appear as valuable materials for future developments of organic tandem solar cells.