A compreensão dos caminhos de desativação não radiativa em polímeros conjugados é fundamental para o uso desses materiais em dispositivos luminescentes, células fotovoltaicas e sensores. Nesta tese, os processos não radiativos em filmes automontados de polímero luminescente foram investigados via análise da supressão de intensidade de fotoluminescência, utilizando a técnica de fluorescência estacionária, e através da medida do tempo de vida do estado excitado com fluorescência resolvida no tempo em arranjo de contagem de fótons. A camada emissiva constituída por poli(p-fenileno vinileno) (PPV) obtido da conversão térmica do precursor poli(cloreto de xilideno tetraidrotiofeno) (PTHT) apresentou tempos de vida entre 150 e 250 ps, e fraca dependência com o comprimento de onda de detecção da emissão. Na presença de uma monocamada contendo azocorante Vermelho do Congo (CR) ou ftalocianina tetrassulfonada de níquel (NiTsPc) atuando como receptor de energia foi observada supressão da fluorescência e encurtamento do tempo de vida (50-100ps). À medida que se aumenta a distância entre as camadas de doador e receptor via interposição de bicamadas de espaçador, a dinâmica do sistema tende à dinâmica de decaimento do estado excitado do PPV na ausência de receptor. A dependência da eficiência com a distância 1/r2 ou 1/r3 apontam para transferência de energia ressonante (RET) típica da interação plano-plano ou plano-camada. Os processos não radiativos foram também estudados em função da diluição de segmentos PPV dispersos em matriz de polieletrólito poli(cloreto de dodecildimetilamônio) PDAC. A diluição dos segmentos conjugados aumenta a eficiência quântica de emissão, torna o mecanismo de desativação mais lento (500 ps) e diminui a dependência do tempo de vida com o comprimento de onda de detecção, devido à menor eficiência dos mecanismos de desativação não radiativa. Na presença de uma camada receptora, a eficiência de transferência de energia é maior para amostras com segmentos mais diluídos indicando que esse mecanismo compete com os processos internos à própria camada emissiva. O tempo de vida aumenta em filmes com mais baixo grau de conjugação e a dependência com o comprimento de onda de emissão é mais forte. Em resumo, a técnica de automontagem se mostrou adequada para obter filmes com propriedades fotofísicas controláveis no nível molecular, que puderam ser estudadas com espectroscopias de fluorescência. / Understanding the pathway of excitation in conjugated polymers is important for using these materials as active layer in devices, photovoltaic cells and sensors. In this thesis, non-radiative processes in layer-by-layer (LbL) films were investigated with measurements of fluorescence quenching in steady-state fluorescence spectroscopy and of the singlet excited state lifetime using time-resolved fluorescence spectroscopy in a single photon counting (SPC) apparatus. The emissive layer of poly(p-phenylene vinylene) (PPV) obtained via thermal conversion of the soluble precursor poly(xylylidene tetrahydrothiophenium) chloride (PTHT) showed lifetime 150-250 ps and weak dependence on the emission wavelength. In the presence of an acceptor layer of either Congo Red (CR) or nickel tetrasulfonated phthalocyanine (NiTsPc) the PL intensity was quenched and the lifetime was shorter (50 -100 ps). Upon increasing the distance between the energy donor (PPV) and acceptor layers by interposing bilayers of inert polyelectrolytes the dynamics tended to the PPV dynamics. The distance-dependence of the energy transfer efficiency (1/r2 or 1/r3) points to a resonant process (RET) with a plane-to-plane or plane-to-slab interaction. The non-radiative processes were also studied for varying dilutions of the PPV segments in a matrix of the polyelectrolyte poly(dodecyl methylamonium chloride) (PDAC). This dilution increased the quantum efficiency and led to longer lifetimes (500 ps) owing to a less effective non-radiative energy transfer. When an energy acceptor layer is present, energy transfer is more efficient for the most diluted systems, indicating that such transfer competes with internal processes in the emissive layer. The lifetime increased in films with low degree of conjugation, for which there was a stronger dependence on the emission wavelength. It is concluded that the LbL methodology was suitable to obtain photophysical film properties that could be controlled at the molecular level, and investigated with varied fluorescence spectroscopies.

Esta tese de doutorado apresenta os resultados do estudo sistemático das propriedades ópticas das interfaces que aparecem em dispositivos orgânicos atuais emissores de luz ou OLEDs. Estamos interessados no entendimento do papel de cada uma das interfaces metal/polímero e ITO/polímero sobre a emissão da camada orgânica ativa emissora de luz. Para tanto, se fez necessário o domínio de todas as etapas de preparação e caracterização de filmes finos orgânicos, desde a síntese química dos polímeros até a preparação de amostras adequadas que permitissem a realização dos objetivos propostos. Ênfase foi dada aos processos de excitação e de relaxação energética dos portadores de carga (elétrons e buracos) em filmes ultrafinos automontados próximos às interfaces, correlacionando-os direta ou indiretamente com os efeitos de interface. Através do desenvolvimento e domínio de uma nova metodologia de preparação de filmes orgânicos, verificamos que a intensidade da luminescência de um filme de prova ultrafino de poli(p-fenileno vinileno) (PPV) com espessura em torno de 1,5 nm sofre grandes variações em uma extensa região próxima às interfaces metálicas de Au, Al e de ITO (óxido de índio-estanho). Esta camada de prova foi gradualmente separada da interface variando-se de forma controlada a espessura de um filme polimérico espaçador opticamente inerte. O perfil de intensidade da fotoluminescência nas proximidades das interfaces foi determinado em função da distância entre as superfícies estudadas (vidro, quartzo, metálica ou ITO) e a camada de prova emissora de PPV. Duas regiões relacionadas a processos radiativos distintos foram bem estabelecidas para as interfaces metálicas: uma região de extinção, nas proximidades da interface (< 20 nm), onde a luminescência é fortemente suprimida e uma outra de aumento da luminescência entre 20 e 90 nm. A grande variação da intensidade da luminescência observada neste trabalho é explicada considerando efeitos de interferência em uma semicavidade óptica, além dos processos de transferência de energia tipo Förster entre estados do PPV e estados de plásmons superficiais no metal. Verificamos que a distribuição espacial da radiação emitida é profundamente alterada por processos não radiativos de transferência de energia e pelas condições impostas pelas interfaces em uma semicavidade óptica. Modificações da superfície de ITO foram realizadas pelo tratamento acídico com água-régia suave. Nós observamos que a refletividade do ITO é fortemente dependente do tempo do tratamento e da espessura do espaçador. Como nos filmes metálicos, a emissão de um filme de prova de PPV sofre alterações nas proximidades da interface contendo ITO. Aqui, os parâmetros materiais (índice de difração, reflectância e comprimento de onda da emissão), a estrutura de superfície do ITO e os fatores geométricos mostram um papel importante. Cálculos da intensidade da emissão nas proximidades das interfaces descrevem de modo satisfatório os resultados experimentais. Do perfil de intensidade calculado próximo das interfaces, concluímos que a espessura e a posição da camada ativa emissora de luz devem ser otimizadas de modo a coincidir com a região de aumento ou amplificação da luminescência. / This PhD thesis is an extensive study of the optical properties of the interfaces of organic light-emitting devices (OLED’s). In particular, we investigated the influence of interfaces metal/polymer and ITO/polymer on the emission of an active layer in such devices. Therefore, it was necessary to dominate all the processes of fabrication and characterization of the multilayered structures used in the present investigation. We have used a very thin PPV probe layer (1.5 nm) to map the optical properties very near the metal/organic and the Indium-Tin Oxide (ITO)/organic interfaces. A new Spin-Layer-by-Layer method was employed which allowed a control of deposition of layers at the monolayer level. Precise variation of the metal/PPV or ITO/PPV separation over the entire substrate surface was achieved by the deposition of an organic inert spacer layer. The ITO surface modifications were carried out by soft acidic aquaregia treatment. A strong modulation of the probe layer emission was observed near the metal and ITO interfaces. These results are explained by calculations which include competing short range radiationless energy transfer and intensity modulation due effects produced by the optical cavity formed by metal/polymer films/air. At small distances (<20 nm) from interface, collective excitations in the metal act as energy acceptors, which open up an efficient nonradiative channel. Here, material parameters (diffraction index, reflectance and emission wavelength, for example), surface treatment and structure as well as geometrical factors may play an important role.

The performance and life time of organic solar cells are critically dependent on the properties of active layer materials and device interfaces. In this manuscript, we developed new organic-inorganic hybrid materials to create intimate contact between donor and acceptor phases and facilitate the interfacial electronic charge transfer through the device. First, the synthesis of versatile triethoxysilane-terminated poly(3-hexylthiophene) P3HT for direct anchoring (grafting-onto) in one step procedure to various metallic oxides was reported. Electro-optical analysis showed an efficient charge transfer from the polymer to nanoparticles; suggesting that these materials are suitable candidates for photovoltaic application. In the second part, we demonstrate for the first time the elaboration of low band gap polymer brushes on metallic oxide surfaces via surface initiated step growth polymerization (grafting-through). In both cases, a higher grafting density, better packing of polymer chains and enhanced optical properties were observed due to the grafting methodology and polymer characteristics. Finally, P3HT brushes were elaborated on indium tin oxide surface (ITO) as hole transporting layer of organic solar cells. Photovoltaic performances showed that P3HT self-assembled monolayer (SAMs) could be promising alternatives to PEDOT:PSS. / Les performances et la durée de vie des cellules solaires organiques sont fortement dépendantes de la qualité des matériaux de la couche active et des interfaces dans le dispositif. Dans ce manuscrit, nous avons développé des nouveaux matériaux hybrides organiques-inorganiques pour favoriser le contact entre les matériaux donneur/accepteur d’électrons et ainsi faciliter le transfert de charges à travers le dispositif. Tout d'abord, la synthèse de poly(3-hexylthiophène) P3HT fonctionnalisé par le triéthoxysilane a permis le greffage direct (« grafting-onto ») sur des oxydes métalliques. L’analyse des propriétés électro-optiques montre un transfert de charge efficace du polymère aux nanoparticules; ce qui suggère que ces matériaux sont des candidats potentiels pour l'application photovoltaïque. Dans la deuxième partie, nous avons montré pour la première fois, l’élaboration de brosses de polymères dits à faible bande interdite sur des surfaces d’oxydes métalliques par la technique « grafting-through ». Une densité de greffage élevée, un meilleur empilement des chaines de polymères et des propriétés optiques améliorées ont été obtenus grâce à la technique de greffage et aux caractéristiques du polymère greffé. Enfin, des brosses de P3HT ont été élaborées sur la surface d’oxyde d'indium et d’étain (ITO) en tant que couche de transport de trous de cellules solaires organiques. Les performances photovoltaïques ont montré que les monocouches auto-assemblées de P3HT (SAM) peuvent être une alternative au PEDOT: PSS.

Polymer-based photovoltaics have the potential to contribute to boosting photovoltaic energy conversion overall. Besides allowing large-area inexpensive processing, polymeric materials have the added benefit of opening new market applications for photovoltaics due to their low-weight and interesting mechanical properties. The energy conversion efficiency values of polymer photovoltaics have reached new record values over the past years. It is however crucial that stability issues are addressed together with efficiency optimization. Understanding fundamental materials aspects is key in both areas. In the work presented in this thesis, the morphology of polymer:fullerene films and its influence on device performance was studied, as well as the effect of light exposure on the surface of fullerene films. Several polyfluorene copolymers were used for the morphology studies, where the effects of changing spin-coating solvent and of side chain engineering were investigated with dynamic secondary ion mass spectrometry (dSIMS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Polymer-enriched surfaces were found in all blend films, even in the cases with homogeneous distributions in the bulk. Side chain engineering of the polymer led to gradual changes in the compositional variations perpendicular to the surface, and to slight variations in the photocurrent. The electronic structure of the fullerene derivative PCBM was studied in detail and the spectroscopic fingerprint of the materials was analysed by comparison with theoretically simulated spectra. Photo-stability studies done in air showed that the surface of fullerene films underwent severe damages at the molecular level, which is evident from changes in the valence band and X-ray absorption spectra. These changes were explained by transitions from sp2-type to sp3 hybridization of the carbon atoms in the cage that resulted in the destruction of the fullerene cage.

A compreensão dos caminhos de desativação não radiativa em polímeros conjugados é fundamental para o uso desses materiais em dispositivos luminescentes, células fotovoltaicas e sensores. Nesta tese, os processos não radiativos em filmes automontados de polímero luminescente foram investigados via análise da supressão de intensidade de fotoluminescência, utilizando a técnica de fluorescência estacionária, e através da medida do tempo de vida do estado excitado com fluorescência resolvida no tempo em arranjo de contagem de fótons. A camada emissiva constituída por poli(p-fenileno vinileno) (PPV) obtido da conversão térmica do precursor poli(cloreto de xilideno tetraidrotiofeno) (PTHT) apresentou tempos de vida entre 150 e 250 ps, e fraca dependência com o comprimento de onda de detecção da emissão. Na presença de uma monocamada contendo azocorante Vermelho do Congo (CR) ou ftalocianina tetrassulfonada de níquel (NiTsPc) atuando como receptor de energia foi observada supressão da fluorescência e encurtamento do tempo de vida (50-100ps). À medida que se aumenta a distância entre as camadas de doador e receptor via interposição de bicamadas de espaçador, a dinâmica do sistema tende à dinâmica de decaimento do estado excitado do PPV na ausência de receptor. A dependência da eficiência com a distância 1/r2 ou 1/r3 apontam para transferência de energia ressonante (RET) típica da interação plano-plano ou plano-camada. Os processos não radiativos foram também estudados em função da diluição de segmentos PPV dispersos em matriz de polieletrólito poli(cloreto de dodecildimetilamônio) PDAC. A diluição dos segmentos conjugados aumenta a eficiência quântica de emissão, torna o mecanismo de desativação mais lento (500 ps) e diminui a dependência do tempo de vida com o comprimento de onda de detecção, devido à menor eficiência dos mecanismos de desativação não radiativa. Na presença de uma camada receptora, a eficiência de transferência de energia é maior para amostras com segmentos mais diluídos indicando que esse mecanismo compete com os processos internos à própria camada emissiva. O tempo de vida aumenta em filmes com mais baixo grau de conjugação e a dependência com o comprimento de onda de emissão é mais forte. Em resumo, a técnica de automontagem se mostrou adequada para obter filmes com propriedades fotofísicas controláveis no nível molecular, que puderam ser estudadas com espectroscopias de fluorescência. / Understanding the pathway of excitation in conjugated polymers is important for using these materials as active layer in devices, photovoltaic cells and sensors. In this thesis, non-radiative processes in layer-by-layer (LbL) films were investigated with measurements of fluorescence quenching in steady-state fluorescence spectroscopy and of the singlet excited state lifetime using time-resolved fluorescence spectroscopy in a single photon counting (SPC) apparatus. The emissive layer of poly(p-phenylene vinylene) (PPV) obtained via thermal conversion of the soluble precursor poly(xylylidene tetrahydrothiophenium) chloride (PTHT) showed lifetime 150-250 ps and weak dependence on the emission wavelength. In the presence of an acceptor layer of either Congo Red (CR) or nickel tetrasulfonated phthalocyanine (NiTsPc) the PL intensity was quenched and the lifetime was shorter (50 -100 ps). Upon increasing the distance between the energy donor (PPV) and acceptor layers by interposing bilayers of inert polyelectrolytes the dynamics tended to the PPV dynamics. The distance-dependence of the energy transfer efficiency (1/r2 or 1/r3) points to a resonant process (RET) with a plane-to-plane or plane-to-slab interaction. The non-radiative processes were also studied for varying dilutions of the PPV segments in a matrix of the polyelectrolyte poly(dodecyl methylamonium chloride) (PDAC). This dilution increased the quantum efficiency and led to longer lifetimes (500 ps) owing to a less effective non-radiative energy transfer. When an energy acceptor layer is present, energy transfer is more efficient for the most diluted systems, indicating that such transfer competes with internal processes in the emissive layer. The lifetime increased in films with low degree of conjugation, for which there was a stronger dependence on the emission wavelength. It is concluded that the LbL methodology was suitable to obtain photophysical film properties that could be controlled at the molecular level, and investigated with varied fluorescence spectroscopies.

Esta tese de doutorado apresenta os resultados do estudo sistemático das propriedades ópticas das interfaces que aparecem em dispositivos orgânicos atuais emissores de luz ou OLEDs. Estamos interessados no entendimento do papel de cada uma das interfaces metal/polímero e ITO/polímero sobre a emissão da camada orgânica ativa emissora de luz. Para tanto, se fez necessário o domínio de todas as etapas de preparação e caracterização de filmes finos orgânicos, desde a síntese química dos polímeros até a preparação de amostras adequadas que permitissem a realização dos objetivos propostos. Ênfase foi dada aos processos de excitação e de relaxação energética dos portadores de carga (elétrons e buracos) em filmes ultrafinos automontados próximos às interfaces, correlacionando-os direta ou indiretamente com os efeitos de interface. Através do desenvolvimento e domínio de uma nova metodologia de preparação de filmes orgânicos, verificamos que a intensidade da luminescência de um filme de prova ultrafino de poli(p-fenileno vinileno) (PPV) com espessura em torno de 1,5 nm sofre grandes variações em uma extensa região próxima às interfaces metálicas de Au, Al e de ITO (óxido de índio-estanho). Esta camada de prova foi gradualmente separada da interface variando-se de forma controlada a espessura de um filme polimérico espaçador opticamente inerte. O perfil de intensidade da fotoluminescência nas proximidades das interfaces foi determinado em função da distância entre as superfícies estudadas (vidro, quartzo, metálica ou ITO) e a camada de prova emissora de PPV. Duas regiões relacionadas a processos radiativos distintos foram bem estabelecidas para as interfaces metálicas: uma região de extinção, nas proximidades da interface (< 20 nm), onde a luminescência é fortemente suprimida e uma outra de aumento da luminescência entre 20 e 90 nm. A grande variação da intensidade da luminescência observada neste trabalho é explicada considerando efeitos de interferência em uma semicavidade óptica, além dos processos de transferência de energia tipo Förster entre estados do PPV e estados de plásmons superficiais no metal. Verificamos que a distribuição espacial da radiação emitida é profundamente alterada por processos não radiativos de transferência de energia e pelas condições impostas pelas interfaces em uma semicavidade óptica. Modificações da superfície de ITO foram realizadas pelo tratamento acídico com água-régia suave. Nós observamos que a refletividade do ITO é fortemente dependente do tempo do tratamento e da espessura do espaçador. Como nos filmes metálicos, a emissão de um filme de prova de PPV sofre alterações nas proximidades da interface contendo ITO. Aqui, os parâmetros materiais (índice de difração, reflectância e comprimento de onda da emissão), a estrutura de superfície do ITO e os fatores geométricos mostram um papel importante. Cálculos da intensidade da emissão nas proximidades das interfaces descrevem de modo satisfatório os resultados experimentais. Do perfil de intensidade calculado próximo das interfaces, concluímos que a espessura e a posição da camada ativa emissora de luz devem ser otimizadas de modo a coincidir com a região de aumento ou amplificação da luminescência. / This PhD thesis is an extensive study of the optical properties of the interfaces of organic light-emitting devices (OLED’s). In particular, we investigated the influence of interfaces metal/polymer and ITO/polymer on the emission of an active layer in such devices. Therefore, it was necessary to dominate all the processes of fabrication and characterization of the multilayered structures used in the present investigation. We have used a very thin PPV probe layer (1.5 nm) to map the optical properties very near the metal/organic and the Indium-Tin Oxide (ITO)/organic interfaces. A new Spin-Layer-by-Layer method was employed which allowed a control of deposition of layers at the monolayer level. Precise variation of the metal/PPV or ITO/PPV separation over the entire substrate surface was achieved by the deposition of an organic inert spacer layer. The ITO surface modifications were carried out by soft acidic aquaregia treatment. A strong modulation of the probe layer emission was observed near the metal and ITO interfaces. These results are explained by calculations which include competing short range radiationless energy transfer and intensity modulation due effects produced by the optical cavity formed by metal/polymer films/air. At small distances (<20 nm) from interface, collective excitations in the metal act as energy acceptors, which open up an efficient nonradiative channel. Here, material parameters (diffraction index, reflectance and emission wavelength, for example), surface treatment and structure as well as geometrical factors may play an important role.

Ce travail porte dans un premier temps sur l’optimisation du matériau constituant la couche d’injection des trous dans les diodes électroluminescentes organiques (OLEDs) et les cellules solaires organiques (OPVCs). Les Polyanilines (PANIs) utilisées dans ce travail sont dispersées dans différents solvants organiques ou dans l'eau. L’effet de l’épaisseur, de la morphologie et de la conductivité des films de PANI sur l’efficacité des cellules solaires a été étudié. Les résultats montrent que la conductivité et l’épaisseur des films de PANI affectent énormément l’efficacité des dispositifs OLEDs ou OPVCs. Le dopant et le solvant utilisés dans la synthèse de la dispersion de PANI jouent aussi un rôle important. Dans un second temps, différentes PANIs ainsi que des latex de PEDOT et des nanotubes de carbone ont été utilisés seuls en tant qu'électrode dans le but d'accéder à des dispositifs "tout polymère". L’influence du pH, de la conductivité, du travail de sortie, la nature du dopant et du solvant sur les propriétés de l’injection de charge ont été analysés. / The optimization of hole injection materials in organic light emitting diodes (OLEDs) and organic photovoltaic cells (OPVCs) is reported. Water and organic solvent-based PANIs were used. We have studied the influence of the thickness, the morphology and the conductivity of PANI films in (OPVCs) performances. The results show that the conductivity and the thickness of the PANI film greatly affect (OLED) and (OPVCs) effectiveness. The dopant and the solvent used in the synthesis of PANI dispersion also play an important role. PANI and PEDOT dispersions as well as carbon nanotube were also used as electrodes without ITO. The effect of pH, conductivity, the work function, the nature of the dopant and the solvent in the injection property were analyzed.

Un nouveau domaine de recherche a vu le jour à la fin du XXe siècle, celui de l’électronique organique provenant de l’union des propriétés de l’électronique avec celles des matériaux semiconducteurs organiques. Les principaux avantages technologiques des matériaux organiques proviennent de leur facilité de mise en œuvre (par exemple :l’impression à pression et température ambiantes) et de leur flexibilité mécanique en comparaison au silicium qui est le matériau semiconducteur le plus utilisé au monde. En raison de ces avantages, de nombreuses perspectives d’applications ont été envisagées telles que les écrans flexibles, l’éclairage à partir de grandes surfaces ou encore les cellules photovoltaïques flexibles. Les performances des semiconducteurs organiques sont actuellement moins bonnes que celles du silicium, mais ont fait des progrès spectaculaires depuis ces dernières années. Les performances des semiconducteurs organiques dépendent de l’efficacité avec laquelle les charges se déplacent dans les matériaux π-conjugués ;le paramètre clé qui caractérise le transport de charges est la mobilité, µ. En raison de l’extraordinaire diversité de structures moléculaires accessibles par la synthèse organique, les performances peuvent espérer un jour approcher celles du silicium, car il n’existe à ce jour pas de limite supérieure imposée à la mobilité des charges dans les matériaux organiques. Dans ce contexte, la contribution des chimistes consiste à développer de nouvelles molécules et macromolécules organiques donnant lieu à des matériaux aux performances toujours accrues. Un aspect important à améliorer est la dimensionnalité du transport de charges qui est comprise entre 1 et 3. En effet, plus celle-ci est faible, plus le transport de charges sera sensible aux défauts. <p><p>Au cours du présent travail, nous nous sommes intéressés à l’amélioration du transport de charges en augmentant la dimensionnalité de ce dernier. Cette approche est basée sur les études théoriques du Dr Antoine Van Vooren relevant du couplage électronique par un pont covalent, mais non conjugué entre des systèmes π tels que les oligothiophènes. En effet, selon ces travaux, le couplage électronique entre deux systèmes π est plus important lorsqu’ils sont reliés par un pont éthylène que lorsqu’ils sont isolés. Le pont permet dès lors le transport de charges dans une nouvelle dimension, favorisant ainsi le transport de charges. L’objectif principal de cette thèse consiste à réaliser la synthèse d’oligo- et polythiophènes pontés par des liens éthylènes et d’en étudier les propriétés afin de contribuer à la démonstration expérimentale qu’un pont covalent entre systèmes π aide au transfert de charges. L’étude a porté sur deux systèmes :le système 1 dans lequel le noyau aromatique est un 2,2’:5’,2’’:5’’,2’’’-quaterthiophène et le système 2 dans lequel le noyau aromatique est un 2,5-bis(thiophèn-2-yl)thiéno[3,2-b]thiophène. Les dimères D1 et D2, servant de systèmes modèles, sont étudiés dans le deuxième chapitre tandis que les polymères P1 et P2, permettant de conclure sur l’effet du pont, sont étudiés dans le chapitre trois. <p><p>Une stratégie de synthèse menant au dimère D1, à l’échelle du gramme, a été développée et les quantités recueillies ont permis d’étudier les propriétés de ce dimère. Cependant, nous n’avons pas pu obtenir de monocristaux D1, faillant ainsi à l’étude de la conformation du pont. Une stratégie de synthèse menant au dimère D2 a été développée bien que les quantités recueillies fussent faibles. Le peu de dimère D2 obtenu rendit l’étude des propriétés de ce dernier compliquée et lacunaire. Suite à l’absence d’information sur la conformation du pont des systèmes modèles, d’autres systèmes pontés, présentant une structure chimique proche, de celle des dimères ont été développés. L’efficacité des voies de synthèse imaginées pour obtenir ces composés ainsi que leurs capacités à cristalliser ont permis d’étudier la conformation du pont de ces nouveaux systèmes pontés. Nous avons pu en conclure que de faibles changements de la structure chimique engendrent des changements significatifs sur la structure cristalline ;rendant difficile la prédiction des structures cristallines des molécules cibles. <p><p>Une voie de synthèse menant au polymère P1 a été développée par couplage de Stille en guise de polymérisation, suite à d’infructueux essais via le couplage de Yamamoto. Les quantités recueillies ont permis d’étudier les propriétés de ce polymère. Nous avons ainsi pu constater que le polymère P1 présente un large domaine de stabilité thermique, mais qu’il est complètement amorphe. Néanmoins, le niveau de la HOMO fait de lui un bon candidat pour le transport de trous. Le polymère P2 a été synthétisé selon la même voie de synthèse et nous avons pu observer les mêmes propriétés que celles du polymère P1.<p><p>L’analyse des propriétés spectroscopiques des polymères P1 et P2 ne nous a pas apporté de preuve de la délocalisation des charges le long de la chaine de polymère. En effet, nous avons mis en évidence un effet d’agrégation et un effet de couplage excitonique des polymères qui a pour conséquence de modifier les propriétés caractéristiques des spectres d’absorption et d’émission dans le domaine UV-vis. Nous avons ensuite étudié leurs propriétés de transport de charges dans des transistors. Cependant, les résultats furent décevants en raison de l’absence d’un ordre cristallin au sein des polymères, ceci indépendamment de la méthode de déposition utilisée. Au final, nous n’avons pas de preuve définitive de l’effet du pont sur le transport de charges. Nous espérons que les tentatives de cristallisation des polymères porteront leurs fruits afin qu’une conclusion sur l’effet du pont éthylène entre deux systèmes π puisse être tirée dans un avenir proche. <p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Semiconducting polymers with a conjugated backbone are important for energy storage, conversion, and biomedical field applications. The self-assembly process of these polymers in solutions depends on the polymer concentration and quality of the solvent. The electrical properties of thin films obtained from the solution phase depend on the self-assembled process. Thin films of conjugated polymer gels with percolating networks of self-assembled structures display improved electrical conductivities. In this dissertation, we studied the impact of the secondary gel matrix formed by a low molecular weight gelator, on the self-assembly of conjugated polymers, the preservation of assembled structures in dried gel films and their electrical properties. The study utilized di-Fmoc-l-Lysine gelator, to form a hybrid gel with poly(3-hexylthiophene) in chloroform. The aggregation of P3HT with the progression of gelation was captured using spectroscopic analysis. The aggregates remain in the interstitial spaces of the fibrillar microstructure of gelator. With restricted mobility and due to higher local concentration, the aggregates formed nanofibriliar structures. Microstructural data indicated the nanostructures formed a percolating network in the dried films with good bulk conductivity, despite conductive polymer content of only 20%. Conjugated polymers require a high boiling point and toxic halogenated solvents to develop gels limiting their applications. By utilizing the amphiphilic nature of the gelator, a thermoreversible gel was obtained in 1-propanol, by combining it with an isoindigo-based DA polymer, engineered with galactose side chains to improve its solubility in eco-friendly solvents. Uniform distribution of aggregated polymer increased the shear moduli of the gels. The electrical conductivity of the dried gels confirmed the existence of percolated aggregates. Additional solvent systems were explored, such as 1-propanol mixed with chloroform. Although P3HT is insoluble in 1-propanol, by adjusting chloroform and 1-propanol ratio, a stable gel was obtained. The poor solvent, 1-propanol, assists the self-assembly of P3HT, improving the electrical performance of dried hybrid gels. The findings from this study contribute to a better understanding of the self-assembly of conjugated polymers utilizing molecular gels as templates. It provides a framework for obtaining semiconducting gels for applications in the biomedical field, and for large-scale fabrication of optoelectronic devices. Semiconducting polymers with a conjugated backbone are important for energy storage, conversion, and biomedical field applications. The self-assembly process of these polymers in solutions depends on the polymer concentration and quality of the solvent. The electrical properties of thin films obtained from the solution phase depend on the self-assembled process. Thin films of conjugated polymer gels with percolating networks of self-assembled structures display improved electrical conductivities. In this dissertation, we studied the impact of the secondary gel matrix formed by a low molecular weight gelator, on the self-assembly of conjugated polymers, the preservation of assembled structures in dried gel films and their electrical properties. The study utilized di-Fmoc-l-Lysine gelator, to form a hybrid gel with poly(3-hexylthiophene) in chloroform. The aggregation of P3HT with the progression of gelation was captured using spectroscopic analysis. The aggregates remain in the interstitial spaces of the fibrillar microstructure of gelator. With restricted mobility and due to higher local concentration, the aggregates formed nanofibriliar structures. Microstructural data indicated the nanostructures formed a percolating network in the dried films with good bulk conductivity, despite conductive polymer content of only 20%. Conjugated polymers require a high boiling point and toxic halogenated solvents to develop gels limiting their applications. By utilizing the amphiphilic nature of the gelator, a thermoreversible gel was obtained in 1-propanol, by combining it with an isoindigo-based DA polymer, engineered with galactose side chains to improve its solubility in eco-friendly solvents. Uniform distribution of aggregated polymer increased the shear moduli of the gels. The electrical conductivity of the dried gels confirmed the existence of percolated aggregates. Additional solvent systems were explored, such as 1-propanol mixed with chloroform. Although P3HT is insoluble in 1-propanol, by adjusting chloroform and 1-propanol ratio, a stable gel was obtained. The poor solvent, 1-propanol, assists the self-assembly of P3HT, improving the electrical performance of dried hybrid gels. The findings from this study contribute to a better understanding of the self-assembly of conjugated polymers utilizing molecular gels as templates. It provides a framework for obtaining semiconducting gels for applications in the biomedical field, and for large-scale fabrication of optoelectronic devices.

The study of conjugated polymers, in particular PPV derivatives, continues to fascinate researchers both from the standpoint of developing new routes to control their structure and photophysical properties; this is also driven by the immense potential since this class of polymers has demonstrated in the context of various devices, such as LEDs, photovoltaics, FETs, etc. Also, there has been great interest in utilizing conjugated polymers in developing sensory devices. This thesis has examined a few interesting aspects that could be used to control the structure and consequently the photophysical properties of PPV derivatives. The first chapter of this thesis provides a brief introduction to conjugated polymers, with an emphasis on PPV based polymers, different synthetic methodologies for their preparation, previous attempts to obtain PPV with controlled conjugation length, and also a brief discussion of conjugated polymer nanoparticles (CPNs) and their preparation by various methods. The second chapter deals with the preparation of conjugated polymer (MEHPPV) nanoparticles by reprecipitation method and utilization of these nanoparticles in detection of nitro explosives in aqueous medium. Nanoparticles of MEHPPV with different sizes were prepared by a simple precipitation method from a THF solution into water. Although these nanoparticles were prepared from very hydrophobic MEHPPV, these nanoparticles were reasonably stable in aqueous medium, especially when their sizes were relatively small; their UV-visible and fluorescence spectra could be readily recorded using simple solution methods. The sizes could be controlled by varying the concentration of the polymer solution used. The CPNs are spherical particles as confirmed by atomic force microscopy (AFM). The emission maximum of the nanoparticles is red shifted compared to a solution of the polymer. The fluorescence spectrum of this aqueous nanoparticle dispersion exhibited very high sensitivity to electron-deficient aromatic compounds, in particular the explosive TNT; the CPNs were able to sense nanomolar concentrations of the explosives. Stern-Volmer constant (KSV) is higher for 2,4,6-trinitro toluene (TNT) than any other analytes studied. Among the different sized nanoparticles studied the bigger one showed highest quenching efficiency. Electron-deficient aromatic molecules were shown to quench the fluorescence of the nanoparticles, possibly by excited state electron transfer mechanism; this hypothesis was supported by quenching experiments carried out using a variety of nitro-aromatic molecules with varying reduction potentials, in addition to a few electron-rich aromatic molecules. A fairly good correlation between the quenching efficiency of the analyte and its reduction potential was noticed; however, in a few instances this correlation failed. This suggested that a second factor, namely the solubility of the analyte in water (its hydrophobicity) also is a key factor as this governs the tendency of the analyte to adsorb on the nanoparticle surface, which clearly is the first step in the quenching process. In the third chapter synthesis and characterization of MEHPPV with reduced conjugation length by utilizing the concept of conjugation breaking using non-coplanar entities are presented. MEHPPV with reduced conjugation length was prepared by incorporating non-coplanar entities, such as biphenyl and binaphthyl units, along the polymer backbone. Both Gilch and Witting-Horner methods were successfully utilized to prepare copolymers; the former approach permitted the variation of the level of the twisted comonomer incorporation, whereas the latter approach only provided an alternating copolymer. Although biphenyl based monomers could not be homopolymerized by Gilch method, it was possible to prepare copolymers using xylylene type comonomers. The polymers prepared by the Gilch method are random copolymers; the solubility decreases with increase in the amount of biphenyl incorporation, which was ascribed to the presence of a substantial fraction of longer conjugated segments in such random copolymers. The non-coplanar entities cause truncation of conjugation length in MEHPPV, as evident from their absorption spectra. The copolymers prepared via the Gilch method exhibited a blue shift of about 57 and 20 nm in the absorption and emission, respectively; while the alternating copolymers prepared by Wittig-Horner-Emmons method exhibited a larger blue-shift of about 84 and 54 nm clearly implying a significantly larger reduction in the conjugation length. The copolymers prepared by Wittig-Horner-Emmons method are alternating in nature and therefore leads to a greater reduction in conjugation length; this was evident from the substantially higher blue-shift in the absorption and fluorescence spectra. An interesting feature in the alternating copolymers is the distinct difference in the relative changes in the absorption and emission spectra of the biphenyl and binaphthyl containing copolymers, which appear to suggest in the latter case there is a greater extent of planarization of the excited state. Both these systems provided some useful insights into the various factors that govern the photophysical properties of this class of truncated conjugated polymers. Further examination of this aspect could reveal some other unique features of these copolymers. In the fourth chapter, an approach to prepare copolymer precursors to unsubstituted PPV that holds the potential to control conjugation length is described. The precursor copolymers were prepared by changing the monomer feed ratio of the two monomers, viz. dithiocarbamate (DTC) and xanthate, using the Gilch copolymerization to generate the precursors having varying extents of DTC and xanthate groups. The percentage composition of the precursor copolymers was calculated using 1H NMR and compared with the values calculated from thermogram; the copolymer composition varies linearly with monomers feed suggesting that any desired composition can be readily accessed. Thermogravimetric analysis (TGA) of the precursors, as a preliminary study to examine the possibility of selective elimination of one of these groups to generate conjugated polymers with varying conjugation lengths, demonstrates that a certain level of selectivity in thermal elimination can be achieved because of the distinctly different thermal labilities of the xanthate and DTC groups. These studies clearly suggest that fine-tuning of the thermally eliminatable groups, specifically using xanthate and DTC, could serve as a useful approach to vary the conjugation length of unsubstituted PPVs, which could have important implication in device fabrication. Clearly further work is needed to characterize the selectively eliminated polymers using other spectroscopic methods, such as UV-visible and fluorescence, before device work could be taken up.