Orientador: Hermes Adolfo de Aquino / Banca: José Antônio Malmonge / Banca: Rinaldo Gregório Filho / Resumo: Os polímeros são muito conhecidos por serem materiais de fácil processamento, leveza, isolantes elétricos e até mesmo térmicos. Essas propriedades viabilizaram várias aplicações tecnológicas desde utensílios domésticos à indústria. No fim do século passado as pesquisas voltaram-se em busca de energias renováveis e novos materiais que associassem as vantagens dos polímeros com as propriedades elétricas dos metais. Com essas pesquisas surgiu uma nova classe de polímeros chamada de Polímeros Condutores Intrínsecos (PCIs) que dispõem de boas propriedades de condução elétrica inerente ao material. Esses PCIs podem ser sintetizados em forma de fibras ou filmes, sozinhos ou com vários outros polímeros para formar blendas com diferentes propriedades. O polipirrol (PPy) é um PCI que proporciona altas condutividades elétricas e boa estabilidade oxidativa, algo difícil de se conseguir com essa classe de polímeros. Esse trabalho teve como objetivo sintetizar amostras de PPy por dois métodos de síntese química: convencional (em solução aquosa) e microemulsão com dodecil sulfato de sódio (SDS - surfactante e dopante). No primeiro método foi variada a razão molar de monômero/oxidante e no segundo variou-se as razões molares de monômero/oxidante/dopante. Para o estudo dessas amostras foram realizadas análises estruturais, morfológicas, térmicas, ópticas e elétricas. De maneira geral, as amostras que apresentaram melhores características morfológicas, ópticas e de condutividade elétrica, foram as obtidas no processo químico em microemulsão, de tal maneira que, quanto maior a quantidade de SDS e menor a temperatura, menor foi o tamanho das partículas de PPy, maior a conjugação das cadeias e maior a dopagem com SDS. / Abstract: The polymers are known to be materials easy processed, slight, electrical insulators and even heat. These properties made possible many technological applications, from household items to the industry. At the end of last century the polls turned in search of renewable energy and new materials that combines the benefits of polymers with the electrical properties of metals. With these studies emerged a new class of polymers called Intrinsic Conducting Polymers (PICs) that have good electrical conduction properties inherent to the material. These PICs can be synthesized in the form of fibers or films, either alone or with various other polymers to form blends with different properties. The polypyrrole (PPy) is a PIC that provides high electrical conductivity and good oxidative stability, something difficult to achieve with this class of polymers. This study aimed to synthesize PPy samples by two methods of chemical synthesis: conventional (aqueous solution) and microemulsion SDS (dodecilsulfate of sodium - surfactant and dopant). In the first method was varied the molar ratio of monomer/oxidant and the second was varied molar ratios of monomer/oxidant/dopant. For the study of these samples were performed structural analyses, morphological, thermal, optical and electrical. In general, samples that showed better morphological characteristics, optical and electrical conductivity were obtained in the chemical process of microemulsion, such a way that the larger the amount of SDS and the lower the temperature, the smaller the particle size of PPy, the greater the conjugation of chains and the higher the doping with SDS. / Mestre

xix, 190 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / The electrical properties of conducting polymer-based devices are investigated in order to better understand charge transport through conducting polymers and charge transfer at conducting polymer interfaces with metals and inorganic semiconductors. Experiments on two specific systems are reported: (1) an anionically functionalized conducting polymer between metal electrodes and (2) nanostructured doped conducting polymer-semiconductor interfaces. Temperature dependent impedance measurements are reported on an anionically functionalized polyacetylene sandwiched between two gold electrodes (Au|P A |Au). These measurements provide key quantities regarding the ionic carriers in this system, such as the characteristic frequency for electrode polarization, ionic DC conductivity, activation energy, effective ion concentration, and hopping frequency. Impedance measurements are also reported on samples where excess electronic carriers had been introduced with a DC bias and at temperatures sufficiently low so as to freeze out the ionic carriers. In addition to providing information about the dielectric relaxation of electronic carriers such as the characteristic frequency for electrode polarization and activation energy, these low-temperature impedance measurements also support the ionic dielectric relaxation assignments. Temperature-dependent potential step experiments, in combination with the dielectric measurements probing ionic carriers, demonstrate the direct connection between the redistribution of ions and an enhancement in carrier injection in the Au|P A |Au system. Further potential step experiments followed by relaxation through either a short- or open-circuit configuration demonstrate that the electric field distribution is closely related to the amount of injected electronic carriers. The electric field distribution changes from being mostly determined by ionic carriers to being jointly determined by both ionic and injected electronic carriers when the density of injected electronic carriers is higher than that of the effective ionic carriers. To investigate charge depletion and transport at length scales less than the depletion width of a semiconductor interface, nanoscale metal-InP contacts with low barrier height were embedded within conducting polymer-InP contacts with high barrier height. Electrical measurements on these hybrid interfaces indicate that charge transport across the nanoscale metal contacts is affected by the neighboring high barrier region when the size of the metal contacts is less than the depletion width of the conducting polymer-InP background. / Adviser: Mark Lonergan

As propriedades protetoras à corrosão dos polímeros condutores, especialmente da poli(anilina) (PANI), têm sido amplamente explorada. Entretanto, o mecanismo pelo qual esta proteção é efetuada ainda não foi completamente elucidado. Evidências mostram que a habilidade protetora à corrosão da PANI está ligada à formação de um par galvânico entre o polímero e o metal. Neste trabalho, foi feito um estudo sobre a formação de um par galvânico entre a PANI e diferentes substratos metálicos (zinco, ferro, níquel e cobre) em meios ácidos e neutros. Medidas de potencial de circuito aberto mostram que há a possibilidade de formação de um acoplamento galvânico e medidas de corrente galvânica mostram que há uma corrente galvânica fluindo entre todos os pares PANI-metal. Durante este trabalho, foi sintetizada uma suspensão à base de epóxi e PANI, a qual foi eletroforeticamente depositada sobre um eletrodo de ferro. Medidas de potencial de circuito aberto e impedância em uma solução aquosa de ácido sulfúrico mostraram que o revestimento à base de PANI protegeu o substrato metálico em questão através da formação de um par galvânico entre o metal e o polímero. / The corrosion protection properties of conducting polymers, especially poly(aniline) (PANI) ones, have been widely exploited. However, the mechanism by which this protection is made has not been completely cleared yet. Evidences show the ability of PANI\'s corrosion protection is connected to the building of a galvanic couple between the polymer and the metal. In this work, a study about the building of a galvanic couple between PANI and distinct metallic substrates (zinc, iron, nickel and copper) in acid and neutral environment was done. Measurements of open circuit potential showed the possibility of the building of a galvanic coupling and measurements of galvanic current showed the flux of a galvanic current between all the couples PANI-metal. In the course of this work, a suspension based on epoxy and PANI was synthesized and electrophoretically depositated on a iron electrode. Measurements of open circuit potential and impedance in a aqueous sulfuric acid solution showed that the revestiment based on PANI protected the metallic substrate by the building of a galvanic couple between the metal and the polymer.

Neste trabalho foi realizado o estudo espectroscópico (UV-VIS-NIR, FTIR, Raman e RMN) dos produtos de polimerização da anilina com persulfato de amônio em condições de síntese diferentes da utilizada na síntese padrão da polianilina (pH inicial = 1). A reação foi realizada em meio de HCl (pH inicial = 3) e em meio tamponado (pH = 3). No primeiro caso foi observada a formação majoritária de oligômeros de anilina tipo cabeça-cauda, enquanto que em meio tamponado são formadas macromoléculas com segmentos do tipo 1,4 de Michael de anilina e benzoquinona monoimina com diferentes graus de hidrólise/oxidação, além de unidades tipo fenazina. Esta caracterização está de acordo com as propostas distintas de dois grupos (Surwade et al. e Stejskal et al.), que a princípio pareciam contraditórias. Ainda com relação aos produtos obtidos em meio tamponado (pH = 3), é observada a formação de microesferas com diâmetro entre 3-7 µm. A microscopia Raman juntamente com a espectroscopia Raman ressonante revelou uma correlação entre estrutura tipo fenazina e a formação das microesferas. / In this work it was performed the spectroscopic study (UV-VIS-NIR, FTIR, Raman e NMR) of the polymerization products of aniline and ammonium persulfate using different reaction conditions in relation to the standard polyaniline synthesis (initial pH = 1). The reaction was performed in HCl medium (initial pH =3) and in buffered medium (pH = 3) In the first case it was observed the major formation of aniline oligomers with head-to-tail coupling, while in buffered medium macromolecules with 1,4 Michael-type segments between aniline and benzoquinone monoimine with different hydrolysis/oxidation ratio of iminic groups are formed, in addition to phenazine-like units. This characterization is in accordance to the distinct proposals of two groups (Surwade et al. e Stejskal et al.), which at first seemed contradictory. Again, relative to the products obtained in buffered solution (pH = 3), it is observed the formation of microspheres whose diameter range is 3-7 µm. The use of Raman microscopy and resonance Raman spectroscopy revealed a correlation between phenazine-like structure and the microspheres formation.

A obtenção de blendas condutoras a base de água, ainda é pouco explorada e apresenta uma interessante alternativa ao uso de compostos poluentes como os cromatos na proteção à corrosão metálica. Os polímeros condutores apresentam propriedades anti-corrosivas e podem ser processados em meio aquoso, eliminando o uso de solventes orgânicos altamente tóxicos e agressivos para o meio ambiente. O presente trabalho consiste no estudo da proteção da corrosão metálica por revestimento de filmes de blendas contendo Poli(anilina) (PANI). As blendas foram obtidas à partir da mistura de uma suspensão aquosa de PANI com uma dispersão aquosa de Poli(metil metacrilato). O uso de técnicas como potencial zeta, espalhamento de luz dinâmico, análise térmica e microscopia eletrônica de varredura permitiram a caracterização da mistura homogênea obtida. Medidas através do método da sonda de quatro pontas mostraram que as blendas apresentam condutividade mesmo com baixas quantidades de PANI e a técnica de espectroscopia Raman mostrou a presença da forma condutora deste polímero nos filmes das blendas. Técnicas como microscopia óptica, potencial a circuito aberto, voltametria linear e espectroscopia de impedância eletroquímica permitiram avaliar a proteção à corrosão de eletrodos metálicos de ferro, cobre e níquel recobertos com filmes das blendas de PANI em diferentes meios corrosivos. As blendas mostraram eficiência contra a corrosão e apresentam-se como um novo material não poluente para a proteção à corrosão metálica. / The development of water-based conducting blends has not yet been very much explored and it presents itself as an interesting alternative to the use of polluting compounds such as chromates in the protection of metals from corrosion. The conducting polymers present anti-corrosion properties and can be processed in aqueous medium, eliminating the use of organic solvents, which are highly toxic and threatening to the environment. This thesis is based on the study of protection from metallic corrosion using poly(aniline) (PANI) coating blends. The blends have been obtained by mixing a PANI aqueous suspension with a poly(methyl metacrylate) aqueous dispersion. Techniques such as zeta potential, dynamic light scattering, thermal analysis and scanning electronic microscopy allowed the characterization of the homogeneous mixture obtained. Measurements carried out by the four-point probe method showed that the blends present conductivity even despite low PANI quantities. In addition, the Raman spectroscopy technique showed the presence of the conducting form of this polymer on the blend films. Techniques such as optical microscopy, open-circuit potential, linear voltammetry and impedance spectroscopy allowed the evaluation of the corrosion protection of the iron, copper, and nickel metallic electrodes coated with PANI blend films in different corrosives mediums. The blends showed efficiency against corrosion and they are therefore a new environmentally friendly material for metallic corrosion protection.

Neste trabalho, desenvolvemos blendas de polímeros biodegradáveis e polímeros condutores com objetivo de avaliar o potencial destes materiais para uso em aplicações biomédicas. O polímero condutor polipirrol (PPY) e os polímeros biodegradáveis poli(-caprolactona) (PCL) e poli(3-hidróxido de butirato) (P3HB) foram escolhidos devido à comprovada biocompatibilidade apresentada por cada um destes três polímeros. O PPY foi sintetizado via polimerização em emulsão, utilizando-se o dodecil sulfato de sódio (SDS) como surfactante e o FeCl3 como oxidante e dopante. A morfologia do polímero obtido foi estudada por microscopia eletrônica de varredura e por microscopia eletrônica de transmissão. O PPY se apresentou como agregado de partículas aproximadamente esféricas, com dimensões da ordem de 80 a 200nm. Verificamos que ocorre uma redução significativa do tamanho das partículas formadas, proporcionalmente ao aumento da concentração de SDS. Os ensaios de microanálise por energia dispersiva (EDS) e de espectroscopia de absorção no infravermelho (FTIR) demonstraram a incorporação de SDS ao PPY, o SDS atuando como contra-íon deste polímero. Isto está de acordo com os resultados de condutividade elétrica obtidos para o polímero sintetizado sem o SDS (1.9S/cm) e com 100mM de SDS (23.3S/cm). A seguir, foram preparadas as blendas, dispersando-se as partículas de PPY em matrizes poliméricas de PCL ou de P3HB, sendo a morfologia destas blendas estudada por microscopia eletrônica de varredura. Em blendas de PCL, as partículas de PPY localizam-se principalmente entre os esferulitos da matriz, devido ao processo de cristalização da PCL. Diferentemente, nas blendas de P3HB estas partículas agruparam-se em várias regiões, e não foram localizadas na superfície dos filmes produzidos. A condutividade elétrica obtida para as blendas de PCL e de P3HB, ambas contendo 15% de PPY, foi respectivamente, 20.8mS/cm e 5.5mS/cm. Esta diferença de valores encontrada, parece estar relacionada à formação de uma rede de partículas de PPY na matriz de PCL. Medidas do ângulo de contato da superfície das blendas de PCL e de P3HB mostraram que elas se tornam progressivamente mais hidrofílicas com o aumento da proporção de PPY. Os resultados obtidos neste trabalho indicam que estas blendas podem ser biocompatíveis, justificando o prosseguimento de novos estudos envolvendo métodos de ensaio in vivo, para uma avaliação mais adequada. / Polymers blends making use of two biodegradable polymers, and a conductive one, were synthesized and characterized in the laboratory, aiming at the development of a new material that would combine adequate properties of biodegradability and electrical conductivity. As such, these blends would be suitable for making special devices to be used in biomedical applications. The well known conducting polymer polypyrrole (PPY), was synthesized, then blended with either poly(-caprolactone) (PCL) and poly(3-hydroxybutyrate) (P3HB), both biodegradable, therefore biocompatible, polymers. PPY particles were obtained along the polymerization route, in which SDS (sodium dodecyl sulfate) acted as a surfactant and FeCl3 as the oxidizing and dopant agent. The PPY samples were characterized by scanning and transmission electron microscopy, as spherical particles having 80-200nm in diameter; it was found that final particle size was inversely related to the concentration of SDS used in the synthesis pathway. The particles were further characterized by energy dispersive microanalysis (EDS) and infrared spectroscopy (FTIR), to demonstrate incorporation of the SDS into the PPY. SDS actually behaves as a counterion of the polymer, according to electrical conductivity results of polymer synthesized without SDS (1.9S/cm) or with 100mM SDS (23.3S/cm). This PPY polymer was then blended with either PCL or PHB matrices. The microstructure of the two resulting blends, as investigated by scanning electron microscopy demonstrates PPY particles mostly located within the interstices of spherulites in the PCL blends, whereas in P3HB blends, they formed irregular patches along the matrix. Electrical conductivity for blends containing 15% PPY were: 20.8mS/cm for PCL blends and 5.5mS/cm for P3HB blends. It can be concluded therefore, that these different values obtained for electrical conductivity were related to the particle distribution within the two matrices. Also, hydrophilic properties of the two blends, according to contact angle measurements, seem to correspond to the content of PPY.

Orientadores: Vitor Baranauskas, Ana Flavia Nogueira / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-12T11:11:13Z (GMT). No. of bitstreams: 1 Valente_GustavoMonteirodaSilva_M.pdf: 2272217 bytes, checksum: c82b3f59d489a35f76f4e4d2a2263828 (MD5) Previous issue date: 2008 / Resumo: Novas fontes de energia limpa de baixo custo devem ser obtidas nas próximas décadas para sustentar o consumo de energia mundial e manter o meio-ambiente livre de gases de efeito estufa. Enquanto células solares inorgânicas são uma fonte limpa de energia, essa tecnologia é restrita devido a seu alto custo de produção. Células solares orgânicas têm sido desenvolvidas para solucionar este problema, pelo menos para dispositivos pequenos, isto é, para aplicações de baixa corrente. Recentemente novos materiais tal como polímeros condutores e nanotubos de carbono vêm sendo utilizados em células solares orgânica de heterojunção. Uma célula solar eficiente deve absorver toda (ou boa parte) da luz solar e gerar e transportar portadores de carga livre para seus eletrodos para assim produzir corrente elétrica e um potencial interno. Neste trabalho usamos o polímero poli[2-methoxy-5-[(3,7-dimethyloctyloxy) phenylene vinylene] (MDMO-PPV) como material absorvedor e transportador de buracos e nanotubos de carbono para dissociação do exciton e tranporte de elétrons. A morfologia e foto-fisica das células, bem como a caracterização do dispositivo é estudada. / Abstract: New sources of low cost and clean energy must be achieved in the coming decades to sustain world consumption while also keeping the environment free of green house gases. While inorganic solar cells are a source of clean energy, they are plagued by high production costs. Organic solar cells have been developed as a solution to this problem as a means to harvest light while keeping production costs low. Recently, new materials such as conductive polymers, carbon nanotubes (CNT) and fullerenes have been utilized in bulk heterojunction organic solar cells1,2. Increasing the effi-ciency of these organic solar cells is crucial for them to become economically viable. An efficient solar cell must harvest all the possible light from the Sun and produce and transport free charges carriers to their electrodes to produce electrical current with a built-in potential. In this work we use a poly[2-methoxy-5-[(3,7-dimethyloctyloxy) phenylene vinylene] (MDMO-PPV) as the absorption and hole transport material and CNT for exciton dissociation and electron transport. The morphology and photophysics of the films, as well as the characteristic J-V curves for the devices were obtained. / Mestrado / Eletrônica, Microeletrônica e Optoeletrônica / Mestre em Engenharia Elétrica

Orientador: João Sinézio de Carvalho Campos / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T06:37:30Z (GMT). No. of bitstreams: 1 Gomes_AlexLinardi_D.pdf: 4308233 bytes, checksum: 4eb5a86fd91e54e1c262eebbc0abe8d1 (MD5) Previous issue date: 2012 / Resumo: As propriedades elétricas apresentadas por alguns polímeros condutores e suas misturas têm contribuído para o avanço tecnológico de diversas áreas como a da medicina e a da microeletrônica. As técnicas de síntese fotoquímica e de obtenção de membranas por deposição em centrífuga tipo spinner usando polímeros de sacrifício têm possibilitado a preparação de misturas poliméricas com boas propriedades condutoras. Este trabalho teve como objetivo preparar misturas poliméricas condutoras de Poli(3-tiofeno acetato de metila)/Poli(butileno succinato) PT3MA/PBS e compósitos de Poli(3-tiofeno acetato de metila)/Poli(fluoreto de vinilideno)/Silicato de zinco dopado com manganês Zn2SiO4:Mn "PT3MA/PVDF/Zn2SiO4:Mn" para obtenção, respectivamente, de membranas ultrafinas biodegradáveis condutoras e filmes aplicáveis a dispositivos eletroluminescentes. Um estudo paralelo sobre as propriedades elétricas das misturas poliméricas obtidas por síntese fotoquímica constituídas por Politiofeno/Poli(fluoreto de Vinilideno) foi realizado para avaliar condutividade dos filmes. Os novos materiais foram caracterizados usando as técnicas de Espectroscopia no Infravermelho por Transformada de Fourier (FTIR), Espectroscopia Raman, Ultravioleta Visível, Ressonância Magnética Nuclear, Perfilometria, Elipsometria, Microscopia Óptica, Microscopia Eletrônica Exploratória, Microscopia de Força Atômica, Difração de Raios-X, Calorimetria Diferencial Exploratória (DSC) e Análises Termogravimétricas (TGA). Os resultados das medidas de condutividade elétrica das membranas ultrafinas biodegradáveis de PT3MA/PBS 80:20 mostram uma condutividade de ~10-4 a ~10-5 S/cm conforme a espessura, valores dentro da faixa de normalidade para politiofenos semicondutores. Os valores de condutividade elétrica apresentadas pelas membranas constituídas pela mistura polimérica Poliânion Poli(tiofeno ácido acético)/Poli(fluoreto de vinilideno) PT3AA-K/PVDF obtida por síntese fotoquímica, apontam um aumento de condutividade de até 10-4 na matriz PVDF. O comportamento óptico-elétrico dos dispositivos monocamadas constituídos por filmes do compósito PT3MA/PVDF/ZnSiO4:Mn foi avaliado por medidas de absorção e emissão em UV-visível e por Curvas Características Tensão x Corrente. As medidas de intensidade de energia luminosa comprovam a capacidade de luminescência do novo material e seu potencial para uso como camada ativa de dispositivos óptico-eletroluminescentes / Abstract: The electrical properties of some conducting polymers and their blends have contributed to the technological advancement in various areas such as medicine and microelectronics. Recently, photochemical synthesis and spinner techniques have been using to prepare polymeric blends with good conducting properties. In this study we report the preparation of conducting polymer blends composed of poly (3-thiophene methyl acetate)/Poly (butylene succinate) PT3MA/PBS and composites of poly (3-thiophene methyl acetate)/Poly (vinylidene fluoride)/manganese doped with zinc silicate "PT3MA/PVDF/Zn2SiO4:Mn" for obtaining, respectively, conducting biodegradable nanomembranes and films applicable to electroluminescent devices. A parallel study on the electrical properties of polymeric blends obtained by photochemical synthesis composes of polythiophene / poly (vinylidene fluoride) was conducted to evaluate the conductivity of the films. The new materials were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy, Visible Ultraviolet, Nuclear Resonance Magnetic (1H NMR), Profilometry, Ellipsometry, Optical Microscopy, Scanning Electron Microscopy (MEE), Atomic Force Microscopy (AFM), X-Ray Diffraction, Differential Scanning Calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. The electrical conductivity measurements of the 80:20 PT3MA/PBS biodegradable nanomembranes show conductivity from 10-4 to 10-5 S/cm depending on the thickness, values within the range typical found for semiconducting polythiophenes. The conductivity values shown by the membranes composed of PT3AA-K/PVDF poly (thiophene acetic acid) polyanion/poly (vinylidene fluoride) blends obtained by photochemical synthesis, indicate an increase in conductivity of up to 10-4 at PVDF matrix. The optical electric behavior of the monolayer devices formed by PT3MA/PVDF/ZnSiO4:Mn composite films was monitored by absorption and emission measurements in UV-visible and by (I-V) Characteristic Curves. The luminous energy intensity measurements show the luminescence ability of the new material and its potential for use as active layer in electroluminescent optical devices / Doutorado / Ciencia e Tecnologia de Materiais / Doutor em Engenharia Química

Supercapacitors have emerged in recent years as a promising energy storage technology. The main mechanism of energy storage is based on electrostatic separation of charges in a region at the electrode-electrolyte interface called double layer. Various electrode materials including carbon and conducting polymers have been used in supercapacitors. Also, supercapacitors offer high life cycle and high power density among electrochemical energy storage devices. Despite their interesting features, supercapacitors present some disadvantages that limit their competitivity with other storage devices in some applications. One of those drawbacks is high self-discharge or leakage. The leakage occurs when electrons cross the double layer to be involved in electrochemical reactions in the supercapacitor’s electrolyte. In this work, the first research project demonstrates that the addition of a very thin blocking layer to a supercapacitor electrode, can improve the energy storage capability of the device by reducing the leakage. However, the downside of adding a blocking layer is the reduction of the capacitance. A second project developed a mathematical model to study how the thickness of the blocking layer affects the capacitance and the energy density. The model combines electrochemical and quantum mechanical effects on the electrons transfer responsible of the leakage. Based on the model, a computational code is developed to simulate and study the self-discharge and the energy loss in hypothetical devices with different thicknesses of the blocking layer. The third research project identified the optimal amount of a surfactant (Triton-X 100) that had a significant effect on the double layer capacitance and conductivity of a spin-coated PEDOT:PSS (poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)) electrode. The effect of the concentration of the surfactant was investigated by measuring the electrochemical properties and the conductivity of different electrodes. The electrodes were fabricated with different concentrations of the surfactant. Scanning electron microscopy characterizations confirmed the structural change in the PEDOT:PSS that contributed to the capacitance and conductivity enhancement. A final research project proposed an approach on how to utilize the modified PEDOT:PSS added to different photoactive dyes to design a photoactive supercapacitor. The new approach showed the possibility of using a supercapacitor device as an energy harvesting as well as a storage device.

De nombreux dispositifs pour l’électronique organique et la bioélectronique reposent sur le transport mixte (électronique et ionique).Le transport électronique dans les matériaux organique est relativement bien compris, mais une compréhension fondamentale du transport des ions est manquante. J'ai développé un modèle analytique qui décrit le transport d'ions dans une jonction planaire entre un électrolyte et un film de polymère conducteur.Le modèle permet des prédictions de l'évolution temporelle du courant et du drift length des ions.Ces prédictions sont validées par des simulations numériques et en utilisant des paramètres réalistes, je montre que le modèle analytique peut être utilisé pour obtenir la mobilité des ions dans le film. De plus, j'ai développé une méthode expérimentale qui permet l'application du modèle analytique et conduit à une estimation de la mobilité des ions dans les polymères conducteurs. Le PEDOT:PSS offre un transport efficace pour les ions, qui peut être mis en relation avec le gonflement important du film dans l'eau. Je montre que la réticulation du film diminue son gonflement ainsi que la mobilité des ions. Comprendre la forte corrélation entre l'hydratation et la conductivité ionique nous permet de développer des matériaux à mobilité ionique définie et importante. A titre d'exemple, le réglage de la mobilité ionique du PEDOT:TOS est présenté en ajustant le rapport relatif de la phase hygroscopique. Pour finir, j'ai effectué des mesures de spectroscopie d'impédance électrochimique au cours d'une expérience de moving front, afin de proposer une interprétation physique des spectres d'impédance mesurés à une jonction polymère conducteur/électrolyte / Many organic electronic and bioelectronics devices rely on mixed (electronic and ionic) transport within a single organic layer. Although electronic transport in these materials is relatively well understood, a fundamental understanding of ion transport is missing. I developed a simple analytical model that describes ion transport in a planar junction between an electrolyte and a conducting polymer film. The model leads to predictions of the temporal evolution of drift length of ions and current. These predictions are validated by numerical simulations and by using realistic parameters, I show that the analytical model can be used to obtain the ion mobility in the film. Furthermore, I developed an experimental method which allows the application of the analytical model and leads to a straightforward estimation of the ion drift mobilities in conducting polymers. PEDOT:PSS was found to support efficient transport of common ions, consistent with extensive swelling of the film in water. Crosslinking the film decreased its swelling and the ion mobility. Understanding the high correlation of hydration and ionic conductivity enables us to engineer materials with high and defined ion mobilities. As an example tuning of ion mobility by adjusting the relative ratio of the hydroscopic phase to PEDOT:TOS is presented. Finally I performed electrochemical impedance spectroscopy during a moving front experiment, in order to give a physical interpretation of the impedance spectra at a conducting polymer/electrolyte junction.