Research Doctorate - Doctor of Philosophy (PhD) / The photochemistry of poly{p-phenylene[1-(tetrahydrothiophen-1-io)ethylene chloride]} (PPTEC), a water soluble precursor of the semiconducting polymer, poly{p-phenylenevinylene} (PPV), has been studied both under atmospheric conditions and in environments devoid of oxygen. UV-visible spectroscopy and photoluminescence data has been used to provide a picture of the mechanistic pathways involved in UV irradiation of the PPTEC material. A new quantitative model for the effect of UV irradiation upon film morphology is presented. The technique of near-field scanning optical lithography (NSOL) has been used to produce arbitrary structures of the semi-conducting polymer poly{p-phenylenevinylene} at sizes comparable with optical wavelengths. Structures on this scale are of interest for integrated optical devices and organic solar cells. The structures are characterised using AFM and SEM and examined in the context of the electric field distribution at the NSOM tip. The Bethe-Bouwkamp model for electric field distribution at an aperture has been used, in combination with the developed model for precursor solubility dependence on UV energy dose, to predict the characteristics of lithographic features produced by NSOL. Fine structure in the lithographic features that are characteristic of the technique are investigated and their origins explained. Suggestions for the improvement of the technique are made. Presented here for the first time is a device manufactured by the technique of NSOL functioning as an optical device. The technique of NSOL is used to manufacture an optical transmission phase grating (or phase mask) of PPV, this was done as a proof of concept for device manufacture by this method and to demonstrate the potential usefulness of the unique characteristics of the technique. The phase mask was characterised using AFM and SEM and examined in the context of how well a diffraction pattern matches with theoretical calculations.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14942号 / 工博第3169号 / 新制||工||1475(附属図書館) / 27380 / UT51-2009-M856 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 小澤 文幸, 教授 大江 浩一, 教授 中村 正治 / 学位規則第4条第1項該当

O presente trabalho envolveu a eletrossíntese de três polímeros da família dos poli(p-fenilenovinileno)s, PPVs, apresentando como substituintes grupos alcóxi de cadeia longa. Esses polímeros foram caracterizados espectroscopicamente (RMN de 1H, IV e UV/VIS), termicamente (TG), por cromatografia por exclusão de tamanho (SEC), eletronicamente por voltametria cíclica e eletricamente por meio de curvas I x V em dispositivos do tipo sanduíche (metal/polímero/metal). Os polímeros foram utilizados na construção de sensores de gases para avaliação da capacidade sensitiva a vapores orgânicos, mostrando-se promissores para utilização em narizes eletrônicos. Construíram-se, também, dispositivos emissores de luz orgânicos (OLEDs) com utilização desses polímeros como camada ativa, no intuito de se conhecer sua aplicabilidade em dispositivos optoeletrônicos. Para tal, foram feitas determinações de luminância e de eficiência quântica de luminância dos OLEDs construídos. Os dispositivos do tipo sanduíche, os OLEDs e as medidas correspondentes foram realizados em Curitiba, em colaboração com o Prof. Dr. Ivo Alexandre Hümmelgen, líder do Grupo de Dispositivos Optoeletrônicos Orgânicos do Departamento de Física da Universidade Federal do Paraná. / The present work describes the electrosynthesis of three polymers of the poly(p-phenylenevinylene) (PPV) family, having at least one long chain alkoxy group as substituent. These polymers were characterized by spectroscopic analyses (1H NMR, IR and UV-Vis), thermogravimetry (TG), size exclusion chromatography (SEC), cyclic voltammetry and electrically by current vs. potential plots obtained from metal/polymer/metal sandwich devices. The polymers were tested as active layers in gas sensors for organic vapour analyses aimed for future use in electronic noses. The same polymers were also employed in organic light emitting diodes (OLEDs) in which the luminance and the luminance quantum efficiency were measured. Both the sandwich devices and the OLEDs were made in Curitiba with the collaboration of Prof. Ivo Hümmelgen, head of the Group of Organic Optoelectronic Devices at the Physics Department of the Federal University of Paraná (UFPR).

O presente trabalho envolveu a eletrossíntese de três polímeros da família dos poli(p-fenilenovinileno)s, PPVs, apresentando como substituintes grupos alcóxi de cadeia longa. Esses polímeros foram caracterizados espectroscopicamente (RMN de 1H, IV e UV/VIS), termicamente (TG), por cromatografia por exclusão de tamanho (SEC), eletronicamente por voltametria cíclica e eletricamente por meio de curvas I x V em dispositivos do tipo sanduíche (metal/polímero/metal). Os polímeros foram utilizados na construção de sensores de gases para avaliação da capacidade sensitiva a vapores orgânicos, mostrando-se promissores para utilização em narizes eletrônicos. Construíram-se, também, dispositivos emissores de luz orgânicos (OLEDs) com utilização desses polímeros como camada ativa, no intuito de se conhecer sua aplicabilidade em dispositivos optoeletrônicos. Para tal, foram feitas determinações de luminância e de eficiência quântica de luminância dos OLEDs construídos. Os dispositivos do tipo sanduíche, os OLEDs e as medidas correspondentes foram realizados em Curitiba, em colaboração com o Prof. Dr. Ivo Alexandre Hümmelgen, líder do Grupo de Dispositivos Optoeletrônicos Orgânicos do Departamento de Física da Universidade Federal do Paraná. / The present work describes the electrosynthesis of three polymers of the poly(p-phenylenevinylene) (PPV) family, having at least one long chain alkoxy group as substituent. These polymers were characterized by spectroscopic analyses (1H NMR, IR and UV-Vis), thermogravimetry (TG), size exclusion chromatography (SEC), cyclic voltammetry and electrically by current vs. potential plots obtained from metal/polymer/metal sandwich devices. The polymers were tested as active layers in gas sensors for organic vapour analyses aimed for future use in electronic noses. The same polymers were also employed in organic light emitting diodes (OLEDs) in which the luminance and the luminance quantum efficiency were measured. Both the sandwich devices and the OLEDs were made in Curitiba with the collaboration of Prof. Ivo Hümmelgen, head of the Group of Organic Optoelectronic Devices at the Physics Department of the Federal University of Paraná (UFPR).

This diploma thesis is focused on the properties characterization of new organic materials with respect to their potential application in organic electro-optic devices. The theoretical part contains a themed literature search on application of organic materials for organic electronics and photonics. The basic principles of these devices are described. The practical part includes the preparation of thin films for organic photovoltaics of two types: based on low molecular weight organic compounds (diketo-pyrrolo-pyrroles derivates) and based on polymer (mixture of copolymer of poly(phenylenevinylene) and molecular senzitizer – derivate of fullerene). The first part of experiment is focused on characterization of optical and electrical properties of selected diketo-pyrrolo-pyrroles derivates and the second part is study the influence of annealing to polymer layer.

Made available in DSpace on 2017-07-20T12:40:16Z (GMT). No. of bitstreams: 1 Alvaro Fontana.pdf: 7055530 bytes, checksum: 4a9069c1fa7120a7895a1587f1fe173e (MD5) Previous issue date: 2015-09-18 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / In this work were performed organic synthesis of the monomer derivatives of poly (p-phenylenevinylene) whose main interest was to obtain a monomer with an aromatic ring having attached two bromine atoms (this step not being performed), a cyano group, a side chain of six carbon atoms and a sulfonic group linked to the end of side chain. The syntheses were performed starting from the compound 2,5-dimethylphenol and adding the aromatic ring an iodine atom, made subsequently replacing the iodine atom by a cyano group, and the sequences of reactions by adding a side chain with six carbon atoms attached at its one end a sulfonic group. The characterization of the obtained compounds was performed by spectroscopy techniques, Infrared, nuclear magnetic resonance 1H and 13C and GC-MS. These analyzes showed that the structures of the proposed monomers were achieved almost entirely. Part of this doctoral work was performed in the laboratory of the Emeritus Professor Dr. Alan Maxwell Bond at Monash University, Melbourne - Australia, such as sandwich doctorate program. The study in Australia comprised learning and application of cyclic voltammetry technique ac coupled to Fourier transform in chemical reactions studying the kinetics of 1 and 2 electron transfer, in this case, taking as an example the molecule N,N,N',N'-Tetramethyl-p-phenylenediamine, TMPD. The molecular solvents used for the study of electron transfer in the molecule TMPD were acetone and acetonitrile, and the following ionic liquids: [BMPIPTFSI], [BMIM] [TFSI], [BMIm][BF4] and [BDMIM] [TF2N]. In all the results obtained it was found the process known as internal reference, where the first electron transfer reaction in the molecule, because it is faster, can be used to compare the values of the thermodynamic and kinetic parameters obtained in the first process with the parameter values obtained in the second electron transfer process in the same molecule. / Neste trabalho foram realizadas sínteses orgânicas de monômeros derivados de poli(p-fenilenovinileno) cujo principal interesse foi a obtenção de um monômero com um anel aromático tendo ligado a ele, dois átomos de bromo (não sendo realizada essa etapa), um grupamento ciano, uma cadeia lateral com seis átomos de carbono, e um grupamento sulfônico ligado a extremidade da cadeia lateral. As sínteses foram realizadas partindo-se do composto 2,5-dimetilfenol e adicionando-se ao anel aromático um átomo de iodo, posteriormente feita a troca do átomo de iodo por um grupo ciano e nas sequências das reações adicionando-se uma cadeia lateral com seis átomos de carbono oposta ao grupo ciano e ligado na extremidade da cadeia lateral um grupo sulfônico. A caracterização dos compostos foi realizada através das técnicas, infravermelho, ressonância magnética nuclear 1H, 13C e CG-MS. Essas análises evidenciaram que as estruturas dos monômeros propostos foram alcançadas em quase sua totalidade. Parte deste trabalho de doutoramento foi realizada no laboratório do professor Emeritus Dr. Alan Maxwell Bond na Monash University em Melbourne – Austrália, como doutorado sanduíche. O estudo feito na Austrália compreendeu a aprendizagem e aplicação da técnica de voltametria cíclica ac acoplada à transformada de Fourier, estudando-se a cinética de transferência de 1 e 2 elétrons, neste caso, utilizando-se como exemplo, a molécula N,N,N′,N′-Tetramethyl-p-phenylenediamine, TMPD. Os solventes moleculares utilizados para o estudo da transferência de elétrons nesta molécula foram acetona e acetonitrila e também os seguintes líquidos iônicos: [BMPIPTFSI], [BMIM][TFSI], [BMIm][BF4] e [BDMIM][TF2N]. Em todos os resultados obtidos constatou-se o processo chamado de referência interna, onde, a primeira reação de transferência de elétrons nesta molécula, por ser mais rápida, pode ser utilizada para comparar os valores dos parâmetros termodinâmicos e cinéticos obtidos no primeiro processo de transferência de elétrons com os valores dos parâmetros obtidos no segundo processo na mesma molécula.

Made available in DSpace on 2017-07-24T19:37:54Z (GMT). No. of bitstreams: 1 Alvaro Fontana.pdf: 7055530 bytes, checksum: 4a9069c1fa7120a7895a1587f1fe173e (MD5) Previous issue date: 2015-09-18 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / In this work were performed organic synthesis of the monomer derivatives of poly (p-phenylenevinylene) whose main interest was to obtain a monomer with an aromatic ring having attached two bromine atoms (this step not being performed), a cyano group, a side chain of six carbon atoms and a sulfonic group linked to the end of side chain. The syntheses were performed starting from the compound 2,5-dimethylphenol and adding the aromatic ring an iodine atom, made subsequently replacing the iodine atom by a cyano group, and the sequences of reactions by adding a side chain with six carbon atoms attached at its one end a sulfonic group. The characterization of the obtained compounds was performed by spectroscopy techniques, Infrared, nuclear magnetic resonance 1H and 13C and GC-MS. These analyzes showed that the structures of the proposed monomers were achieved almost entirely. Part of this doctoral work was performed in the laboratory of the Emeritus Professor Dr. Alan Maxwell Bond at Monash University, Melbourne - Australia, such as sandwich doctorate program. The study in Australia comprised learning and application of cyclic voltammetry technique ac coupled to Fourier transform in chemical reactions studying the kinetics of 1 and 2 electron transfer, in this case, taking as an example the molecule N,N,N',N'-Tetramethyl-p-phenylenediamine, TMPD. The molecular solvents used for the study of electron transfer in the molecule TMPD were acetone and acetonitrile, and the following ionic liquids: [BMPIPTFSI], [BMIM] [TFSI], [BMIm][BF4] and [BDMIM] [TF2N]. In all the results obtained it was found the process known as internal reference, where the first electron transfer reaction in the molecule, because it is faster, can be used to compare the values of the thermodynamic and kinetic parameters obtained in the first process with the parameter values obtained in the second electron transfer process in the same molecule. / Neste trabalho foram realizadas sínteses orgânicas de monômeros derivados de poli(p-fenilenovinileno) cujo principal interesse foi a obtenção de um monômero com um anel aromático tendo ligado a ele, dois átomos de bromo (não sendo realizada essa etapa), um grupamento ciano, uma cadeia lateral com seis átomos de carbono, e um grupamento sulfônico ligado a extremidade da cadeia lateral. As sínteses foram realizadas partindo-se do composto 2,5-dimetilfenol e adicionando-se ao anel aromático um átomo de iodo, posteriormente feita a troca do átomo de iodo por um grupo ciano e nas sequências das reações adicionando-se uma cadeia lateral com seis átomos de carbono oposta ao grupo ciano e ligado na extremidade da cadeia lateral um grupo sulfônico. A caracterização dos compostos foi realizada através das técnicas, infravermelho, ressonância magnética nuclear 1H, 13C e CG-MS. Essas análises evidenciaram que as estruturas dos monômeros propostos foram alcançadas em quase sua totalidade. Parte deste trabalho de doutoramento foi realizada no laboratório do professor Emeritus Dr. Alan Maxwell Bond na Monash University em Melbourne – Austrália, como doutorado sanduíche. O estudo feito na Austrália compreendeu a aprendizagem e aplicação da técnica de voltametria cíclica ac acoplada à transformada de Fourier, estudando-se a cinética de transferência de 1 e 2 elétrons, neste caso, utilizando-se como exemplo, a molécula N,N,N′,N′-Tetramethyl-p-phenylenediamine, TMPD. Os solventes moleculares utilizados para o estudo da transferência de elétrons nesta molécula foram acetona e acetonitrila e também os seguintes líquidos iônicos: [BMPIPTFSI], [BMIM][TFSI], [BMIm][BF4] e [BDMIM][TF2N]. Em todos os resultados obtidos constatou-se o processo chamado de referência interna, onde, a primeira reação de transferência de elétrons nesta molécula, por ser mais rápida, pode ser utilizada para comparar os valores dos parâmetros termodinâmicos e cinéticos obtidos no primeiro processo de transferência de elétrons com os valores dos parâmetros obtidos no segundo processo na mesma molécula.

Nesse trabalho apresentamos o estudo das propriedades ópticas e elétricas de filmes e dispositivos eletrônicos de polímeros luminescentes, poli(p-fenilenovinilenos) - PPVs, semicondutores, polianilinas - PANI, e derivados desses dois polímeros. São apresentadas todas as etapas de preparação e caracterização dos dispositivos, desde as rotas de síntese dos polímeros, até a modelagem de dispositivos eletroluminescentes e de transistores de efeito de campo. Os filmes luminescentes foram caracterizados por propriedades de absorção e emissão ópticas, e função pseudo-dielétrica, mostrando dependência com a presença de grupos laterais. Filmes de PANI, por sua vez, foram caracterizados através de medidas de condutividade complexa, e os resultados obtidos mostram-se típicos de sistemas sólidos desordenados. Para interpretá-las, foi utilizado o modelo de distribuição aleatória de barreiras de energia livre (random free energy barrier model - RFEB) aplicado como ajuste aos resultados experimentais. Outra característica importante dos PPVs, estudada nessa tese, foi à degradação em condições ambientais sob iluminação. Esse efeito foi acompanhado por medidas de absorção óptica e de elipsometria, mostrando que a combinação dos efeitos do oxigênio e da luz é a principal responsável pela degradação desse material. Para explicar tal efeito, elaboramos um modelo baseado nas propriedades individuais dos cromóforos do polímero e na substituição de ligações vinílicas C=C por ligações carbonilas C=O, cuja comparação com os resultados experimentais forneceu uma estimativa para a fração degradada do polímero como função do tempo de iluminação. Foram caracterizados dispositivos emissores de luz de PPVs através de medidas corrente vs. tensão e de condutividade complexa, que através do ajuste por modelos de circuitos equivalentes e pelo modelo RFEB forneceu grandezas fundamentais como a resistividade e a constante dielétrica da camada polimérica. Finalizando, transistores de efeito de campo de poli(o-metoxianilina) - POMA (um derivado da PANI) apresentaram modulação pela tensão de porta, e um modelo baseado nas propriedades de condução da POMA levando-se em conta gradientes de mobilidade e de densidade de portadores ortogonais à superfície do polímero foi elaborado e se ajustou muito bem aos resultados experimentais. / In this thesis we report the electrical and optical characterization of polymeric thin-film and luminescent and electronic devices. The studied materials were the luminescent poly(p-phenylenevinylenes) - PPVs, semiconducting polyanilines - PANI and their derivatives. All the steps in the material preparation are described: the synthesis and the film preparation. Also, the technological details of the fabrication of the devices, light-emitting diodes (LEDs) and field-effect transistor (FETs), are presented. Luminescent films were studied by optical absorption and emission and by ellipsometry measurements, giving emphasis on the influence of lateral groups. The PANI films were electrically investigated by the analysis of the complex conductivity, whose results were adjusted by the random free energy barrier model used for disordered solids. Another important investigation was related to the photodegradation of the luminescent polymers, a deleterious effect owing to a concomitant action of oxygen and light. To explain such effect we proposed a model based on the properties of individual cromophores of the molecules, and in the incorporation of ketone groups (C=O), cleaving the vinyl C=C bonds. The luminescent devices were electrically and optically characterized. The current density vs. voltage and complex impedance were fit by macroscopic models taking into account a hopping process, and an equivalent circuit was also used to study ITO/polymer/metal structures. Finally, the field-effect transistor made by poly(o-methoxyaniline) were experimentally studied and a model that assumes gradients of carrier density and mobility orthogonal to the film surface fit with good agreement the ISD vs. VSD for different gate voltages, VG.

Emissive conjugated polymers, namely PPV, PPP, polyfluorenes, etc, have gained considerable attention in recent times, specifically because of their potential application in the fields of PLED’s, displays, FET’s and sensors. The main target of the present work is the synthesis and utilization of dithiocarbamate (DTC) precursor polymers for: (a) generation of segmented conjugated polymers of poly[2-methoxy-5-((2'-ethylhexyl)oxy)-1,4- phenylenevinylene], MEHPPV-x, for color control and the study of their thermal elimination kinetics, (b) modulating phase separation and energy transfer in MEHPPV-x blends, (c) generation of tunable two-color patterns of conjugated polymers and (d) modification of the precursor polymer backbone by grafting and the study of its fluorescence modulation in the presence of different probe molecules. In the first part of this work, various dithiocarbamate (DTC) precursor copolymers, MDP-x, containing two types of leaving groups viz. methoxy and diethyldithiocarbamate with precise control over the DTC composition, were synthesized. Thermal elimination of these precursor polymers generated segmented MEHPPV with controlled conjugation, and hence the tuning of color from green to red is achieved (figure 1). These copolymers were synthesized via a modified Wessling’s route previously developed in our laboratory.1 The advantage of the DTC precursor over the acetate and xanthate precursor routes was that the elimination can be carried out at lower temperature (160OC) for the generation of segmented MEHPPV-x.2 (Figure 1) Kinetic parameters, namely activation energy (Ea) and pre-exponential factor (A), associated with the thermal elimination process of MDP-x to MEHPPV-x were determined in solution and as well as in thin films by following the evolution of the absorption spectra during the elimination process (figure 2). It was seen that the activation energy required for the elimination process was similar in both thin film and solution, whereas the pre-exponential factor was two order magnitude higher in thin films.2 This fact holds good for all the DTC compositions investigated. The thermal degradation products, carbon disulphide and diethyl amine, were analyzed using a mass spectrometer coupled with TGA instrument, confirming the selective elimination of the DTC groups. (Figure 2) Phase separation and energy transfer characteristics of segmented MEHPPV blends containing two different distributions of conjugation lengths, namely MEHPPV-8 (LC) and MEHPPV-100 (HC), were investigated using FL, UV and confocal fluorescence microscopic studies (figure 3). The phase separation and energy transfer in blends of the HC and LC were (Figure 3) modulated by addition of selective non-solvent for HC, namely cyclohexane, to the film casting solution. Typically, the extent of energy transfer to HC from LC is reduced in the presence of high volume fraction of cyclohexane.3 A novel way to generate two-color patterned substrates of MEHPPV was developed based on the control of “molecular conjugation length” using standard photo-acid generator based photolithographic methods (figure 4). This approach relies on the use of a single precursor containing controllable amounts of two types of thermally eliminatable groups, only one of which eliminates in the presence of an acid while the other that is labile even in its absence. An important feature of this approach is that the colour of the unexposed regions can be controlled by varying the composition of the MDP-x precursor. (Figure 4) Benzyl diethyl dithiocarbamate (BDTC) is known to act as iniferter (initiator-transfer agent and terminator). MDP-x precursor polymers, which contain similar benzyl dithiocarbamate groups, were used as macro-iniferter for grafting various acrylates, viz, (Figure 5) methyl acrylate, benzoyloxy ethyl acrylate and t-butyl acrylate, on to the precursor backbone, which resulted in MEHPPV-g-polyacrylate after acid catalyzed thermal elimination of the residual methoxy groups (figure 5).4 The t-butyl acrylate-grafted precursor polymers, namely, MDP-g-PtBA on thermal elimination in presence of acid underwent simultaneous acid-catalyzed thermal elimination as well as the complete hydrolysis of the t-butyl groups, leading to the formation of water soluble MEHPPV-grafted with polyacrylic acid chains, namely MEHPPV-g-PAA (figure 6). These PAA-grafted MEHPPV’s were shown to respond to various probe molecules and their optical responses were studied using fluorescence spectroscopy. These polymers could sense methyl viologen at very low concentrations. Single-tail ammonium surfactants and non-ionic surfactant, like triton-X-100, caused a dramatic enhancement of fluorescence in solution, due to the modulation of the conjugated backbone conformation, and as a consequence the break up of intra-chain inter-chromophore excitons (figure 6). (Figure 6) Fof figures and molecular formula pl see the original thesis)

Nesse trabalho apresentamos o estudo das propriedades ópticas e elétricas de filmes e dispositivos eletrônicos de polímeros luminescentes, poli(p-fenilenovinilenos) - PPVs, semicondutores, polianilinas - PANI, e derivados desses dois polímeros. São apresentadas todas as etapas de preparação e caracterização dos dispositivos, desde as rotas de síntese dos polímeros, até a modelagem de dispositivos eletroluminescentes e de transistores de efeito de campo. Os filmes luminescentes foram caracterizados por propriedades de absorção e emissão ópticas, e função pseudo-dielétrica, mostrando dependência com a presença de grupos laterais. Filmes de PANI, por sua vez, foram caracterizados através de medidas de condutividade complexa, e os resultados obtidos mostram-se típicos de sistemas sólidos desordenados. Para interpretá-las, foi utilizado o modelo de distribuição aleatória de barreiras de energia livre (random free energy barrier model - RFEB) aplicado como ajuste aos resultados experimentais. Outra característica importante dos PPVs, estudada nessa tese, foi à degradação em condições ambientais sob iluminação. Esse efeito foi acompanhado por medidas de absorção óptica e de elipsometria, mostrando que a combinação dos efeitos do oxigênio e da luz é a principal responsável pela degradação desse material. Para explicar tal efeito, elaboramos um modelo baseado nas propriedades individuais dos cromóforos do polímero e na substituição de ligações vinílicas C=C por ligações carbonilas C=O, cuja comparação com os resultados experimentais forneceu uma estimativa para a fração degradada do polímero como função do tempo de iluminação. Foram caracterizados dispositivos emissores de luz de PPVs através de medidas corrente vs. tensão e de condutividade complexa, que através do ajuste por modelos de circuitos equivalentes e pelo modelo RFEB forneceu grandezas fundamentais como a resistividade e a constante dielétrica da camada polimérica. Finalizando, transistores de efeito de campo de poli(o-metoxianilina) - POMA (um derivado da PANI) apresentaram modulação pela tensão de porta, e um modelo baseado nas propriedades de condução da POMA levando-se em conta gradientes de mobilidade e de densidade de portadores ortogonais à superfície do polímero foi elaborado e se ajustou muito bem aos resultados experimentais. / In this thesis we report the electrical and optical characterization of polymeric thin-film and luminescent and electronic devices. The studied materials were the luminescent poly(p-phenylenevinylenes) - PPVs, semiconducting polyanilines - PANI and their derivatives. All the steps in the material preparation are described: the synthesis and the film preparation. Also, the technological details of the fabrication of the devices, light-emitting diodes (LEDs) and field-effect transistor (FETs), are presented. Luminescent films were studied by optical absorption and emission and by ellipsometry measurements, giving emphasis on the influence of lateral groups. The PANI films were electrically investigated by the analysis of the complex conductivity, whose results were adjusted by the random free energy barrier model used for disordered solids. Another important investigation was related to the photodegradation of the luminescent polymers, a deleterious effect owing to a concomitant action of oxygen and light. To explain such effect we proposed a model based on the properties of individual cromophores of the molecules, and in the incorporation of ketone groups (C=O), cleaving the vinyl C=C bonds. The luminescent devices were electrically and optically characterized. The current density vs. voltage and complex impedance were fit by macroscopic models taking into account a hopping process, and an equivalent circuit was also used to study ITO/polymer/metal structures. Finally, the field-effect transistor made by poly(o-methoxyaniline) were experimentally studied and a model that assumes gradients of carrier density and mobility orthogonal to the film surface fit with good agreement the ISD vs. VSD for different gate voltages, VG.