Conducting metallopolymers have been investigated for a variety of applications due to their ability to take advantage of both the mechanical processability of the polymer material, as well as the optical and electronic properties of the metal. Our project goal is to design, synthesize and characterize novel iridium(III)-containing conducting metallopolymers for use as the active layer in polymer light-emitting diodes. We have utilized thiophene functionalized ligands that can be readily electropolymerized into conducting polymer thin films and can be easily incorporated into a device structure. Iridium(III) was chosen as the metal center due to its promising photophysical properties, as similar complexes have demonstrated high luminescent quantum yields and short phosphorescent lifetimes. The coordination environment around the metal can be altered synthetically to tune the emission wavelength across the visible spectrum. The synthetic control over the polymer backbone, as well as the iridium(III) ligand environment, allowed us to independently vary each component, which has provided a variety of materials. The materials are characterized through 1H and 13C NMR, mass spectrometry, elemental analysis, electrochemistry, X-Ray diffraction and X-Ray Photoelectron Spectroscopy. The photophysical properties of the materials are studied through UVvii Visible absorption spectroscopy, UV-Vis-NIR spectroelectrochemistry and steadystate/ time-resolved emission spectroscopy. / text

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Neste trabalho é apresentado o estudo e o desenvolvimento de um sistema eletrônico de teste, para avaliação de desempenho de diodos emissores de luz poliméricos - PLEDs, ou de mostradores de informações com até 35 PLEDs em matriz passiva produzidos em laboratório. Os requisitos de acionamento e controle, baseados nas características estruturais e elétricas de PLEDs e mostradores de PLEDs, foram cuidadosamente estudados para definição dos circuitos mais adequados para o sistema de controle. O equipamento desenvolvido permite ajustar níveis de tensão e corrente elétricas, freqüência e largura de pulso do sinal de alimentação, de forma a possibilitar variações de emissão de luz nos dispositivos acionados. O sistema foi avaliado utilizando-se um mostrador de informações de PLEDs em matriz passiva, que antes passou por caracterizações estruturais e elétricas, sendo que os resultados serviram para ajuste da região de trabalho da tensão e corrente elétricas e freqüência de alimentação. Os resultados dos testes demonstraram que o circuito projetado atende a todos os requisitos de projeto e aos objetivos para os quais foi proposto. O acionamento do mostrador de referência com o sistema desenvolvido permitiu avaliar o seu desempenho em relação à emissão de luz, analisando características como luminância, cromaticidade e radiometria, frente a variações de tensão e corrente elétricas e largura de pulso do sinal de alimentação. Estas informações permitem a criação de uma base de dados que auxiliam o pesquisador durante a avaliação de desempenho e de reprodutibilidade de PLEDs ou mostradores de PLEDs construídos em laboratório. / In this work it is presented the study and development of an electronic system of test for performance evaluation of polymer light-emitting diodes - PLEDs, or displays with up to 35 PLEDs in passive-matrix produced in laboratory. The drive and control requirements, based in structural and electric characteristics of PLEDs and PLEDs displays, carefully had been studied for definition of adequate circuits for control system. The developed equipment allows adjusting voltage and current levels, frequency and pulse width of signal power, to make possible variations of light emission in the motion devices. The system was evaluated using passive-matrix PLED display, that before passed for structural and electric characterizations, being that the results had served for voltage, current and frequency adjustment of signal power. The tests results had demonstrated that projected circuit takes care of all requirements and objectives for which was considered. The drive of reference display with the developed system allowed to performance evaluate of its light-emitting characteristics, as luminance, chromaticity and photometry, front voltage, current and pulse width variations of signal power. This information allows a database creation that assists researcher during performance evaluation and reproducibility of PLEDs or PLEDs displays produced in laboratory.

In this research, we investigated a novel rigid-rod polymer sPBI for mono-layer polymer light emitting diode (PLED) fabrication and luminescence emission. sPBI could be a luminescent polymer with a low threshold voltage of 4.5 V and green light electroluminescence emission (530 nm). Its SO3H pendant attached to the p-phenyl ring improved electronic delocalization along the backbone resulted in a red shift of the absorption spectrum. By attaching propanesulfonated pendants to the heterocyclic moiety of intractable fully conjugated sPBI, water-soluble rigid-rod polyelectrolyte sPBI-PS(Li+) was synthesized to promote its processibility in water or common organic solvent. This water-soluble rigid-rod polyelectrolyte sPBI-PS(Li+) was fabricated for polymer light-emitting electrochemical cells (PLECs) with LiCF3SO3 (LiTf) or LiN(CF3SO2)2 (LiTfSI) dopants for investigating the influence of propanesulfonated pendants as well as dopants on the opto-electronic emission and the room-temperature DC conductivity. The effect of lithium salts (LiTf or LiTfSI) on photoluminescence color of doped sPBI-PS(Li+) films was negligible. sPBI-PS(Li+) PLECs doped with 0.41 and 1.01 wt. % of LiTfSI showed higher green light electroluminescence emission (514 nm) with a lower threshold voltage of 3.0 V and -4.6 V, respectively. Emission brightness of the sPBI-PS(Li+) PLEC did not raise upon increasing the ionic conductivity of the luminescent layer.

ABSTRACT Light emitting diodes of non-fully conjugated coil-like homopolymers and fully conjugated rigid-rod homopolymers with electron withdrawing or donating group were studied. A series of Poly[2,2-(m-2-X-phenylene)-4-4¡A-hexafluoroisopropane- bibenzoxazoles] (6F-PBO-X, with X = amine, hydrogen and nitro) and poly-p-(2-X- phenylene)-benzobisoxazole (PBO-X, with X = amine, hydrogen and nitro) were synthesized for light emitting diode applications to observe electroluminescence emission affected by electron withdrawing or donating group. All polymers were fabricated identically to form bi-layer light emitting diodes. In the devices, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonite)(PEDOT:PSS) was applied to be a hole transport layer; indium tin oxide (ITO) was the anode; and aluminum was the cathode. Devices of the non-fully conjugated coli-like polymers (6F-PBO-X) and the fully conjugated rigid-rod polymers (PBO-X) all showed threshold voltage about 4 V. In the electroluminescence (EL) spectrum, the maximum intensity of non-fully conjugated polymer (6F-PBO-X) with amine (-NH2), hydrogen (-H) or nitro (-NO2) functional group was at 499 nm, 505 nm and 515 nm, respectively, showing a 20 nm wavelength shift. From ¡VNH2, -H and ¡VNO2 groups, their Commission International de l`Eclairage (C. I. E.) coordinates were (0.30, 0.46), (0.34, 0.45) and (0.40, 0.46), respectively. The EL maximum intensity for fully conjugated rigid-rod polymer PBO-X was at 521 nm (-NH2) and 474 nm (-NO2) showing a 50 nm wavelength shift. Their C. I. E. coordinates were (0.42, 0.45) and (0.25, 0.38), respectively. This is attributed to the fully conjugated, collinear, coplanar, rigid-rod polymers (PBO-X) backbone readily affected by the push-pull functional groups showing a large red shift.

Neste trabalho é apresentado o estudo e o desenvolvimento de um sistema eletrônico de teste, para avaliação de desempenho de diodos emissores de luz poliméricos - PLEDs, ou de mostradores de informações com até 35 PLEDs em matriz passiva produzidos em laboratório. Os requisitos de acionamento e controle, baseados nas características estruturais e elétricas de PLEDs e mostradores de PLEDs, foram cuidadosamente estudados para definição dos circuitos mais adequados para o sistema de controle. O equipamento desenvolvido permite ajustar níveis de tensão e corrente elétricas, freqüência e largura de pulso do sinal de alimentação, de forma a possibilitar variações de emissão de luz nos dispositivos acionados. O sistema foi avaliado utilizando-se um mostrador de informações de PLEDs em matriz passiva, que antes passou por caracterizações estruturais e elétricas, sendo que os resultados serviram para ajuste da região de trabalho da tensão e corrente elétricas e freqüência de alimentação. Os resultados dos testes demonstraram que o circuito projetado atende a todos os requisitos de projeto e aos objetivos para os quais foi proposto. O acionamento do mostrador de referência com o sistema desenvolvido permitiu avaliar o seu desempenho em relação à emissão de luz, analisando características como luminância, cromaticidade e radiometria, frente a variações de tensão e corrente elétricas e largura de pulso do sinal de alimentação. Estas informações permitem a criação de uma base de dados que auxiliam o pesquisador durante a avaliação de desempenho e de reprodutibilidade de PLEDs ou mostradores de PLEDs construídos em laboratório. / In this work it is presented the study and development of an electronic system of test for performance evaluation of polymer light-emitting diodes - PLEDs, or displays with up to 35 PLEDs in passive-matrix produced in laboratory. The drive and control requirements, based in structural and electric characteristics of PLEDs and PLEDs displays, carefully had been studied for definition of adequate circuits for control system. The developed equipment allows adjusting voltage and current levels, frequency and pulse width of signal power, to make possible variations of light emission in the motion devices. The system was evaluated using passive-matrix PLED display, that before passed for structural and electric characterizations, being that the results had served for voltage, current and frequency adjustment of signal power. The tests results had demonstrated that projected circuit takes care of all requirements and objectives for which was considered. The drive of reference display with the developed system allowed to performance evaluate of its light-emitting characteristics, as luminance, chromaticity and photometry, front voltage, current and pulse width variations of signal power. This information allows a database creation that assists researcher during performance evaluation and reproducibility of PLEDs or PLEDs displays produced in laboratory.

In this thesis, we investigated several photoelectric material systems consisted of conjugated polymers by means of computer simulation. We combined several theory and simulation methods to meodeling different subjects from atomic to mesoscopic scale. We dealt with the problems such as quantum efficiency, structure characteristic, and the phase behavior in material. We hope to have better understanding of the relationship between structure characteristic and functional property in material. It will help an engineering designer to adjust the variables that optimize characteristics linking the synthesis of advanced materials with desired physical properties. This work can be divided into three parts. Long side chain substituted PPV polymers applied in light-emitting diode material : Molecular dynamics simulations were employed to investigate structure features and segment orientation of four poly(phenylene vinylene) (PPV)-like conjugated polymers with long flexible side chains at room temperature. In the simulations, the main chains of the polymers were found to be semi-rigid and to exhibit a tendency to coil into ellipsoidal helices or form zigzag conformations of only limited regularity. It was shown that continuous segments of a chain which are quasi-coplanar along the backbone are in a range of 2~4 repeat units. This implies that long-range electron transfer along same backbones of these polymers may not happen but may be mediated by interchain interactions. The ordered orientation and coupling distance of interchain aromatic rings are found to correlate with important optical properties of materials. Then we combined molecular dynamics simulation and density matrix methods modeling of amorphous light-emitting polymers. A simplified method combining molecular dynamics (MD) simulation and density matrix (DM) theory was developed for the prediction of optical properties of long side chain substituted poly(phenylene vinylene) (PPV) polymers. This MD+DM method takes account of the complexity of molecular packing of polymer chains. The method has been tested to simulate the absorption spectra of four model systems. The wavelengths of absorption maxima of the calculated spectra of these four conjugated polymers are in reasonable agreement with experimental data. The simulation also demonstrated that the importance of including interchain interactions in the calculation. Ion-conducting polymer sPBI-PS(Li+): To understand the mechanism of ionic migration in the amorphous matrixes of polymer electrolytes is crucial for their applications in modern technologies. Here, molecular dynamics (MD) simulation was carried out to investigate the ionic conduction mechanism of a particular conjugated rigid-rod polymer, sPBI-PS(Li+). The backbone of this polymer is poly[(1, 7- dihydrobenzo[1, 2-d:4,5-d¡¦]diimidazole- 2,6-diyl)-2-(2-sulfo)-p-phenylene]. The polymer has pendants of propane sulfonate Li+ ionomer. The MD simulations showed that the main chains of sPBI-PS(Li+) are in layer-like structure. The further detailed structure analysis suggested that the £k-electron of this polymer is not delocalized among aromatic rings. This agrees with the experimental result that sPBI-PS(Li+) shows no electronic conductivity and the conductivity of this polymer is mainly ionic. The calculated migration channels of lithium ions and electrostatic potential distributions indicated clearly that the polymer matrix is anisotropic for the migrations of ions. The migration of lithium ions along the longitudinal direction is more preferable than that along the transverse direction. The relaxations of the polymer host were found to play important roles in the transfer process of lithium ions. The hopping of lithium ion from one -SO3-1 group to another is correlated strongly with characteristic motions of -SO3-1 group on a time scale of about 10-13 s. Self-assembly functional material. Dissipative particle dynamics (DPD) simulations were carried out to investigate mixed ionic and non-ionic molecules, sodium tetradecyl sulfate (STS) and tetradecyl triethoxylated ether (C14E3) aqueous system. Different types of mixed micelles are formed depending on the concentrations of STS and C14E3. Our results are in good agreement to the early NMR measurements. From the investigation of surfactant aggregation, we understand the self-assembly mechanism and classical phase behavior in general diblock copolymer. Further, we investigated the self-assembly process on a particular mushroom-shaped supramolecular film material from molecular character to phase behavior. The miniaturized rod-coil triblock copolymers (PS-PI-RCBC) HEMME had been found to self-assemble into well-ordered nanostructures and unusual head to tail multilayer structure. The purpose of our study is to obtain fundamental understanding the connection of the inherent morphological characterization of single molecule and the mechanism of phase behavior of this polar self-assembly system. Dissipative particle dynamics simulation was carried out to study the mechanism of phase behavior of the solvent-copolymers system. We found that the solvent-induced polar effect under different temperature is important in the process of self-assembly of block copolymers. In different temperature the solvent induces hybrid structure aggregation. Our results are consistent with experimental observations and give evidence for a special mechanism governing the unusual phase behavior in thin films of modulated phases. The sizes and stabilization energies of mushroom-shaped supramolecular clusters were predicted by molecular modeling method. Clusters of sizes from 16 to 90 molecules were found to be stable. In combination of classical and simple quantum mechanical calculations, the band gaps of HEMME clusters with various sizes were estimated. The band gap was converged at 2.45 eV for cluster contains 90 molecules. Nonlinear optical properties of the material were investigated by the semi-empirical quantum mechanical calculations of molecular dipole moment and hyperpolarizabilities. Significant second-order nonlinear optical properties were shown from these calculated properties.

The thesis is focused on the study of electric and dielectric properties of thin film organic materials that can be used as an active layer of photovoltaic cells. Primarily were studied the properties of the layers on the glass substrates, which consist of a thin active layer of phthalocyanines. On the samples were first measured current-voltage characteristics (in the dark and during the exposure) and the basic parameters of the photovoltaic conversion were determined. Finally were measured frequency dependencies (impedance spectra, in the dark and during the exposure) and the parameters of a model of the structure with organic semiconductor were determined. The obtained results will be used to optimize the properties of photovoltaic cells.