Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work presents an LED electrothermal design methodology applied to a street lighting system. The methodology aims to provide indicatives of the optimal LED operating point for lighting systems design, considering electrical, thermal and photometric system features. Different projects are developed according to the methodology, the theoretical results are compared with fluid dynamics simulation and demonstrated by experimental results. A research including luminous flux, luminous efficacy and flicker is performed considering the LED current ripple, defining acceptable levels of ripple based on the optimal operational point. The methodology is applied by developing a lighting system composed of an LED driver and a thermal dissipation system, comprising a luminaire, a heatsink and fans. The lighting system includes electrothermal feedback control. The results provide high power factor with low current harmonic distortion to the power grid. The LED operational temperature ensures the luminous flux maintenance over the system lifetime. / Este trabalho apresenta uma metodologia de projeto eletrotérmico de LEDs aplicada a um sistema de iluminação pública. A metodologia tem o objetivo de proporcionar indicativos do melhor ponto de operação do LED para o projeto de sistemas de iluminação, considerando os aspectos elétricos, térmicos e fotométricos envolvidos no sistema. Diferentes projetos são desenvolvidos utilizando a metodologia, os resultados teóricos obtidos são comparados com simulações computacionais de dinâmica dos fluidos e comprovados através de resultados experimentais. Um estudo do fluxo, eficácia e cintilação luminosa é também realizado considerando a ondulação de corrente aplicada aos LEDs, definindo os níveis aceitáveis de ondulação com base no ponto ótimo de operação. Para aplicação da metodologia é desenvolvido um sistema de iluminação pública composto por um circuito de acionamento dos LEDs e um sistema de dissipação térmica, formado por uma luminária, um dissipador de calor e ventiladores. O sistema de iluminação possui controle com realimentação eletrotérmica. Os resultados obtidos proporcionam alto fator de potência com baixa distorção harmônica ao sistema elétrico e temperatura de operação que garante a manutenção do fluxo luminoso dos LEDs durante toda a vida útil do sistema.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-02-11T13:22:33Z No. of bitstreams: 1 pedrosantosalmeida.pdf: 19972618 bytes, checksum: 95d8213caa2ed63781c9a0e651a913c6 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-02-26T12:01:23Z (GMT) No. of bitstreams: 1 pedrosantosalmeida.pdf: 19972618 bytes, checksum: 95d8213caa2ed63781c9a0e651a913c6 (MD5) / Made available in DSpace on 2016-02-26T12:01:23Z (GMT). No. of bitstreams: 1 pedrosantosalmeida.pdf: 19972618 bytes, checksum: 95d8213caa2ed63781c9a0e651a913c6 (MD5) Previous issue date: 2014-12-11 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho apresenta um estudo sobre o acionamento de diodos emissores de luz (LEDs) a partir da rede elétrica. Este estudo envolve uma análise sobre as características térmicas, elétricas e fotométricas dos LEDs visando a adequada caracterização estática e dinâmica da carga. Em seguida, com o objetivo de propor conversores com uma eficiência global superior, propõe-se a utilização de conversores ressonantes como estágio de controle de potência. Este estágio é precedido de um estágio pré-regulador do fator de potência, de forma a garantir uma baixa distorção harmônica total da corrente drenada da rede. Um estudo sistemático acerca das topologias de correção do fator de potência e de conversores ressonantes que podem compor cada um destes dois estágios é feito, visando compilar as características, vantagens e desvantagens de cada uma para o acionamento de LEDs. A partir deste estudo, foi possível propor uma estrutura integrada de conversor ressonante com um pré-regulador de alto fator de potência, que se mostrou adequado para acionar uma carga de 72 LEDs associados em série, com uma potência nominal aproximada de 100 W. O protótipo do conversor proposto atingiu uma eficiência global acima de 92%, com um fator de potência superior a 0,97 e distorção harmônica da corrente de entrada de cerca de 20%, com total observância aos parâmetros de qualidade de energia impostas pelas normatizações nacional e internacional. O projeto deste conversor também permitiu a eliminação dos capacitores eletrolíticos no circuito de potência do protótipo através da redução da capacitância; somente foram empregados capacitores de filme metalizado, o que contribui para elevar a vida útil do conversor, compatibilizando-a com a vida útil dos LEDs sendo acionados. / This work presents a study regarding the driving of light-emitting diodes (LEDs) fed from mains power. This study involves an analysis of the thermal, electrical and photometrical characteristics of the LEDs, aiming an adequate static and dynamical characterization of the load. Then, with the goal of proposing driving converters with a superior global efficiency, it is proposed the use of resonant conversion as the power control stage of the LED drivers. This stage is preceded by a power factor pre-regulator stage, so that a low total harmonic distortion on the input current can be achieved. A systematic study of the power factor correction topologies and resonant converters which might compose each of these two stages is done, therefore compiling the characteristics, advantages and disadvantages of each for the driving of LEDs. From this study, it was proposed an integrated converter structure of a resonant converter with a high power factor pre-regulator, which showed good compliance when driving an LED load composed of 72 series-associated LEDs, with nominal power of ca. 100 W. A prototype of the proposed converter has reached a global efficiency above 92%, with a power factor greater than 0.97 and total harmonic distortion of input current of ca. 20%, along with total compliance with the power quality parameters imposed by national and international standards. The design of this converter also permitted the elimination of the electrolytic capacitors from within the power circuitry of the prototype through capacitance reduction; only metalized film capacitors were employed, contributing to enhance the lifespan of the converter, making it compatible with the lifespan of the LEDs being driven.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-06-10T11:59:43Z No. of bitstreams: 1 marcelopaschoaldias.pdf: 2362586 bytes, checksum: de75d2d7f7b0ebf296ee1a44eeb6874f (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-07-13T13:48:14Z (GMT) No. of bitstreams: 1 marcelopaschoaldias.pdf: 2362586 bytes, checksum: de75d2d7f7b0ebf296ee1a44eeb6874f (MD5) / Made available in DSpace on 2016-07-13T13:48:14Z (GMT). No. of bitstreams: 1 marcelopaschoaldias.pdf: 2362586 bytes, checksum: de75d2d7f7b0ebf296ee1a44eeb6874f (MD5) Previous issue date: 2012-08-29 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esta dissertação tem como foco principal a avaliação do emprego de um conversor de baixo custo, operando em baixa frequência, para o acionamento de diodos emissores de luz (LEDs) usados em luminárias de baixa potência. A proposta considera inicialmente um conversor CA-CC conhecido como pré-regulador boost de alto fator de potência operando em baixa frequência, ou seja, um único acionamento liga-desliga para cada semiciclo da rede elétrica. Um protótipo experimental com potência de saída de 11 W foi implementado e comprova a possibilidade de emprego do conversor pretendido. Neste caso, foi observada por meio de avaliação fotométrica uma redução de 11% na eficácia luminosa do conjunto luminoso, em comparação com operação CC ideal, algo que se atribui à natureza descontínua da corrente nos LEDs. O pré-regulador apresentou um fator de potência de 0,97 e uma eficiência de 59%, em especial devido ao uso de um transformador abaixador de baixa frequência sobredimensionado. Pelo fato de impor à lâmpada uma corrente descontínua, o conversor proposto não emprega capacitores eletrolíticos, característica que contribui para uma elevada vida útil do circuito de acionamento. Um circuito similar, orientado à iluminação pública e que dispensa o uso de transformadores abaixadores, também é avaliado com apoio de simulação computacional. Neste caso, pode ser esperada uma eficiência global muito mais elevada. Outro pré-regulador baseado no mesmo princípio, porém empregando uma topologia tipo Ćuk, também é avaliado por meio de simulações, permitindo-se antever uma proposta de baixo custo, acionamento simplificado, elevada eficiência global, elevada eficácia luminosa e elevada vida útil. Finalmente, um estudo complementar desta dissertação considera a influência do posicionamento geométrico dos LEDs para a distribuição luminosa no plano de trabalho. Uma análise matemática e experimental é conduzida neste sentido e contribuiu para a alocação das unidades luminosas ao longo da barra de suporte da luminária de baixa potência implementada. / This work is mainly focused on the evaluation of the use of a low-frequency and low-cost converter intended to drive light emitting diodes employed in low power lighting fixtures. The proposal considers at first a high power factor boost pre-regulator converter featuring a low frequency switching of the main power device, which is driven twice each electric mains cycle. An experimental prototype with output power of 11 W is implemented and proves the concept feasibility. In this case, photometry studies show a reduction of 11% in the LEDs luminous efficacy, as compared to an ideal DC operation, which is due to the discontinuous nature of the output current. The boost pre-regulator presented a power factor of 0.97 and a global efficiency of 59%, something that can be imputed to the use of an underrated low frequency transformer. Despite some disadvantages, the discontinuous nature of LEDs current allows the converter to avoid using electrolytic capacitors, what confers an extended lifetime to the proposed driver. A similar circuit, which does not need transformers at all and is devised to be employed in street lighting, is also evaluated by means of numerical simulation. Moreover, another low frequency pre-regulator based on the Ćuk converter is evaluated with the aid of computer simulation, and the results show that it could be attained in practice a high global efficiency, high luminous efficacy and extended driver lifetime. Finally, a complementary study accomplished during this dissertation evaluates the influence of the geometric positioning of the LEDs for the luminous distribution over a given plane to be lit. Mathematical and experimental analysis have been developed contributing for the right allocation of lighting unities along the heatsink bar which bears the lighting fixture prototype.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-04-24T15:04:21Z No. of bitstreams: 1 luizfernandoalvesguedes.pdf: 8533376 bytes, checksum: 1fb75359e16225fb5b36b42d374e4b7a (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-04-24T16:59:50Z (GMT) No. of bitstreams: 1 luizfernandoalvesguedes.pdf: 8533376 bytes, checksum: 1fb75359e16225fb5b36b42d374e4b7a (MD5) / Made available in DSpace on 2017-04-24T16:59:50Z (GMT). No. of bitstreams: 1 luizfernandoalvesguedes.pdf: 8533376 bytes, checksum: 1fb75359e16225fb5b36b42d374e4b7a (MD5) Previous issue date: 2012-12-17 / Este trabalho tem o objetivo de estudar, projetar, simular e obter resultados experimentais, a partir de um conversor flyback operando no modo descontínuo (DCM), para acionar uma luminária de diodos emissores de luz (LEDs). Além disso, deseja-se que o conversor possua elevado fator de potência, alta eficiência, baixa distorção harmônica da corrente de entrada, vida útil elevada (através da possibilidade de substituir de capacitores eletrolíticos por capacitores de filme metálico) e baixo custo. Inicialmente, o trabalho apresenta um breve estudo da iluminação a LEDs, o modelo elétrico simplificado dos LEDs, bem como uma revisão de alguns conversores aplicados ao acionamento deste tipo de fonte luminosa. Em seguida é analisada a operação do conversor flyback em modo DCM alimentado a partir da retificação (em ponte) da tensão da rede elétrica. Além do estudo teórico, a simulação do conversor é apresentada de modo a validar o projeto do conversor e servir de base de comparação com os resultados experimentais. O projeto do transformador (indutores acoplados) do conversor flyback tem destaque especial neste trabalho, pois, este elemento é fundamental para elevar a eficiência do conversor. Portanto, parte deste trabalho é dedicada ao estudo de perdas do transformador. Isto é feito através de uma adaptação de técnicas consagradas nesta área por meio de uma compilação didática visando a repetitividade do estudo. A partir do estudo teórico sobre as perdas no transformador, programas elaborados no MATLAB e no MICROSOFT EXCEL auxiliam o projeto do elemento magnético do conversor flyback. Estes dois programas, visam facilitar o exaustivo equacionamento das perdas e auxiliam no desenvolvimento de um projeto com elevada eficiência do transformador flyback elevando, consequentemente, a eficiência global do conversor. Empregando os programas elaborados, o projeto é calculado e resultados experimentais são obtidos a partir de medições realizadas em um protótipo em escala. Estes resultados são analisados e comparados com os resultados teóricos e de simulação. Ao final, é realizada uma análise simplificada do custo dos componentes do conversor e também são apresentadas as principais conclusões deste trabalho. / This work aims to study, design, simulate and obtain experimental results from a flyback converter operating in discontinuous mode (DCM), to trigger a fixture of light emitting diodes (LEDs). Furthermore, it is desired that the converter has high power factor, high efficiency, low harmonic distortion of input current, high life (through the possibility of replacing the electrolytic capacitors for metal film capacitors) and low cost. Initially, the paper presents a brief study of lighting LEDs, LEDs for simplified electrical model, as well as a review of some converters used to drive this type of light source. Then it analyzed the operation of the flyback converter in DCM mode fed from the rectification (bridged) the utility voltage. Besides the theoretical study, the simulation of the converter is presented in order to validate the design of the converter as a basis for comparison with experimental results. The transformer design (coupled inductors) flyback converter has special emphasis in this work, because this element is essential to raise the efficiency of the converter. So part of this work is devoted to the study of transformer losses. This is done by an adaptation of standard techniques in this area via a teaching order to build repeatability study. From the theoretical study on the losses in the transformer, programs developed in MATLAB and MICROSOFT EXCEL aid the design of the magnetic element of the flyback converter. These two programs are designed to facilitate the comprehensive equating of losses and assist in developing a project with high efficiency flyback transformer raising therefore the overall efficiency of the converter. Employing the programs drawn up, the project is calculated and experimental results are obtained from measurements performed on a prototype scale. These results are analyzed and compared with the theoretical results and simulation. At the end we provide a simplified analysis of the cost of the converter components and also presents the main conclusions of this work.

Submitted by Geandra Rodrigues (geandrar@gmail.com) on 2018-10-24T15:44:07Z No. of bitstreams: 1 leisabrandrios.pdf: 3333252 bytes, checksum: eb46615b96454ef8cb84c80277532dff (MD5) / Approved for entry into archive by Renata Lopes (renatasil82@gmail.com) on 2018-11-06T13:27:31Z (GMT) No. of bitstreams: 1 leisabrandrios.pdf: 3333252 bytes, checksum: eb46615b96454ef8cb84c80277532dff (MD5) / Made available in DSpace on 2018-11-06T13:27:31Z (GMT). No. of bitstreams: 1 leisabrandrios.pdf: 3333252 bytes, checksum: eb46615b96454ef8cb84c80277532dff (MD5) Previous issue date: 2017-02-17 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, filmes finos de Óxido de Índio-Estanho (ITO) foram crescidos sobre substratos de vidro e de quartzo, pela técnica de deposição por pulverização catódica com radiofrequência assistida por um campo magnético constante do inglês “RF Magnetron Sputtering” à temperatura ambiente. O objetivo do trabalho foi estudar a influência dos parâmetros de deposição nas propriedades elétricas, ópticas e estruturais desses filmes. Caracterizações elétricas, ópticas e estruturais foram realizadas, respectivamente, por medidas de Efeito Hall, absorção óptica no UV-VIS e difração de Raios-X. Observou-se que os parâmetros de deposição - potência de pulverização e pressão de trabalho - têm forte influência sobre as propriedades elétricas e estruturais dos filmes finos ITO, mas a transmitância óptica na região visível (400 ˂ λ ˂ 700) nm sempre esteve acima de 80% para todos os filmes a 550 nm. Por meio das medidas de difração de Raios-X verificamos que os filmes apresentaram pequena orientação na direção [111] e a cristalinidade dos filmes aumentou com o acréscimo da potência de pulverização. A otimização dos parâmetros de crescimento reduziu a resistividade elétrica dos filmes, principalmente devido ao aumento da concentração e da mobilidade dos portadores de carga. Os melhores filmes finos foram obtidos com a potência de pulverização de 140 W, pressão de trabalho de 0,08 mbar e fluxo de argônio de 300 sccm, com baixa resistividade elétrica, e mobilidade e concentração de portadores elevadas de, respectivamente, 8,81 x 10⁻⁴ Ωcm, 9,98 cm²/Vs e 6,30 x 10²⁰ cm⁻³, aliados a uma alta transmitância óptica de 97,7% em 550nm e gap óptico de 3,78 eV. O filme otimizado foi utilizado como cátodo em um diodo emissor de luz orgânico (OLEDs) que apresentou uma eficiência satisfatória quando comparado a um dispositivo similar feito com ITO comercial. O próximo passo foi produzir um diodo emissor de luz orgânico transparente (TOLED), que emite luz para ambos os lados usando filmes transparentes de ITO para ânodo e cátodo. Para isso, as películas de ITO foram depositadas sobre camadas orgânicas, que são sensíveis a potências de pulverização elevadas. Assim, uma nova série de deposições com diferentes pressões de trabalho foram realizadas mantendo-se a potência fixa em 40 W. O melhor filme com esta potência menor foi obtido com pressão de trabalho de 0,08 mbar e fluxo de argônio de 300 sccm. Estes filmes apresentaram, como resistividade elétrica, mobilidade e concentração de portadores, 3,99 x 10⁻³ Ωcm, 2,07 cm²/Vs e 7,55 x 10²⁰ cm⁻³, respectivamente. Eles também mostraram uma transmitância acima de 92% para 400 < λ < 700 nm e gap óptico de 3,50 eV. Através das medidas de XRD, verificamos que todos os filmes depositados com baixa potência de pulverização apresentaram uma banda amorfa com picos de difração referentes a direção [111] com baixa intensidade, indicando que as películas são praticamente amorfas. Finalmente, serão apresentados os resultados da caracterização de TOLEDs, utilizando os filmes de ITO otimizados fabricados com uma potência de 40 W. / In this work, thin films of Indium-Tin Oxide (ITO) were grown onto glass and quartz substrates by R.F. Magnetron Sputtering deposition technique at room temperature. The objective of this work was to study the influence of deposition parameters on the electrical, optical and structural properties of these films. Electrical, optical and structural characterizations were performed, by Hall Effect measurements, UV-VIS optical absorption and X-ray diffraction, respectively. It was observed that the deposition parameters – sputtering power and working pressure– have a strong influence on the electrical and structural properties of ITO thin films, but the optical transmittance in the visible region (400 ˂ λ ˂ 700) nm was always above 80 % for all films at 550 nm. By means of the XRD measurements, we verified that the films showed small orientation in the direction [111] and the crystallinity of the films increased with the increase of the sputtering power. The optimization of growth parameters reduced the electrical resistivity of the films mainly because of the increase of carrier concentration and carrier mobility. Thin films with the best electrical properties were obtained with sputtering power of 140 W, working pressure of 0.08 mbar and argon flow of 300 sccm. The best ITO thin films had electrical resistivity of 8.81 x 10⁻⁴ Ωcm, mobility of 9.98 cm²/Vs, and carrier concentration of 6.30 x 10²⁰ cm⁻³ together with a high optical transmittance of 97.7 % at 550 nm and a band gap of 3.78 eV. The optimized film was used as cathode in an organic light-emitting diode (OLEDs) that presented a satisfactory efficiency when compared to a similar device made with commercial ITO. The next step was to produce a Transparent Organic Light Emitting Diode (TOLED), which emits light from both sides by using ITO transparent films for both anode and cathode. To do so, ITO films were deposited on top of organic active layers, which are sensitive to high sputtering powers. So a new series of depositions with different working pressures were performed with a fixed power of 40 W. The best film with this smaller power was obtained with working pressure of 0.08 mbar and argon flow of 300sccm. These films presented, as electrical resistivity, mobility and carrier concentration, 3.99 x 10⁻³ Ωcm, 2.07 cm2 / Vs and 7.55 x 10²⁰ cm⁻³, respectively. They also showed a transmittance above 92 % for 400 < λ < 700 nm and band gap of 3.50 eV. Through X rays difraction measurements, we verified that all films deposited with low sputtering power presented an amorphous band with diffraction peaks referring to the [111] direction with low intensity, indicating that the films are practically amorphous. Finally, the results of the characterization of TOLEDs presented, using the optimized ITO films made with a sputtering power of 40 W.

The present thesis deals with a theoretical study of electronic structures in -conjugated molecular materials with focus on their application in organic elec-tronics. We also discuss a modified and efficient symmetrized DMRG algorithm for studying excited states in these systems. In recent times, organic conjugated systems have emerged as potential candidates in a wide range of fascinating fields by virtue of their tunable electronic properties, easy processability and low cost. Tunability in the electronic and optical properties primarily are centered on the or-dering and nature of the low-lying excited states. Probing these important excited states also demands development of efficient and adaptable techniques. Chapter 1 provides a basic overview of conjugated organic polymers which have been utilized over decades in diverse fields as in organic light emitting diodes (OLED), organic solar cells (OSC) and non-linear optical (NLO) devices. These systems also contribute significantly to theoretical understanding as they pro vide important insights of one and quasi-one dimensional systems. In this chapter, we have given basic description of the electronic processes in OLED and OSC along with a brief theoretical description of -conjugated organic systems. Chapter 2 gives an account of the numerical techniques which are necessary for the study of low-dimensional strongly correlated systems like -conjugated sys-tems. For this purpose, effective low-energy model Hamiltonians viz. Huckel,¨ Hubbard and Pariser-Parr-Pople Hamiltonians are discussed. Exact diagonalization technique within the diagrammatic valence bond (DVB) basis and density matrix renormalization group (DMRG) technique are discussed in details. We have also given brief accounts of the methods employed to study real-time dynamics. A short description of different computational techniques for the study of NLO properties in -conjugated systems is also provided. Engineering the position of the lowest triplet state (T1) relative to the first excited singlet state (S1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. In chapter 3, we have carried out model exact calculations of substituted polyene chains to understand the fac-tors that affect the energy gap between S1 and T1. The factors studied are backbone dimerization, different donor-acceptor substitutions and twisted backbone geome-try. The largest system studied is an eighteen carbon polyene which spans a Hilbert space of about 991 million in the triplet subspace. We show that for reverse inter-system crossing (RISC) process, the best choice involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in OSC. In chapter 4, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dy-namics. In the non-interacting model, SF is absent. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interac-tion between them involves transfer terms, intersite electron repulsions and site-charge—bond-charge repulsion terms. Initial wave packet is construc ted from ex-cited singlet state of one molecule and ground state of the other. Time develop-ment of this wave packet under the influence of intermolecular interactions is fol-lowed within the Schrodinger¨ picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, 21A state leads to significant SF yield while the 11B state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, the lowest excited state will have sufficient 2 1A char-acter and hence gives significant SF yield. Because of rapid internal c onversion, the nature of the lowest excited singlet will determine the SF contribution to OSC effi - ciency. Furthermore, we find the fission yield depends considerably on th e stacking arrangement of the polyene molecules. In chapter 5, we have given an account of a new modified algorithm for symmetry adaptation within symmetrized density matrix renormalization group (SDMRG) technique. SDMRG technique has been an efficient method for studying low-lying eigenstates in one and quasi-one dimensional electronic systems. However, SDMRG method until now, had bottlenecks involving construction of linearly in-dependent symmetry adapted basis states as the symmetry matrices in the DMRG basis were not sparse. Our modified algorithm overcomes this bottleneck. T he new method incorporates end-to-end interchange symmetry (C2), electron-hole symmetry (J) and parity or spin-flip symmetry (P) in these calculations. The one-to-one correspondence between direct-product basis states in the DMRG Hilbert space for these symmetry operations renders the symmetry matrices in the new ba-sis with maximum sparseness, just one non-zero matrix element per row. Using methods similar to those employed in exact diagonalization technique for Pariser-Parr-Pople (PPP) models, developed in the eighties, it is possible to construct or-thogonal SDMRG basis states while bypassing the slow step of Gram-Schmidt orthonormalization procedure. The method together with the PPP model which incorporates long-range electronic correlations is employed to study the correlated excited states of 1,12-benzoperylene. In chapter 6, we have studied the correlated excited states of coronene and ova-lene within Pariser-Parr-Pople (PPP) model employing symmetry adapted density matrix renormalization group technique. These polynuclear aromatic hydrocar-bons can be considered as graphene nanoflakes and study of their ele ctronic struc-tures will shed light on the electron correlation effects in these finite-size gr aphene analogues. The electron correlation effect usually diminishes on going from one-dimensional to higher-dimensional systems, yet, it is significant within these fin ite-size graphene derivatives where it depends on the molecular topology. We have characterized these low-lying energy states by calculating bond orders, spin den-sities in the lowest triplet state and two-photon absorption cross-sections for low-lying two-photon states. vi

Les diodes électroluminescentes organiques (OLED) ont une durée de vie limitée. Cette limitation est notamment due à la présence d'impuretés dans le matériau électroluminescent. Ces impuretés proviennent principalement des électrodes. Nous pensons que l'ajout de couches de matériaux entre les électrodes et le matériau électroluminescent peut retarder l'arrivée des impuretés. Cette couche ajoutée doit avoir plusieurs caractéristiques dont principalement :être conductrice, ne pas absorber la lumière, être facilement mise en oeuvre et être d'une grande pureté. Nous pensons que des matériaux de type discotique possédant une mésophase aux températures d'utilisation de la OLED peuvent remplir ce cahier des charges.<p>Nous avons choisi d'étudier les composés discotiques à base de triphénylène, car celui-ci n'absorbe pas dans le visible. Nous avons tout d'abord étudié les 2,3,6,7,10,11-Hexa-(alkylthio)triphénylènes (HATT). Les HATT possèdent déjà les propriétés physiques que nous recherchons à l'exception des propriétés thermotropes. Nous avons donc étudié la possibilité de modifier celles-ci.<p>La synthèse de plusieurs HATT possédant six chaînes alkylsulfanyles identiques n'a pas donné les résultats attendus du point de vue des propriétés thermotropes. Nous avons alors synthétisé des molécules possédant plusieurs chaînes alkylsulfanyles différentes. Après différents essais, nous avons trouvé un mélange de molécules possédant plusieurs chaînes latérales différentes ayant les propriétés physiques recherchées. Mais ce matériau est composé d'un grand nombre de molécules et sa purification est difficile. Les techniques classiques de purification des composés organiques ne donnant pas une pureté suffisante, ou étant inapplicables sur une mésophase cristal liquide à température ambiante, nous avons donc recherché d'autres techniques de purification ou d'obtention des propriétés thermotropes désirées.<p> Nous avons étudié la purification par raffinage de zone des matériaux à l'aide d'une impureté que nous avons ajoutée et suivie au cours des manipulations. Le raffinage de zone montre une bonne purification lors de l'utilisation d'une transition de phase entre une phase cristalline et une phase liquide. Par contre, lors de l'utilisation d'une transition impliquant une mésophase (cristal liquide ou cristal plastique), une faible (ou une absence de) purification est observée. Ces deux dernières études ont été faites sur des 2,3,6,7,10,11-Hexa(alkyloxy)triphénylènes (HAOT) que nous avons synthétisés et purifiés au préalable. <p>Les gels de silice fonctionnalisés que nous avons utilisés montrent une purification des cations métalliques durs et, dans une moindre mesure, des cations métalliques intermédiaires dans le concept dur-mou. Le phosphore, seul élément non-métallique que nous ayons étudié, est l'élément dont la baisse de concentration est la moins efficace.<p>La seconde approche pour obtenir des mélanges possédant une mésophase cristal liquide à température ambiante est la formation de mélanges de molécules synthétisées et purifiées isolément. Parmi les mélanges de molécules que nous avons effectués, nous avons pu observer une plage de concentration de mélanges ternaires qui possède les propriétés thermotropes recherchées.<p>Nous avons donc obtenu un matériau cristal liquide à température ambiante grâce à un mélange de molécules. Le matériau ainsi formé absorbe peu dans le visible, possède potentiellement une bonne mobilité des porteurs de charges électriques, est facilement obtenu à une pureté suffisante. Ce mélange de molécules possède donc les propriétés que nous recherchons pour être utilisé comme couche de matériau ajoutée aux OLED.<p> / Doctorat en sciences, Spécialisation chimie / info:eu-repo/semantics/nonPublished

White organic light-emitting diodes (OLEDs) are promising candidates for future solid-state lighting applications and backplane illumination in large-area displays. One very specific feature of OLEDs, which is currently gaining momentum, is that they can enable tunable white light emission. This feature is conventionally realized either through the vertical stacking of independent OLEDs emitting different colors or in lateral arrangement of OLEDs. The vertical design is optically difficult to optimize and often results in efficiency compromises between the units. In contrast, the lateral concept introduces severe area losses to dark regions between the subunits, which requires a significantly larger overall device area to achieve equal brightness. Here we demonstrate a color-tunable, two-color OLED device realized by side-by-side alignment of yellow and blue p-i-n OLEDs structured down to 20 μm by a simple and up-scalable orthogonal photolithography technique. This layout eliminates the problems of conventional lateral approaches by utilizing all area for light emission. The corresponding emission of the photo-patterned two-unit OLED can be tuned over a wide range from yellow to white to blue colors. The independent control of the different units allows the desired overall spectrum to be set at any given brightness level. Operated as a white light source, the microstructured OLED reaches a luminous efficacy of 13 lm W−1 at 1000 cd m−2 without an additional light outcoupling enhancement and reaches a color rendering index of 68 when operated near the color point E. Finally, we demonstrate an improved device lifetime by means of size variation of the subunits.

White organic light-emitting diodes (OLEDs) are promising candidates for future solid-state lighting applications and backplane illumination in large-area displays. One very specific feature of OLEDs, which is currently gaining momentum, is that they can enable tunable white light emission. This feature is conventionally realized either through the vertical stacking of independent OLEDs emitting different colors or in lateral arrangement of OLEDs. The vertical design is optically difficult to optimize and often results in efficiency compromises between the units. In contrast, the lateral concept introduces severe area losses to dark regions between the subunits, which requires a significantly larger overall device area to achieve equal brightness. Here we demonstrate a color-tunable, two-color OLED device realized by side-by-side alignment of yellow and blue p-i-n OLEDs structured down to 20 μm by a simple and up-scalable orthogonal photolithography technique. This layout eliminates the problems of conventional lateral approaches by utilizing all area for light emission. The corresponding emission of the photo-patterned two-unit OLED can be tuned over a wide range from yellow to white to blue colors. The independent control of the different units allows the desired overall spectrum to be set at any given brightness level. Operated as a white light source, the microstructured OLED reaches a luminous efficacy of 13 lm W−1 at 1000 cd m−2 without an additional light outcoupling enhancement and reaches a color rendering index of 68 when operated near the color point E. Finally, we demonstrate an improved device lifetime by means of size variation of the subunits.

A new dual-boron-cored luminogen ligated with a nitrogen-containing multidentate ligand and four bulky phenyl rings was readily synthesized. The unique molecular structure endows this BN-containing luminogen with rich photophysical properties in either solution or in the solid state, including a large Stokes shift, aggregation induced emission activity and reversible piezochromism. Furthermore, this BN-containing luminogen exhibits good capabilities for imaging living cells and sensing of fluoride anions.