O presente trabalho tem como objetivo estudar os processos radiativos e não radiativos em filmes automontados de poli(p-fenileno vinileno), ou PPV, sintetizados e processados no Grupo de Polímeros Prof. Bernhard Gross (GPBG) do IFSC. Além de adquirir conhecimento das propriedades ópticas fundamentais, tais como, os mecanismos básicos responsáveis pela emissão de luz, foram investigados os efeitos da temperatura, da redução da dimensionalidade através do tamanho efetivo de conjugação, das impurezas e dos defeitos estruturais. Foram realizados estudos das propriedades ópticas desse material através das seguintes técnicas espectroscópicas: fotoluminescência (PL), absorção óptica, fotoluminescência por excitação seletiva (PLE). As propriedades estruturais e de superfícies do PPV foram estudadas por infravermelho (IR) e microscopia de força atômica (AFM). A adsorção de camadas alternadas do polímero precursor poli(cloreto de tetrahidrotiofeno de xilideno) (PTHT) e do íon de cadeia longa dodecilbenzenosulfônico (DBS) propiciou a formação de filmes finos com controle de monocamada. A introdução do DBS permitiu a conversão rápida (~10min) destes filmes em PPV a temperaturas muito mais baixas (~100 'graus'C) e com baixa incorporação de defeitos do que aquelas usadas convencionalmente. A boa qualidade estrutural e o alto grau de conjugação destes filmes de PPV foram responsáveis pela boa resolução dos espectros de absorção e emissão, o que permitiu fazer um estudo teórico mais detalhado das propriedades ópticas básicas deste material. Demonstramos que as transições ópticas em polímeros conjugados podem ser descritas pela intensidade da linha de zero-fônon 'I IND.o', pela sua largura 'TAU' e posição 'E IND.o', bem como pelo acoplamento entre os níveis eletrônicos e vibracionais descrito pelo fator Huang-Rhys S. Mostramos que estes parâmetros são profundamente influenciados pela desordem conformacional da cadeia introduzida pela temperatura e pela variação do grau de conjugação. Em especial, consideramos explicitamente a estrutura vibracional do PPV levando-se em conta a aproximação teórica de Franck-Condon de modo a explicar o espectro de emissão experimental. Fomos capazes de reproduzir os espectros de PPV quando consideramos três modos vibracionais efetivos com energias correspondentes em 330, 1164 e 1550 cm-1, que correspondem a estruturas vibracionais intensas do PPV obtidas por espectroscopia de absorção infravermelho e Raman. Do estudo da forma de linha obtivemos pela primeira vez que acoplamento elétron-fônon parametrizado pelo fator S possui diferente dependência com a temperatura para cada um dos modos efetivos. Desta forma, pudemos obter aspectos fundamentais do acoplamento entre os estados eletrônicos e o movimento nuclear em polímeros conjugados que ainda não tinham sido estudados em detalhe na literatura. / The subject of this work is the investigation of the radiactive and non-radiactive processes in poly (p-phenylene vinylene) self-assembled films (PPV), which were synthesized and processed at the Grupo de Polímeros Bernhard Gross (GPBG) of the IFSC. Besides the investigation of the fundamental optical properties, such as the basic mechanisms responsible for light emission, temperatures effects, dimensional reduction, impurities and structural effects were investigated. We investigation the optical properties of this material using the following spectroscopic techniques: photoluminescence (PL), optical absorption and selective excitation photoluminescence (PLE). The structural and superficial properties of PPV were investigated by infrared absorption (IR) and atomic force microscopy (AFM). The adsorption of alternated layers of the precursor polymer poly(xylylidenetetrahydrothiophenium chloride) (PTHT) and the long chain ion dodecylbenzenesulfonate (DBS) permitted the formation of thin films with monolayer control. The introduction of the DBS allowed the rapid conversion (~10min) of this films into PPV at much lower temperatures (~100 oC) and with less defect incorporation than conventional PPV films. The good structural quality and the high conjugation degree of this films were responsible for the high resolution of the vibronic structures in the absorption and emission spectra, which allowed us to make a detailed theoretical study of this material’s basic optical properties. We have shown that the optical transitions in conjugated polymers may be described by the intensity of the zero-phonon line Io, its width 'TAU' and position Eo, as well as by the electronic and vibrational coupling described by the Huang-Rhys factor, S. These parameters are highly influenced by the chain conformational disorder introduced by the temperature and the variation of the conjugation degree. In order to explain the experimental emission spectra we have explicitly considered the vibrational structure of PPV taking into account the theoretical Franc-Condon approximation. We have been able to reproduce these spectra considering three effective vibrational modes with energies at 330, 1164 and 1550 cm-1, which correspond to intense PPV vibrational structures obtained by infrared and Raman absorption spectroscopy. Studying the line shape we found that the electron-phonon coupling of each effective mode, parameterized by the S factor, has different temperature dependence. This work has allowed us to investigate fundamental aspects of the coupling between electronic states and nuclear movement in conjugated polymers that had not yet been studied in detail in the literature.

As células eletroquímicas emissoras de luz são dispositivos eletroluminescentes cuja camada ativa é uma mistura de um material eletroluminescente e um eletrólito sólido a base de sais de metais alcalinos, geralmente lítio. A presença dos íons na camada ativa modificam o mecanismo de funcionamento das células quando comparadas ao diodos emissores de luz. Nas células, a concentração de íons nas interfaces eletródicas forma uma dupla camada elétrica que auxilia a injeção de cargas na camada ativa, por sua vez e na presença dos íons, o material eletroluminescente sofre dopagem se tornando condutor, os portadores injetados irão se encontrar numa região da camada ativa recombinando-se e emitindo luz. Compreender as interações dos diversos materiais que formam a camada ativa é fundamental para otimizar o desempenho do dispositivo. Neste trabalho estudamos a interação do ADS108GE, um polímero luminescente, e um eletrólito sólido a base de poli (óxido de etileno) (PEO) e LiCF3SO3 ou LiB(C2O4)2. O LiB(C2O4)2 foi sintetizado neste trabalho para estudar a viabilidade de se substituir o LiCF3SO3 que é o sal tipicamente utilizado nas células. Foram utilizadas técnicas de Análise Dinâmico-Mecânica (DMA), Espectroscopia Vibracional no Infravermelho (FTIR), Microscopia de Força Atômica (AFM), Difração de Raios-X (DRX), Microscopia Óptica de Varredura no Campo Próximo (IR-SNOM), Impedância Elétrica e Voltametria Cíclica. Os resultados de DMA em conjunto com DRX e AFM, permitiram estabelecer que o aumento da concentração de sal contribui para mudanças morfológicas que se relacionam com o aumento da fração de fase amorfa e independem do ânion, demonstrando que estes efeitos estão ligados à interação PEO-Lítio. Por outro lado, os espectros de FTIR e resultados de impedância elétrica mostram que o aumento da concentração de LiCF3SO3 gera agregação do sal diminuindo a condutividade, a mobilidade iônica e o número de portadores efetivos, enquanto para o LiB(C2O4)2 não se observa tal efeito. O IR-SNOM permitiu identificar nas misturas utilizadas como camada ativa que o ADS108GE forma estruturas globulares embebidas numa matriz de PEO. Do ponto de vista operacional, as células a base de LiB(C2O4)2 possuem uma eficiência maior do que as a base LiCF3SO3 e maior estabilidade. / Light-emitting electrochemical cells are electroluminescent devices whose active layer is a mixture of an electroluminescent material and a solid electrolyte based on alkaline salts, usually a lithium salt. The ions within thea ctive layer change the devices working mechanism when compared to light emitting diodes. In the cells, there is an ion build up at electrodic interfaces creating an electric double layer allowing charge injection in the active layer. The electroluminescent material is doped by these injected charges becoming conductive. These injected charges recombine emitting light. In order to optimize devices performance, it is fundamental to study materials interactions when mixed as an active layer. In this work, we studied the interactions between ADS108GE, a luminescent polymer, and a solid electrolyte based on polyethylene oxide and LiCF3SO3 or LiB(C2O4)2. LiB(C2O4)2 was prepared in this work to assess its feasibility as LiCF3SO3 substitution which is the typical choice. We used the following techniques in this work: Dynamical Mechanical Analysis (DMA), Infrared Vibration Spectroscopy (FTIR), Atomic Force Microscopy AFM), X-Ray Diffraction (XRD), Infrared Scanning Near-Field Optical Microscopy (IRSNOM), Electrical Impedance and Cyclic Voltammetry. From DMA, XRD and AFM results, it is possible to conclude that as we increase salt concentration, the active layer has morphological changes related to an increasing fraction of an amorphous phase. These effects are anion independent showing that PEO-Li interactions are the responsible ones. On the other hand, FITR and electrical impedance experiments show that increasing LiCF3SO3 concentration leads to salt aggregation decreasing conductivity, ionic mobility and the effective number of carriers, moreover, we do not see this effect with LiB(C2O4)2. IR-SNOM identified that ADS108GE were organized as globular structures embedded in a PEO matrix. The cells made with LiB(C2O4)2 were more efficient than those based on LiCF3SO3 and were even more stable.

Au cours de cette thèse, nous avons synthétisé de nouveaux composés en utilisant des macrocycles de porphyrines comme socle pour nos architectures. L'objectif était d'étudier leurs propriétés en optique linéaire et non linéaire. Plus précisément, nous avons synthétisé et caractérisé trois groupes de dendrimères de type fluorényl-porphyrine, une série de porphyrines organométalliques dérivés du ruthénium, et commencé une dernière série de nouvelles porphyrines. Les corrélations entre les propriétés et la structure ont été étudiés, le processus de transfert d'énergie du donneur vers la porphyrine a aussi été évalué. En introduction, nous avons présenté le contexte général de la chimie des porphyrines basé sur quatre aspects: (1) la structure chimique, (2) les voies de synthèse, (3) les propriétés en optique linéaire (4) et en optique non linéaire. Nous avons ensuite présenté les différents travaux qui ont été effectués dans notre groupe, et conclut en proposant de nouvelles structures basées sur ces résultats. Dans le premier chapitre, nous présentons la synthèse d'un groupe de dendrimères dérivés de thiényl-porphyrines. Les unités thiényles font le pont entre les dendrons conjugués de type fluorényle et le coeur de la porphyrine. Le transfert d'énergie pour ces molécules est efficace et ces dernières présentent des propriétés en optique non linéaire qui sont intéressantes avec une amélioration de l'absorption à deux photons (ADP). Dans le deuxième chapitre, nous présentons la synthèse d'une série de composés à base de ruthénium dérivés de la Tétrafluorényl- porphyrine (TFP), pour des applications en optique non linéaire (üNL). Dans le troisième chapitre, nous présentons la synthèse de deux nouveaux dendrons avec des antennes fluorényles terminales greffées en position 9 d'un troisième fluorényle, respectivement par voie conjuguées ou non conjuguées. Puis deux nouveaux dendrimères ont été obtenus par couplage de Sonogashira à partir de ces dendrons sur le coeur porphyrine TFP. Le transfert d'énergie de ces dendrons vers la porphyrine est efficace. Ces molécules présentent des propriétés en optique non linéaire qui sont intéressantes et les résultats en ADP sont très prometteurs. Dans le quatrième chapitre, nous présentons la synthèse de porphyrines avec des bras fluorénones terminales. Ces porphyrines émettent également une luminescence rouge et le transfert d'énergie est très efficace. Comme perspectives, un nouveau type de porphyrine méso-alcynyle est envisagé, pour l' instant nous avons juste synthétisé la génération 0 de cette série de dendrimères: Les quatre bras tluorényles sont pontés au coeur de la porphyrine avec des liens alcynyles, et les études optiques de ces prototypes sont en cours. / During this thesis, we have elaborated new compounds using the porphyrin macrocycle as the basic platform of our architectures. The aim, after their syntheses, was to study the linear optical (LO) and non-linear optical (NLO) properties of these new molecules. More precisely, we have synthesized and characterized three groups of fluorenyl-porphyrin dendrimers, a series of ruthenium organometallic porphyrins, and started a series of new type of porphyrin. Their correlations on optical property-structure have been discussed, as well as the energy transfer processes from the donor fragments to porphyrin core acceptor. In the introduction, we presented the general background of the porphyrin chemistry based on four aspects: ( I) structure, (2) synthetic methods, (3) LO properties and (4) NLO properties. We further reviewed prior porphyrin studies done in our group and proposed new molecular designs based on these results. In the first chapter, we synthesized a group of thienyl porphyrin cored dendrimers. The thienyl units connect the conjugated fluorenyl dendrons to porphyrin ring by alkynyl bridges. The energy transfer (ET) of these porphyrins is very efficient and they present interesting NLO properties with enhanced Two-photon absorption (TPA). In the second chapter, we synthesized a series of ruthenium compounds based on Tetra-fluorenyl porphyrin core (TFP) for NLO applications. In the third chapter, we synthesized two new dendrons with two terminal fluorenyl antennae fi xed on the 9 position of the fluorenyl units in conjugated or non-conjugated way respecti vely. Then two new porphyrin dendrimers were obtained by Sonogashira coupling reaction of these dendrons on TFP porphyrin core. Their ET from dendrons to porphyrin core is very efficient. They present interesting LO properties and the TPA results are very promising. In the fourth chapter, we synthesized a group of TFP cored porphyrins with terminal fluorenone anns. These porphyrins emit red luminescence and the ET is very efficient from the linear arms toward their cores. As perspective, a new type of meso-alkynyl porphyrin series is considered, for the moment we synthesized only the generation 0 of the dendrimers: the four fluorenyl arms of this porphyrin are bridged to the centre ring by alkynyl chains, and the optical studies of this prototype are in progress.

by Yeung Mei Ki. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 122-127). / Text in English; abstracts in English and Chinese. / by Yeung Mei Ki. / Abstract --- p.i / 論文摘要 --- p.iii / Acknowledgements --- p.iv / Table of Contents --- p.v / List of Figures --- p.viii / List of Tables --- p.xi / Abbreviations --- p.xii / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Polymer light emitting devides --- p.1 / Chapter 1.1.1 --- Development history of PLEDs --- p.3 / Chapter 1.1.2 --- Basic structure of the PLEDs --- p.4 / Chapter 1.1.3 --- Operation principle of the PLEDs --- p.7 / Chapter 1.1.4 --- Electroluminescent (EL) polymers --- p.9 / Chapter 1.2 --- Research motivation and aim of study --- p.11 / Chapter 1.3 --- Thesis outline --- p.16 / Chapter Chapter 2 --- Instrumentation / Chapter 2.1 --- Thermal analysis --- p.18 / Chapter 2.1.1 --- Thermogravimetry (TG) --- p.19 / Chapter 2.1.2 --- Differential scanning calorimetry (DSC) --- p.22 / Chapter 2.2 --- Spectroscopic analysis --- p.27 / Chapter 2.2.1 --- Fourier transform infrared spectroscopy (FTIR) --- p.27 / Chapter 2.2.2 --- X-ray photoelectron spectroscopy (XPS) --- p.32 / Chapter 2.2.3 --- Photoluminescence spectroscopy (PL) --- p.36 / Chapter Chapter 3 --- Experimental metods to charaterize the elimination of / Chapter 3.1 --- Introduction --- p.41 / Chapter 3.2 --- Synthesis of the PPV precursor polymer --- p.43 / Chapter 3.3 --- Average molecular weight of the PPV precursor --- p.46 / Chapter 3.4 --- Thermal elimination of the precursor polymer --- p.48 / Chapter 3.5 --- Thermal stability of the PPV precursor polymer --- p.50 / Chapter 3.5.1 --- Sample preparation --- p.50 / Chapter 3.5.2 --- Experimental --- p.51 / Chapter 3.5.3 --- Results and discussion --- p.52 / Chapter 3.6 --- Structural changes of the precursor polymer during elimination --- p.57 / Chapter 3.6.1 --- Sample preparation --- p.57 / Chapter 3.6.2 --- Experimental --- p.58 / Chapter 3.6.3 --- Results and discussion --- p.58 / Chapter 3.7 --- Chemical composition of the precursor polymer upon elimination --- p.67 / Chapter 3.7.1 --- Sample preparation --- p.67 / Chapter 3.7.2 --- Experimental --- p.67 / Chapter 3.7.3 --- Results and discussion --- p.68 / Chapter 3.8 --- Effect of the conjugation length of the polymer on photoluminescence --- p.74 / Chapter 3.8.1 --- Sample preparation --- p.76 / Chapter 3.8.2 --- Experimental --- p.78 / Chapter 3.8.3 --- Results and discussion --- p.79 / Chapter 3.9 --- Conclusions --- p.89 / Chapter Chapter 4 --- Experimental methods to characterize the water absorption by PEDOT:PSS / Chapter 4.1 --- Introduction --- p.90 / Chapter 4.2 --- Determination of the water content of PEDOT:PSS at different relative humidity using TG --- p.93 / Chapter 4.2.1 --- Experimental --- p.94 / Chapter 4.2.2 --- Results and discussion --- p.96 / Chapter 4.3 --- Determination of bounded water content of PEDOT:PSS at different RH by DSC --- p.98 / Chapter 4.3.1 --- Experimental --- p.98 / Chapter 4.3.2 --- Results and discussion --- p.100 / Chapter 4.4 --- Determination of bounded water content of PEDOT:PSS at different RH by FTIR --- p.108 / Chapter 4.4.1 --- Experimental --- p.109 / Chapter 4.4.2 --- Results and discussion --- p.112 / Chapter 4.5 --- Conclusions --- p.118 / Chapter Chapter 5 --- Conclusions --- p.120 / References --- p.122

One of the major challenges in the field of organic semiconductors is to develop molecular design rules and processing routes which optimise the charge carrier mobility, whilst independently controlling the radiative and non-radiative processes. To date there has existed a seeming trade-off between charge carrier mobility and photoluminescence efficiency, which limits the development of some devices such as electrically pumped laser diodes. This thesis investigates fluorescence enhancement strategies for high-mobility polymer semiconductor systems and the mechanisms by which they currently display poor emission properties. Four independent approaches were taken and are detailed as follows. 1. Solubilising chain engineering It is shown that for the high mobility polymer poly(indacenodithiophene-co-benzothiadiazole), the addition of a phenyl- initiated side chain can enhance the solid-state fluorescence quantum yield, exciton lifetime and exciton diffusion length significantly in comparison to that without phenyl-addition. 2. Energy transfer to a highly fluorescent chromophore It is shown that for the high mobility polymer poly(indacenodithiophene-co-benzothiadiazole) efficient energy transfer to a more emissive squaraine dye molecule is possible despite fast non-radiative decay short exciton diffusion lengths. This results in a significant fluorescence enhancement, which in turn facilitates an order of magnitude increase of the efficiency of polymer light emitting diodes made from this material combination. 3. Energy gap engineering The well known Energy Gap Law predicts an increase in the non-radiative rate as the optical bandgap of an organic chromophore decreases in energy. In combination with this, almost all polymer semiconductors reported to date with high charge carrier mobility have low optical bandgaps. Therefore, molecular design principles which act to increase the optical bandgap of polymer semiconductors whilst retaining a high mobility were sought out. One specific system was successfully identified and showed a significant fluorescence enhancement compared to is predecessor poly(indacenodithiophene-co-benzothiadiazole) in both the solution and the solid state. It is found that the Frenkel exciton lifetime in this new system is a factor of four larger which also results in a significantly increased exciton diffusion length. An inter-chain electronic state is also identified and discussed. 4. Hydrogen substitution For some low-bandgap material systems such as erbium chromophores, high energy vibrational modes such as the C-H stretching mode can act as non-radiative pathways. The effect of hydrogen substitution with deuterium and fluorine was therefore investigated in a series of polythiophene derivative families. It was found that in the solid state, fluorescence and exciton lifetime enhancement occurred when the backbone hydrogen atoms were replaced with fluorine. However, evidence is given that this was not owing to the initial hypothesis, and is more likely owing to structural differences which occur in these substituted material systems.

O auto sombreamento das folhas posicionadas nas porções inferiores do dossel de plantas pode limitar a produtividade em cultivos tutorados. Assim, a produtividade do tomateiro pode ser aumentada por meio da suplementação luminosa posicionada no interior do dossel, técnica conhecida como interlighting. O sistema de condução do tomateiro também interfere na distribuição da radiação solar, além de afetar os tratos culturais, a competição intra e entre plantas e a relação entre as partes vegetativas e reprodutivas. Desta forma, o objetivo deste trabalho foi avaliar a influência do sistema de condução de minitomate cultivar \'Sweet Grape\' em diferentes números de hastes por planta (duas, três e quatro hastes) e da suplementação luminosa com módulos de LED na produtividade e qualidade dos frutos, na eficiência do uso de água e nutrientes, além da morfologia das plantas e fatores relacionados ao manejo cultural, em ambiente protegido nas condições climáticas do sudeste brasileiro. Ao longo do ciclo de cultivo foram avaliados os seguintes parâmetros: volume irrigado, pH, condutividade elétrica, porcentagem e volume da solução drenada pelos vasos. As colheitas foram realizadas semanalmente, a partir de 90 dias após o transplante. Os frutos colhidos foram classificados, contados e pesados para a obtenção do número e massa de frutos grandes, médios, pequenos, comercial, não comercial e total. Amostras de frutos e tecidos foliares foram coletadas em cinco períodos e avaliadas quanto ao teor de sólidos solúveis, pH, acidez titulável e concentração de ácido ascórbico nos frutos e teor de nutrientes nas folhas. Além disso, ao final do ciclo cultural, foram realizadas as medições dos seguintes parâmetros morfológicos nas plantas: comprimento de hastes, número de cachos normais e bifurcados por hastes e diâmetro apical, mediano e basal das hastes. A suplementação luminosa apresentou aumento no número e na massa de frutos grandes e médios, elevando a produtividade total em 12%. Plantas com duas e três hastes apresentaram maior acúmulo de massa total de frutos, porém plantas com três hastes apresentaram maior massa de frutos não comerciais, com redução na massa de frutos comerciais. A maior eficiência no uso de água e nutrientes foi alcançada em plantas cultivadas com duas hastes. Plantas com quatro hastes demandaram mais solução nutritiva comparada às plantas com duas e três hastes. Esta maior demanda de solução, acarretou em aumento da condutividade elétrica da solução drenada. Plantas com quatro hastes apresentaram maiores teores de sólidos solúveis nos frutos. A suplementação luminosa também resultou em aumento do teor de sólidos solúveis e ligeiro aumento no teor de ácido ascórbico nos frutos. A suplementação luminosa favoreceu o acúmulo de nitrogênio, fósforo e potássio nas folhas do tomateiro. Desta forma, conclui-se que a suplementação luminosa é uma estratégia de manejo tecnicamente viável nas condições climática estudada. O sistema de condução de haste afeta a produtividade e qualidade dos frutos do tomateiro. Plantas com duas hastes além de apresentar maior produtividade de frutos comerciais, mostrou-se a estratégia mais eficiente no uso da água e nutrientes. / The auto shading of leaves located within lower part of plant canopy can limit productivity of the tutored crops. Therefore, tomato productivity can be enhanced through supplementation of light positioned within the canopy using a technique known as interlighting. In addition, management system also affects the distribution of solar radiation, cultural practices as well as intra and between plants competition, which changes the relationship between vegetative and reproductive parts. The objective of this study was to evaluate the influence of different numbers of stems per plant (two, three and four stems) and light supplementation with LED modules in productivity and quality of the fruit of cherry tomato cv. \"Sweet Grape\". Furthermore, it was quantified the efficient use of water and nutrients, plant morphology and factors related to cultural management. The experiment was conducted in a greenhouse located in Piracicaba, southeastern Brazil, using a randomized block design with four replications. Throughout crop cycle were evaluated the following parameters: Irrigated water volume, pH, electrical conductivity, percentage and volume of drained solution. Fruit samples were collected weekly from 90 days after transplantation of tomato seedlings. The harvested fruits were sorted, counted and weighed to obtain number and weight of large, medium, small, commercial, non-commercial and total fruits. Fruit samples and leaf tissues were collected in five periods for quantifying soluble solids, pH, titratable acidity and concentration of ascorbic acid in fruit and nutrient content in the leaves. Furthermore, in the end of the crop cycle, measurements of the following plant morphological parameters were performed: length stems, number of normal and bisected by stems clusters and apical, middle and basal diameter of the stems. Our findings showed that light supplementation induced higher number and mass of large and medium commercial fruit, increasing total productivity by 12%. Two- and three-stem plants had higher total mass accumulation of fruit, but three-stem plants had greater mass of non-commercial fruit, with a reduction in the mass of commercial fruits. The more efficient use of water and nutrients was achieved by two-stem plants. Four-stem plants demanded more nutrient solution compared to two- and three-stem plants, resulting in an increased electrical conductivity of the drained nutrient solution. Four-stem plants had higher soluble solids in the fruit. The light supplementation also resulted in an increase of soluble solids and a slight increase in the ascorbic acid content in fruits. The light supplementation favored the accumulation of nitrogen, phosphorus and potassium within tomato leaves. We concluded that the light supplementation is a technically feasible management strategy in the climatic conditions studied. The management system affects the productivity and quality of cherry tomato fruits. Two stem plants had higher productivity of commercial fruits, as well as it proved to be the most effective strategy in the use of water and nutrients.

No description available.

Due to its truly two dimensional (2D) character and its particular lattice, single layer graphene (SLG) possesses exceptional properties: it is semimetallic, transparent, strong yet flexible ... Complementary features such as the insulating character of hexagonal boron nitride (h-BN) and semiconducting properties of transition metal dichalcogenides (TMDs) enable the whole spectrum of electronic devices to be built with combinations of these 2D materials. Due to this and the ease of exfoliation with a sticky tape, a vast amount of research was sparked. The mechanical exfoliation method, however, is only suitable for novel or proof-of-concept devices. The trend nowadays in electronics is towards transparent, lightweight, flexible, embedded smart devices and sensors in everyday objects such as windows and mirrors, garments, windshields, car seats, parachutes...These demands are already met inherently by these new materials, thus the challenges remaining are within their synthesis, deposition and processing, where more scalable ways of production and device fabrication need to be developed. This thesis explores innovative approaches using established techniques that aim to bridge the gap between proof-of-concept devices and real applications of 2D materials in future commercial level technologies. Methods to create graphene and engineer its properties are employed with a special focus on scalability and adaptability towards the industry. These graphene materials have been processed using pioneering schemes to create different optoelectronic devices and sensors. The techniques employed here for synthesis, transfer and deposition, device processing and characterization of graphene and derivatives, are suitable for their use in large manufacturing and mass-production. Depending on the application envisaged, different materials are used and optimize in order to balance good performance, cost-effectiveness and suitability/scalability of the process for the specific target the device was designed for.

No description available.

Neste trabalho, foram realizados estudos de propriedades elétricas e de eletroluminescência em diodos emissores de luz (OLED) contendo modulação energética de poços de potencial para elétrons e buracos (tipo I), poços esses posicionados na região central da camada ativa. A camada ativa é composta por poços simples e duplos, de espessura de 5 e 10nm, de Poli (fenilenovinileno), PPV (Eg = 2,4 eV), dispostos entre duas barreiras de Polifluoreno ou PFO (Eg = 3,0 eV) de espessura 40 nm. Os filmes de PFO foram obtidos a partir de uma solução em Clorofórmio via spin coating e os de PPV a partir de um precursor solúvel em agua via spin assistant LbL, técnica essa que permitiu o crescimento alternado de filmes de PFO e filmes extremamente finos de PPV mesmo em vista da ortogonalidade de seus solventes. Camadas injetoras de polieletrólitos foram depositadas adjacentes ao catodo para diferenciar injeção eletrônica da injeção de buracos. Foram feitos dispositivos contendo somente uma camada de PFO de 80 nm, chamados referência, para comparação do efeito dos poços nos dispositivos com um e dois poços de potencial. Na caracterização foram utilizadas as técnicas de microscopia confocal, com o intuito de demonstrar o crescimento efetivo das camadas, e medidas elétricas de corrente (IxV) e eletroluminescência (LxV) por voltagem. Medidas do perfil de intensidade ao longo do filmes e espectros de fotoluminescência em três regiões distintas da área total do dispositivo mostraram que as camadas de PPV de aproximadamente 5 e 10 nm estavam homogêneas e que recobriam bem as camadas de PFO. Os espectros de eletroluminescência dos dispositivos mostraram que as diferenças energéticas entre os orbitais π (ΔEHOMO= 0,54 eV) e π* (ΔELUMO = 0,37 eV) do PFO e PPV foram suficientes para causar o aprisionamento e recombinação dos portadores dentro do poço, resultando em emissões características do PPV com picos bem definidos próximos a 520 nm, bastante distintas das emissões dos dispositivos referência, contendo somente PFO (banda larga e não definida de emissão com λ > 480 nm). A presença dos poços de potencial alterou significativamente as propriedades dos dispositivos levando a diminuição da voltagem de acendimento (Von) para 3,5 V mesmo para dispositivos contendo camada injetora que dificultava a injeção eletrônica. Quando há apenas um poço de potencial na camada ativa dos dispositivos, com ou sem camada injetora, o regime de corrente para voltagens abaixo de 3,5 V é ôhmico e unipolar, sendo ditado por buracos, mas quando a voltagem é maior do que 3,5 V o regime de corrente fica limitado pelo portador minoritário, o elétron. Surpreendentemente, quando são colocados dois poços na camada ativa, separando os portadores, tanto corrente como a formação excitônica e consequente recombinação, ficam sujeitas a um processo de tunelamento do portador majoritário, o buraco. / In this work, studies of electrical properties and electroluminescence in organic light emitting diodes (OLED) containing energetic modulation of potential wells for charge carriers (type I), positioned in the central region of active layer. The active layer is composed of single and double wells of Poly (phenylenevinylene), PPV (2.4 eV), arranged between two barriers of polyfluorene, PFO (3.0 eV), with 40 nm thickness. The PFO films were obtained from a chloroform solution by spin coating and PPV from a water soluble precursor via spin assistant LbL technique, a technique that has allowed the alternate growth of PFO films and extremely thin PPV films from a orthogonal solvent to chloroform, water. Injection layers of polyelectrolytes were deposited adjacent to the cathode to differentiate electronic injection from hole injection. Confocal microscopy measurements showed that the PPV layer of 5 to 10nm thickness were homogeneous and covered PFO layers entirely. Electroluminescence measurements of the devices showed that the energetic difference between π (ΔEHOMO = 0.54 eV) and π* (ΔELUMO = 0.37 eV) orbitals from PFO and PPV were enough to cause the charge carriers efficient trapping and recombination in the well, resulting in PPV characteristic emission peaks near to 520 nm, quite different from the reference device emission containing only PFO (broad emission band in the lower energy range). The current measurements showed that the presence of potential wells in the middle of the active layer is responsible for effective change in electrical properties of devices such as carrier density n, μ the mobility and conductivity. When there is only one potential well in the active layer, with or without injection layer, the current regime for voltages below 3.5 V is ohmic and unipolar, being dictated by holes, but when the voltage is greater than 3.5 V current regime is limited by the minority carrier, the electron. Surprisingly, when two wells are placed in the active layer, separating the carriers, both current as the excitonic formation and subsequent recombination are subject to a tunneling process by the majority carrier, the hole.