O trabalho tem por objetivo o estudo e o desenvolvimento de interferômetros recuperadores com baixa tensão de meia onda utilizando moduladores eletro-ópticos para serem aplicados em sistemas Interferométricos de luz branca. Ele dá continuidade às pesquisas do autor em seu mestrado, em que foi desenvolvido e testado um sistema de sensoriamento eletro-óptico capaz de medir diretamente tensões de até 69,4 kVRMS. Desta forma aperfeiçoa-se o sistema de processamento de sinais ópticos desenvolvendo um novo interferômetro recuperador, baseado em óptica integrada. Para o desenvolvimento do tema proposto, inicialmente foi feito uma revisão da literatura/bibliografia, baseada em livros, artigos e teses, visando identificar o \"estado da arte\" relacionado aos moduladores eletro-ópticos para definir o tipo de modulador mais adequado à aplicação em vista. O estudo resultou na escolha de um componente em óptica integrada que foi aplicado numa configuração inédita em um protótipo de transformador de potencial óptico para medição de elevados níveis de tensão elétrica. As características de desempenho deste protótipo foram comparadas com as do protótipo previamente construído. Como resultado deste trabalho, amplia-se o conhecimento e fixa-se em âmbito nacional o domínio sobre as técnicas de construção de interferômetros recuperadores baseados em óptica integrada aplicáveis à recuperação de sinais ópticos em sistemas interferométricos para medição de altas tensões. / This work has as objective the study and development of low half-wave voltage recovery interferometers using electro-optical modulators to be applied to white light interferometric systems. This work is a continuation in the research carried out by the author to obtain his master degree, in which it was developed and tested an electro- optic sensing system capable to measure direct voltage to 69.4 kVrms. In the present work the optical signals processing system is improved by developing a new recovery interferometer based on integrated optics. To develop the proposed subject, initially a review of the literature, based on books, articles and thesis, has been done aiming to identify the State of the Art related to electro-optic modulators and helping to define the most suitable type of modulator for the desired application. The study resulted in the selection of an integrated optical device arranged in an unpublished configuration that was applied to a prototype of optical voltage transformer, intended to measure high voltage levels. The performance of this prototype was compared with a previous version. The results of this work increase the knowledge of the construction techniques of recovery interferometers based on integrated optic devices applicable to the recovering of optical signals in interferometric systems for high voltage measurement.

Neste trabalho, são estudadas as alterações das propriedades ópticas lineares e não lineares de soluções de azocompostos devidas aos mecanismos de isomerização e às alterações das propriedades estruturais com a temperatura. A dependência da transição pipi* com a estrutura linear dos azocompostos é notada já nas medidas dos espectros de absorção em função da temperatura para o isômero trans. Através do conhecimento dos níveis de energia e dos tempos de relaxação via isomerização, foi possível obter a dinâmica entre os isômeros cis e trans. As medidas não lineares forneceram propriedades interessantes associadas aos estados de energia dos compostos. Por exemplo, através de experimentos de varredura-z e de excitação e prova, foi possível ver que os azocompostos apresentam uma alta transparência quando excitados, a qual desaparece com o término da isomerização. Medidas em função do comprimento de onda mostraram que a transparência observada está presente em toda a banda pipi* e não ocorre na banda npi* . Também foi observado que o tempo de isomerização muda de acordo com o comprimento de onda de excitação, o que pode estar relacionado com a superposição das duas bandas. Os resultados obtidos em femtossegundos foram essenciais para descrever o processo dinâmico de fotoisomerização, observado, por completo, através de medidas com varredura-Z em picossegundos e nanossegundos. Essas medidas forneceram os valores das seções de choque dos isômeros cis, que são difíceis de serem quantificadas devido ao curto tempo de vida desse isômero. Além dos resultados ressonantes, foram feitos experimentos de absorção de dois fótons em femtossegundos usando a técnica de varredura-Z. Esses estudos mostraram a dependência das seções de choque de absorção de dois fótons com características estruturais das moléculas, tais como comprimento de conjugação, grupos push-pull e planaridade. Os resultados ressonantes e não ressonantes obtidos em femtossegundos serviram de base para a calibração da técnica de varredura-Z com pulsos de luz branca. Essa técnica se mostrou adequada para a obtenção dos espectros das não linearidades ópticas ressonantes e não ressonantes em uma única medição (de 5 minutos), diminuindo assim flutuações do laser durante o experimento. / This work reports on the temperature dependence of linear and nonlinear properties of azocompounds solutions due to isomerization mechanisms. The dependence of pipi* transitions on the linear structure of azocompounds is already noticeble in the measurements of absorption spectra as function of the temperature for the trans isomer. Knowing the energy levels and the relaxation times through isomerization, it was possible to obtain the exchange dynamics between cis and trans conformations. Nonlinear measurements provided interesting properties associated with the energy levels of de compounds. For exemple, through Z-scan and pumpprobe experiments, it was possible to verify that azocompounds present a high transparency when excited and that this transparency disapears when the izomerization ends. The wavelength change has shown that the observed transparency is present along the complete pipi* band, but not in the npi* band. It was also observed that the isomerization time changes with the exciting wavelength, which may be related to the superposition of both bands. The results obained with femtoseconds pulses were essential to completily describe the photoisomerization process observed with Z-scan measurements using picoseconds and nanoseconds pulses. These measurements provided values of the crosssection of the cis conformation, which are difficult to be quantified due to the short lifetime of this isomer. Besides ressonant results, experiments of two-photon absorption in the femtosecond regime using the Z-scan technique were made. These studies shown the dependence of the two photons absorption cross-section on structural features of molecules such as conjugation length, push-pull groups and planarity. The ressonant and nonressonant results obteined with femtoseconds have provide the calibration of the Z-scan technique with white light pulses. This technique has been found able to obtain the spectra of ressonat and nonressonant nonlinearities in a single measurement (about 5 minutes), diminishing laser fluctuation during the experiment.

O trabalho tem por objetivo o estudo e o desenvolvimento de interferômetros recuperadores com baixa tensão de meia onda utilizando moduladores eletro-ópticos para serem aplicados em sistemas Interferométricos de luz branca. Ele dá continuidade às pesquisas do autor em seu mestrado, em que foi desenvolvido e testado um sistema de sensoriamento eletro-óptico capaz de medir diretamente tensões de até 69,4 kVRMS. Desta forma aperfeiçoa-se o sistema de processamento de sinais ópticos desenvolvendo um novo interferômetro recuperador, baseado em óptica integrada. Para o desenvolvimento do tema proposto, inicialmente foi feito uma revisão da literatura/bibliografia, baseada em livros, artigos e teses, visando identificar o \"estado da arte\" relacionado aos moduladores eletro-ópticos para definir o tipo de modulador mais adequado à aplicação em vista. O estudo resultou na escolha de um componente em óptica integrada que foi aplicado numa configuração inédita em um protótipo de transformador de potencial óptico para medição de elevados níveis de tensão elétrica. As características de desempenho deste protótipo foram comparadas com as do protótipo previamente construído. Como resultado deste trabalho, amplia-se o conhecimento e fixa-se em âmbito nacional o domínio sobre as técnicas de construção de interferômetros recuperadores baseados em óptica integrada aplicáveis à recuperação de sinais ópticos em sistemas interferométricos para medição de altas tensões. / This work has as objective the study and development of low half-wave voltage recovery interferometers using electro-optical modulators to be applied to white light interferometric systems. This work is a continuation in the research carried out by the author to obtain his master degree, in which it was developed and tested an electro- optic sensing system capable to measure direct voltage to 69.4 kVrms. In the present work the optical signals processing system is improved by developing a new recovery interferometer based on integrated optics. To develop the proposed subject, initially a review of the literature, based on books, articles and thesis, has been done aiming to identify the State of the Art related to electro-optic modulators and helping to define the most suitable type of modulator for the desired application. The study resulted in the selection of an integrated optical device arranged in an unpublished configuration that was applied to a prototype of optical voltage transformer, intended to measure high voltage levels. The performance of this prototype was compared with a previous version. The results of this work increase the knowledge of the construction techniques of recovery interferometers based on integrated optic devices applicable to the recovering of optical signals in interferometric systems for high voltage measurement.

Luminescent materials find numerous applications in recent times and have enriched human lives in several different ways. From display and lighting technologies to security, sensing and biological investigations, luminescent organic compounds have become indispensible and often preferred over their inorganic counterparts. The versatility of organic materials arises from their comparative low costs, ease of fine-tuning, low toxicity and the possibility to develop flexible devices. Even until very recent times, the investigations and usage of organic luminescent materials were mostly limited to solution-state properties. However, with progress of available characterisation techniques and parallel development of their usage in solid-state devices and other applications (e.g. security, forensics, sensing etc.), significantly greater attention has been paid to the development and investigations of solid-state emissive organic materials. In solid-state applications, apart from the molecular properties of any given material, their cumulative i.e. bulk physical properties are of even greater importance. Thus, investigations of structure-property relationships in organic luminescent compounds to understand their molecular and bulk properties are of fundamental interest. In this thesis, NPI (1,8-naphthalimide) and BODIPY (boron-dipyrromethene) dyes were investigated to provide a broad overview of their structure-property correlations. Among commonly encountered organic luminescent materials, NPIs and BODIPYs have emerged as two broad classes of luminescent organic compounds, finding applications as functional luminescent materials in various fields. However, lack of understanding for controlling the cumulative emissive properties of these compounds has limited their usage as active solid-state emitters in various applications. This thesis presents several new insights into the molecular and bulk emissive properties of these two classes of luminescent dyes (NPIs and BODIPYs). The contents of the six chapters contained in this thesis are summarised below. Chapter 1 summarises the available understanding of the basic concepts of photoluminescence and the design strategies to develop solid-state luminescent and AIE (aggregation-induced emission) active materials. This chapter also emphasises in the basic nature of the NPI and BODIPY compounds, their substitution patterns and their inherent characteristics and touches upon the relatively unexplored properties of NPI and BODIPY based materials. The importance and scope of the work reported in the thesis is outlined at the end of the chapter. Chapter 2 describes a detailed investigation of a series of seven (4-oxoaryl substituted) NPI compounds (1-7) providing an insight into the molecular and cumulative photophysical behaviour of these compounds. The low ICT characteristics of the NPIs, coupled with the twisted geometry, facilitated solid-state luminescence in these materials. The solution and solid-state luminescent properties of these compounds can be directly correlated to their structural rigidity, nature of substituents and solid-state intermolecular interactions (e.g. π-π stacking, C-H•••O interactions etc.). The solid-state crystal structures of the NPI siblings are profoundly affected by the pendant substituents. All of the NPIs (1-7) show antiparallel dimeric π-π stacking interactions in the solid-state which can further extend in parallel, alternate, orthogonal or lateral fashion depending on the steric and electronic nature of the C-4′ substituents. Structural investigations including Hirsfeld surface analysis methods reveal that while strongly interacting systems show weak to moderate emission in their condensed states, weakly interacting systems show strong emission yields under the same conditions. The nature of packing and extended structures also affects the emission colors of the NPIs in the solid-state. DFT computational studies were utilized to understand the molecular and cumulative electronic behavior of the NPIs. Apart from the investigation of solid-state luminescence, other functional potentials of these NPIs were also explored. One of the compounds (i.e. 4) shows chemodosimetric response towards aqueous Hg(II) species with a ‘turn-on’ response. Also, depending on the molecular flexibility of the compounds, promising AIEE (aggregation-induced emission enhancement) features were observed in these NPIs. Later (in Chapter 3), we developed a systematic investigation in a series of purely organic NPIs, restricting various parameters, to attain a thorough understanding of such AIEE properties. Chapter 3 describes a detailed experimental and computational study in order gain an insight into the AIE (aggregation-induced emission) and AIEE mechanisms in NPI compounds. Systematic structural perturbation was used to fine tune the luminescence properties of three new 1,8-naphthalimides (8-10) in solution and as aggregates. The NPIs (8-10) show blue emission in solution state and the fluorescence quantum yields depend on their molecular rigidity. In concentrated solutions of the NPIs, intermolecular interactions were found to result in quenching of fluorescence. In contrast, upon aggregation (in THF:H2O mixtures), two of the NPIs show aggregation-induced-emission-enhancement (AIEE). The NPIs also show moderately high solid-state emission quantum yields (~10-12.7 %). The AIEE behaviors of the NPIs depend on their molecular rigidity and nature of intermolecular interactions. The NPIs (8-10) show different extents of intermolecular (π-π and C-H•••O) interactions in their solid-state structures depending on their substituents. Detailed photophysical, computational and structural investigations suggest that only an optimal balance of structural flexibility and intermolecular communication is the effective recipe for achieving AIEE characteristics in these NPIs. Chapter 4 presents the design, synthesis and detailed investigations and potential applications of a series of NPI-BODIPY dyads (11-13). The NPI and BODIPY moieties in these dyads are electronically separated by oxoaryl bridges and the compounds only differ structurally with respect to methyl substitutions on the BODIPY fluorophore. The NPI and BODIPY moieties retain their optical features in these molecular dyads (11- 13). Dyads 11-13 show dual emission in solution state originating from the two separate fluorescent units. The variations of the dual emission in these compounds are controlled by the structural flexibility of the systems. The dyads also show significant AIES (Aggregation-Induced-Emission Switching) features upon formation of nano-aggregates in THF-H2O mixtures with visual changes in emission from green to red color. Whereas the flexible and aggregation prone system (i.e. compound 11) shows aggregation-induced enhancement of emission, rigid systems with less favorable intermolecular interactions (i.e. compound 12-13) show aggregation-induced quenching of emission. The emission-intensity vs. the structural-flexibility correlations were found to be reverse in solution and aggregated states. Photophysical and structural investigations suggest that the intermolecular interactions (e.g. π-π stacking etc.) play major role in controlling emission of these compounds in aggregated states. Similar trends were also observed in the solid-state luminescence of these compounds. The applications of the luminescent dyads 11-13 as live-cell imaging dyes was also investigated. Chapter 5 describes investigations of photophysical properties of a series of six BODIPY dyes (14-19) in which there is a systematic alteration of a common -C6H4Si(CH3)3 substituent. Inrelated constitutional isomers, the systematic increment of steric congestion and lowering of molecular symmetry around the BODIPY core result in a steady increment of solution and solid- state fluorescence quantum yields. The increasing fluorescence quantum yields (solution, solid state) with increasing steric congestions show that the molecular free rotation and aggregation-induced fluorescence quenching of BODIPYs can be successfully suppressed by lowering the flexibility of the molecules. Photophysical and DFT investigations reveal that the electronic band gap in any set of these constitutional isomers remain almost similar. However, the crystal structures of the compounds reveal that the solid-state colour and quantum yields of the compounds in solid-state are also related to the nature of intermolecular interactions. Chapter 6 demonstrates the use of DFT computational methods to understand the effect of alkyl groups in governing the basic structural and electronic aspects of BODIPY dyes. As demonstrated in Chapter 4 and Chapter 5, apparently electronically inactive alkyl groups can be of immense importance to control the overall photophysics of BODIPYs. In this context, a systematic strategy su was utilized considering all possible outcomes of constitutionally-isomeric molecules to understand the effects of alkyl groups on the BODIPY molecules. Four different computational methods were employed to ascertain the unanimity of the observed trends associated with the molecular properties. In line with experimental observations, it was found that alkyl substituents in BODIPY dyes situated at 3/5-positions effectively participate in stabilization as well as planarization of such molecules. Screening of all the possible isomeric molecular systems was used to understand the individual properties and overall effects of the typical alkyl substituents in controlling several basic properties of such BODIPY molecules.

Neste trabalho, são estudadas as alterações das propriedades ópticas lineares e não lineares de soluções de azocompostos devidas aos mecanismos de isomerização e às alterações das propriedades estruturais com a temperatura. A dependência da transição pipi* com a estrutura linear dos azocompostos é notada já nas medidas dos espectros de absorção em função da temperatura para o isômero trans. Através do conhecimento dos níveis de energia e dos tempos de relaxação via isomerização, foi possível obter a dinâmica entre os isômeros cis e trans. As medidas não lineares forneceram propriedades interessantes associadas aos estados de energia dos compostos. Por exemplo, através de experimentos de varredura-z e de excitação e prova, foi possível ver que os azocompostos apresentam uma alta transparência quando excitados, a qual desaparece com o término da isomerização. Medidas em função do comprimento de onda mostraram que a transparência observada está presente em toda a banda pipi* e não ocorre na banda npi* . Também foi observado que o tempo de isomerização muda de acordo com o comprimento de onda de excitação, o que pode estar relacionado com a superposição das duas bandas. Os resultados obtidos em femtossegundos foram essenciais para descrever o processo dinâmico de fotoisomerização, observado, por completo, através de medidas com varredura-Z em picossegundos e nanossegundos. Essas medidas forneceram os valores das seções de choque dos isômeros cis, que são difíceis de serem quantificadas devido ao curto tempo de vida desse isômero. Além dos resultados ressonantes, foram feitos experimentos de absorção de dois fótons em femtossegundos usando a técnica de varredura-Z. Esses estudos mostraram a dependência das seções de choque de absorção de dois fótons com características estruturais das moléculas, tais como comprimento de conjugação, grupos push-pull e planaridade. Os resultados ressonantes e não ressonantes obtidos em femtossegundos serviram de base para a calibração da técnica de varredura-Z com pulsos de luz branca. Essa técnica se mostrou adequada para a obtenção dos espectros das não linearidades ópticas ressonantes e não ressonantes em uma única medição (de 5 minutos), diminuindo assim flutuações do laser durante o experimento. / This work reports on the temperature dependence of linear and nonlinear properties of azocompounds solutions due to isomerization mechanisms. The dependence of pipi* transitions on the linear structure of azocompounds is already noticeble in the measurements of absorption spectra as function of the temperature for the trans isomer. Knowing the energy levels and the relaxation times through isomerization, it was possible to obtain the exchange dynamics between cis and trans conformations. Nonlinear measurements provided interesting properties associated with the energy levels of de compounds. For exemple, through Z-scan and pumpprobe experiments, it was possible to verify that azocompounds present a high transparency when excited and that this transparency disapears when the izomerization ends. The wavelength change has shown that the observed transparency is present along the complete pipi* band, but not in the npi* band. It was also observed that the isomerization time changes with the exciting wavelength, which may be related to the superposition of both bands. The results obained with femtoseconds pulses were essential to completily describe the photoisomerization process observed with Z-scan measurements using picoseconds and nanoseconds pulses. These measurements provided values of the crosssection of the cis conformation, which are difficult to be quantified due to the short lifetime of this isomer. Besides ressonant results, experiments of two-photon absorption in the femtosecond regime using the Z-scan technique were made. These studies shown the dependence of the two photons absorption cross-section on structural features of molecules such as conjugation length, push-pull groups and planarity. The ressonant and nonressonant results obteined with femtoseconds have provide the calibration of the Z-scan technique with white light pulses. This technique has been found able to obtain the spectra of ressonat and nonressonant nonlinearities in a single measurement (about 5 minutes), diminishing laser fluctuation during the experiment.

Made available in DSpace on 2016-03-15T19:35:52Z (GMT). No. of bitstreams: 1 DENIS PAVEL CABEZAS HUAMAN.pdf: 1718725 bytes, checksum: b98f52c6b4dac9b37a33cc5bc62d871e (MD5) Previous issue date: 2015-03-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The project aims to study the disturbances (responses) of the low solar atmosphere caused by solar flares, using Hα, 30 THz (10 μm), UV/EUV, soft and hard X-rays observations, and a wide range of radio waves emissions (microwaves, millimeter, sub-millimeter). This set of multispectral data enabled us to (i) examine in detail various aspects of the phenomena, (ii) determine the origin of the radio emission during the gradual phase, and therefore (iii) understand the mechanism of the particles acceleration. The data we used for the completion of this study are based on Hα and 30 THz (10 μm) observations, made by the high cadence flare imaging system installed at OSM4 and CASLEO5 observatories, additionally data from HASTA (H-Alpha Solar Telescope for Argentina) telescope installed at OAFA6 observatory. In the sub-millimeter and millimeter domain at 212, 405 GHz and 45, 90 GHz, were from SST (Solar Sub-millimeter Telescope) and from POEMAS (POlarization Emission of Millimeter Activity at the Sun) solar radio telescopes, respectively. Complementary radio observations in the microwave range (0.2-15 GHz) from RSTN (Radio Solar Telescope Network) were considered. In addition, solar observations obtained by RHESSI (Reuven Ramaty High Energy Solar Spectroscopic Imager), Fermi and GOES (Geostationary Operational Environmental Satellite) satellites in X-ray channels, and from AIA (Atmospheric Imaging Assembly) and HMI (Helioseismic and Magnetic Imager) instruments, onboard the SDO (Solar Dynamics Observatory) satellite, respectively. / O trabalho tem como objetivo estudar as perturbações da baixa atmosfera solar produzidas pelas explosões solares, usando observações em Hα, 30 THz (10 μm), UV/EUV, raios X e uma ampla faixa de emissões em ondas de rádio (microondas, milimétrica, submilimétrica); com o propósito de determinar a natureza dos processos físicos envolvidos. Este conjunto de dados multiespectrais nos permitiu (i) analisar os diferentes aspectos das explosões tanto na fase impulsiva como gradual, (ii) determinar a origem da emissão em rádio durante a fase gradual, e consequentemente (iii) entender melhor os mecanismos de aceleração das partículas. Os dados em Hα e 30 THz foram fornecidos pelo sistema de aquisição de dados com alta resolução temporal, instalado nos observatórios OSM1 e CASLEO2, adicionalmente dados do telescópio HASTA (H-Alpha Solar Telescope for Argentina) instalado no observatório OAFA3. Enquanto as observações em rádio, os dados foram do rádio polarímetro POEMAS (POlarization Emission of Millimeter Activity at the Sun) nas frequências de 45 e 90 GHz, do telescópio SST (Sub-millimeter Solar Telescope) nas frequências 212 e 405 GHz, ambos instalados no CASLEO. Dados na faixa de microondas (0,2-15 GHz) obtidos pela rede RSTN (Radio Solar Telescope Network). Além disso, foram considerados observações do Sol obtidas pelos satélites RHESSI (Reuven Ramaty High Energy Solar Spectroscopic Imager), Fermi e GOES (Geostationary Operational Environmental Satellite) para raios X, e dos instrumentos AIA (Atmospheric Imaging Assembly), HMI (Helioseismic and Magnetic Imager), a bordo do satélite SDO (Solar Dynamics Observatory), respectivamente.