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Luminescent boron containing materials find numerous applications in modern technologies such as display/lighting, bio-imaging and sensing. Thus, investigations of structure-property relationships in organic luminescent compounds to understand their molecular and bulk properties are of fundamental importance. The main thrust of this thesis is the development of facile synthetic routes for boron containing novel polyads and study their structure-property correlations and to utilize this information to design functional materials with desired properties such as multiple emission, bio imaging, anion sensing and organic photo voltaic characteristics. This thesis contains seven chapters and the contents of each chapter are described below. Chapter 1 This chapter is a concise overview of the recent developments in the chemistry of boron based molecular systems such as triarylborane and BODIPYs. This chapter also highlights the basic nature of broad emissive materials. In addition, an advance in the frontier areas such as bio imaging is discussed in brief. Chapter 2 This chapter describes the structure and optical properties of a new triad (Borane-Bithiophene-BODIPY) 1. Triad 1 exhibits unprecedented tricolour emission when excited at borane centred high energy absorption band and also acts as a selective fluorescent and colorimetric sensor for fluoride ion with ratiometric response. The experimental results are supported by computational studies. Chapter 3 Two fluorescent compounds with similar absorption profiles and complementarily emissive properties can be regarded as the ideal couple for the generation of white-light. Two structurally close and complementarily fluorescent boron based molecular siblings 2 and 3 were prepared. The luminescence properties of individual triads were modulated to an extent to complement each other by controlling the intramolecular energy transfer in triads by fine-tuning the dihedral angle between fluorophores in 2 and 3. A binary mixture of 2 and 3 emitted white-light. Chapter 4 This chapter deals with a straight forward strategy for the generation of white-light emission in aqueous media. Using a blue-emissive AIE-active (aggregation-induced emission) 1, 8-naphthalimide- based sensitizer and a boron-dipyrromethene based red emitter as a dopant, water dispersible nanostructures with tunable emission features are produced. The white-light emissive (WL) nano-aggregates are stable at neutral pH and have been elegantly utilized for four-colour cell imaging (including near- infrared imaging). Chapter 5 This chapter describes the design and development of a NIR emitting triarylborane decorated styryl-BODIPY (4) via a facile synthetic route. Incorporation of TAB entities results in a significantly red shifted broad emission in 4 (compared to compound M3 which is devoid of TAB unit). The near coplanar orientation of Ar3B planes and BODIPY core results in a highly efficient (TAB to BODIPY) EET process in 4. Conjugate 4 acts as a highly selective and sensitive fluoride sensor with naked eye visual response as well as ratiometric fluorescent response. The dual emission in fluoride bound 4 possibly results from the restricted partial TAB to BODIPY energy transfer. Chapter 6 This chapter describes how the energy of transitions of the broad emissive molecular triads can be fine-tuned by judiciously changing the spacer oligothiophene length. A series of triarylborane and BODIPY conjugates (TAB-π-BODIPY) has been designed, and synthesized by a combined strategy of changing the connection mode between the two units, extending the conjugation size by introducing terthiophene, quaterthiophene, and pentathiophene units. The electrochemical and photophysical behavior of these conjugates were investigated. The experimental findings were rationalized by density functional theory calculations. Chapter 7 This chapter describes design and development of boron based novel electron acceptor BDY for the bulk-heterojunction solar cell. The electron mobility values of BDY was found to be of the order of standard PCBM. Bulk-heterojunction was fabricated using BDY as the electron acceptor layer. The power conversion efficiency of the newly developed solar cells with BDY as electron acceptor is much higher than the value obtained for standard cells with PCBM as the electron acceptor.

Les travaux présentés concernent l'exploration des techniques de localisation utilisées en analyse de défaillance dans le but de les appliquer au domaine de la sécurité numérique des circuits et systèmes intégrés. Ces travaux contribuent, d'une part à étendre le champ d'application des techniques d'analyses de vulnérabilités, et d'autre part à apporter des éléments de réponses sur la faiblesse des implémentations cryptographiques sur circuits de type FPGA. Cette thèse s'inscrit donc dans une démarche à la fois de prévention mais aussi de veille technologique en matière d'attaque en apportant un complément d'information sur la faiblesse des implémentations matérielles de systèmes sécurisés. Dans le cadre de l'évaluation des composants de traitement de l'information par les laboratoires agréés (CESTI), l'analyse de vulnérabilité, et plus spécifiquement la cryptanalyse matérielle, a pour but d'éprouver la sécurité des systèmes d'information (composants cryptographiques, carte bancaire, systèmes de cryptage, etc..) dans le but de tester leur résistance face aux attaques connues. En parallèle, dans le cadre de l'analyse de défaillance des circuits utilisés dans le domaine spatial, la localisation de défauts consiste à collecter et analyser les données d'un circuit défaillant afin d'identifier la source du défaut à l'aide de puissants outils. La combinaison de ces deux activités nous a permis dans un premier temps, d'exploiter la lumière émise par un circuit comme un signal de fuite de type « side-channel » par le biais d'une méthode d'attaque semi-invasive par canal auxiliaire, Differential Light Emission Analysis (DLEA). Cette attaque, basée sur un traitement statistique des courbes d'émission de lumière, a permis d'extraire les sous-clés utilisées par un algorithme DES implanté sur circuit FPGA. Dans un second temps, nous avons proposé une seconde technique basée sur la stimulation laser consistant à exploiter l'effet photoélectrique afin d'améliorer les attaques par canaux auxiliaires « classiques ». Pour cela, une attaque DPA améliorée par stimulation laser a été mise en place. Ainsi nous avons démontré que le balayage du faisceau laser sur certains éléments du cryptosystème (algorithme DES implanté sur FPGA) augmente sa signature DPA permettant ainsi de diminuer sensiblement le nombre de courbes de consommation nécessaires pour extraire les sous-clés utilisées par l'algorithme. / The purpose of failure analysis is to locate the source of a defect in order to characterize it, using different techniques (laser stimulation, light emission, electromagnetic emission...). Moreover, the aim of vulnerability analysis, and particularly side-channel analysis, is to observe and collect various leakages information of an integrated circuit (power consumption, electromagnetic emission ...) in order to extract sensitive data. Although these two activities appear to be distincted, they have in common the observation and extraction of information about a circuit behavior. The purpose of this thesis is to explain how and why these activities should be combined. Firstly it is shown that the leakage due to the light emitted during normal operation of a CMOS circuit can be used to set up an attack based on the DPA/DEMA technique. Then a second method based on laser stimulation is presented, improving the “traditional” attacks by injecting a photocurrent, which results in a punctual increase of the power consumption of a circuit. These techniques are demonstrated on an FPGA device.

Les liquides ioniques sont des fluides non volatiles, constitués de cations et d’anions, qui sont conducteurs ioniques, isolants électriques, et peuvent avoir des valeurs de capacité très élevées. Ces liquides sont susceptibles non seulement de remplacer les électrolytes solides, mais également de susciter des champs électriques intenses (>SI{10}{megavoltpercentimetre}) au sein d’une couche dite double couche électronique (electric double layer, EDL) à l’interface entre le liquide et le matériau sur lequel il est déposé. Ceci conduit à une injection de porteurs de charge bidimensionelle avec des densités allant jusqu’à SI{e15}{cm^{-2}}. Cet effet de grille remarquablement fort des liquides ioniques est réduit en présence d’états piégés ou de rugosité de surface. À cet égard, les dicalchogénures de métaux de transitions, de très haute qualité cristalline et atomiquement plats, font partis des semi-conducteurs les plus adaptés aux grilles EDL.Nous avons réalisé des transistors à effet de champ avec des EDL dans des nanotubes multi-couches de ce{WS2}, avec des performances comparables à celles de transistors EDL sur des ilots de ce{WS2}, et meilleurs que celles de nanotubes de ce{WS2} avec une grille solide. Nous avons obtenu des mobilités allant jusqu’à SI{80}{squarecentimetrepervoltpersecond} pour les porteurs n et p, et des ratios de courants on/off dépassant SI{e5}{} pour les deux polarités. Pour de forts dopages de type électron, les nanotubes ont un comportement métallique jusqu’à basse température. De plus, utiliser un liquide ionique permet de créer une jonction pn de manière purement électrostatique. En prenant avantage de cet effet, nous avons pu réaliser un transistor photoluminescent dans un nanotube.La possibilité de susciter de très forte densités de charges donne la possibilité d’induire des phases métalliques ou supraconductrices dans des semi-conducteurs a large bande interdite. Nous avons ainsi réussi à induire par effet de champ une phase métallique à basse température dans du diamant intrinsèque avec une surface hydrogénée, et nous avons obtenu un effet de champ dans du silicone dopé métallique.Les liquides ioniques offrent beaucoup d’avantages, mais leur champ d’application est encore réduit par l’instabilité du liquide, ainsi que par les courants de fuites et l’absorption graduelle d’impuretés. Un moyen efficace de s’affranchir de ces inconvénients, tout en conservant la possibilité d’induire de très fortes densités de porteurs, est de gélifier le liquide ionique. Nous sommes allés plus loin en fabriquant des gels ioniques modifiés, avec les cations fixés sur une seule surface et les anions libres de se mouvoir au sein du gel. Cet outil nous a permis de réaliser une nouvelle diode à effet de champ de faible puissance. / Ionic liquids are non-volatile fluids, consisting of cations and anions, which are ionically conducting and electrically insulating and hold very high capacitances. These liquids have the ability to not only to replace solid electrolytes, but to create strongly increased electric fields (>SI{10}{megavoltpercentimetre}) in the so-called electric double layer (EDL) on the electrolyte/channel interface, which leads to the injection of 2D charge carrier densities up to SI{e15}{cm^{-2}}. The remarkably strong gate effect of ionic liquids is diminished in the presence of trapped states and roughness-induced surface disorder, which points out that atomically flat transition metal dichalcogenides of high crystal quality are some of the semiconductors best suited for EDL-gating.We realised EDL-gated field-effect transistors based on multi-walled ce{WS2} nanotubes with operation performance comparable to that of EDL-gated thin flakes of the same material and superior to the performance of backgated ce{WS2} nanotubes. For instance, we observed mobilities of up to SI{80}{squarecentimetrepervoltpersecond} for both p- and n-type charge carriers and our current on-off ratios exceed SI{e5}{} for both polarities. At high electron doping levels, the nanotubes show metallic behaviour down to low temperatures. The use of an electrolyte as topgate dielectric allows the purely electrostatic formation of a pn-junction. We successfully fabricated a light-emitting transistor taking advantage of this utility.The ability of high charge carrier doping suggests an electrostatically induced metal phase or superconductivity in large gap semiconductors. We successfully induced low temperature metallic conduction into intrinsic diamond with hydrogen-terminated surface via field-effect and we observed a gate effect in doped, metallic silicon.Ionic liquids have many advantageous properties, but their applicability suffers from the instability of their liquid body, gate leakage currents and absorption of impurities. An effective way to bypass most of these problems, while keeping the ability of ultra-high charge carrier injection, is the gelation of ionic liquids. We even went one step further and fabricated modified ion gel films with the cations fixed on one surface and the anions able to move freely through the film. With this tool, we realised a novel low-power field-effect diode.

Oxigênio molecular singlete [O2(1Δg)], uma espécie excitada, desempenha um papel importante em sistemas químicos e biológicos. É um poderoso eletrófilo, que reage com moléculas ricas em elétrons através de cicloadições [2+2], [4+2] e reações tipo ene. Ácidos graxos poliinsaturados, proteínas e DNA são alvos vulneráveis para o ataque de O2(1Δg). Os endoperóxidos de derivados de naftaleno são muito úteis e versáteis como fontes limpas de O2(1Δg), uma vez que são quase quimicamente inertes. Por outro lado, o desenvolvimento de novas fontes de O2(1Δg) ainda é uma tarefa desafiadora. Os derivados de naftaleno são capazes de armazenar O2(1Δg) por reação de cicloadiação [4+2] e liberá-lo em temperaturas amenas, o que os torna muito adequados para uso em estudos biológicos. A síntese destes compostos está baseada em modificações nos substituintes ligados nas posições 1 e 4 da estrutura do naftaleno. Na primeira parte deste trabalho, a síntese de três endoperóxidos derivados do naftaleno solúveis em água foi realizada. DHPNO2 e NDPO2 foram preparados de acordo com métodos similares descritos na literatura. A síntese de um novo endoperóxido dicatiônico derivado do naftaleno (NBTEO2) foi desenvolvida, contendo dois grupos de cloreto de amônio quaternário nas posições 1,4 do anel aromático. O intermediário chave na síntese dos três endoperóxidos é o BBMN, o qual foi preparado a partir da bromação radicalar do 1,4-dimetilnaftaleno. Nossos resultados têm indicado que este composto dicatiônico pode ser uma fonte química de O2(1Δg) em potencial, e pode ser explorado em estudos com mitocôndrias, onde o papel biológico de O2(1Δg) é investigado. A segunda parte deste trabalho foi dedicada a investigar a geração de O2(1Δg) através das reações entre hidroperóxidos de lipídeos (ácido oleico, linoleico e colesterol), hidroperóxidos orgânicos (cumeno e t-butila), bem como peróxido de hidrogênio com NO2+, utilizando o composto NO2BF4. Evidências da geração de O2(1Δg) foram obtidas através de medidas de emissão de luz na região do infravermelho próximo, no comprimento de onda de 1270 nm. Além disso, a prova inequívoca da presença de O2(1Δg) foi demonstrada através da caracterização espectral direta da emissão de luz no infravermelho próximo. O uso de azida de sódio como captador físico de O2(1Δg), juntamente com as medidas da quimiluminescência, contribuíram para identificar a geração desta espécie na reação entre hidroperóxidos de lipídeos e NO2BF4. Embora seja uma abordagem química, nossos resultados adicionaram informações importantes sobre a peroxidação lipídica, principalmente quando espécies reativas de nitrogênio estão envolvidas. O O2(1Δg) poderia ser gerado como um subproduto da peroxidação lipídica em condições onde espécies reativas de nitrogênio interagem com hidroperóxidos lipídicos. Isto pode contribuir para um melhor entendimento deste evento complexo com implicações fisiológicas ou fisiopatológicas. / Singlet molecular oxygen [O2(1Δg)], an excited species, plays an important role in chemical and biological systems. It is a powerfull electrophile, reacting with electron rich molecules through [2+2] cycloadditions, [4+2] cycloadditions and ene reactions. Polyunsaturated fatty acids, proteins and DNA are vulnerable targets for O2(1Δg) reaction. Naphthalene derivatives endoperoxides are very useful and versatile as a clean source of O2(1Δg), once they are almost chemically inert. On the other hand, developing new sources of O2(1Δg) are still a challenging task. Naphthalene derivatives are able to trap O2(1Δg) by [4+2] cycloaddition and release it in mild temperatures, which make them very suitable for biological studies. The synthesis of these compounds is based on modifications in substituents bonded in 1,4 positions of nafhthalene backbone. In the first part of present work, the synthesis of three water soluble naphthalene derivatives endoperoxides was performed. DHPNO2, NDPO2 were prepared according to similar methods described in the literature. A new di-cationic naphthalene derivative endoperoxide (NBTEO2) synthesis was developed, containing two quaternary ammonium chloride groups in 1,4-positions of aromatic ring. The key intermediate: for the synthesis of the three endoperoxides is the compound BBMN, which was prepared from radicalar bromination of 1,4-dimethylnaphthalene. Our results have indicated that this di-cationic compound can be a potential chemical source of O2(1Δg) and may be explored in mitochondrial studies where O2(1Δg) biological role is investigated. The second part of this work is dedicated to the investigation of generation of O2(1Δg) through reaction of lipid hydroperoxides (oleic acid, linoleic acids and cholesterol), organic hydroperoxides (cumene and t-butyl), as well as hydrogen peroxide with NO2+, using the compound NO2BF4. Evidences of generation of O2(1Δg) were obtained recording the monomol light emission measurement in near infrared region at wavelength of 1270 nm. Moreover, the proof of the presence of O2(1Δg) was unequivocally demonstrated by the direct spectral characterization of near-infrared light emission. The use of sodium azide as a physical quencher of O2(1Δg), associated to chemiluminescence measurements, contributed to identify the generation of this species in the reaction of lipid hydroperoxides and NO2BF4. Although, it is a chemical approach, our results add important information about lipid peroxidation, mainly when reactive species of nitrogen are involved. O2(1Δg) might be generate as a byproduct of lipid peroxidation, in conditions where reactive nitrogen species interact with lipid hydroperoxides. This might contribute to a better understand of this complex event and physiological or physiopathological implications

Poly-p-phenylenebenzazoles (PBXs) are heterocyclic aromatic rigid-rod liquid-crystalline polymers with fully conjugated backbone having excellent thermo-oxidative, as well as dimensional stabilities. PBXs are considered to be multifunctional polymers of superior mechanical tenacity, non-linear optical response, and electrical properties. The fully conjugated PBX polymers are deemed to have excellent opto-electronic properties. In the last decade, molecular light emitting diodes (LEDs) have been investigated intensively for having distinct advantages as an advanced opto-electronic technology. This dissertation leads to rigid-rod polymer thin-films and mono-layer devices fabricated from acidic solutions. Photoluminescence (PL) spectra for poly-p-phenylenebenzobisthiazole (PBT) freestanding film were measured over a temperature range of 67 K to 300 K showing distinct electron-phonon interaction. Using an Mg cathode, the mono-layer PBT LEDs displayed a diodic electric response with a threshold voltage as low as 1 V. A blue shift in the maximum emission wavelength of the electroluminescence (EL) spectra was also observed with increasing electrical injection energy. For the multi-layer LEDs based on PBT using the same electrodes, the p-type/n-type bi-layer structure showing the most enhanced EL emission, and the tri-layer heterojunction had the least threshold voltage using the same electrodes. Our results indicated that the heterojunction architecture could be applied to balance charge carriers for increasing EL intensity. Meanwhile, the investigation also revealed the advantage in using the extra PBT layer for increasing both EL emission intensity and injection efficiency by lowering its threshold voltage. Two schemes for making uniaxial freestanding films and LED devices for polarized optical absorption and emission were processed from uniaxial poly-p-phenylenebenzobisoxazole (PBO) fiber. The PL of the uniaxial PBO films demonstrated an emission intensity ratio I¡ü/I¡æas high as 5. Anisotropically processed mono-layered PBO LED showed a markedly decreased threshold voltage from 7 V of the isotropic PBO device to 5 V. The polarization effects in optical absorption, PL and EL emissions were acquired and correlated with the uniaxial orientation of the rigid-rod PBO polymer. The molecular modification investigated the opto-electronic properties of poly-2,2'-m-phenylene-5,5'-bibenzimidazole (Pbi) with PBT physical blends, and monolithic 6F-PBO-OH-co-6F-PBO-di(OC10H21) copolymers. Partially conjugated polymer Pbi and fully conjugated polymer PBT were mixed for luminescence study. Their absorption spectra showed superposition of individual absorption response indicating no inter-molecular energy transfer. However, the PL and the EL emission demonstrated a blue shift with increasing Pbi content. This was attributed to the rigid-rod configuration or the aggregation of PBT perturbed by mixing with coil-like Pbi. It was recognized that the backbone of the fully conjugated rigid-rod PBT was collinear having more charge delocalization than that of not fully conjugated coil-like Pbi. The diode threshold voltage of the physical blends varied from 4 V to 14 V with decreasing PBT content. Another molecular modification was changing the composition of 6F-PBO copolymers. Their PL emission exhibited excellent chromatic tuning range from green to blue emission. The Commission Internationale de l¡¦Eclairage (C. I. E.) coordinates of the copolymer EL emission were from (0.25, 0.53) to (0.24, 0.31) covering a wide visible range and demonstrating a white light emission. Atomic substitution of the rigid-rod polymers was utilized to examine individual atomic contribution for luminescence emission. The hydrogen bond effect for PBO-OH and PBO was evidenced in a major Stoke¡¦s shift to a longer wavelength because of protonic transfer on the excited state. Elemental electronegativities affected the delocalization of the £k electron leading to a blue shift in absorption spectra as shown in case of PBO and PBT. The PBO molecule was more collinear and co-planar, providing more charge delocalization than PBT. However the absorption edge of the PBT was about 30 nm higher than that of PBO. This suggested that the electronegativities affected the molecular delocalization. Using the solid-state physics with pseudofunction (PSF) calculation, there was good match between absorption spectra and calculated excitation energies for the rigid-rod polymer systems.

Oxigênio molecular singlete [O2(1Δg)], uma espécie excitada, desempenha um papel importante em sistemas químicos e biológicos. É um poderoso eletrófilo, que reage com moléculas ricas em elétrons através de cicloadições [2+2], [4+2] e reações tipo ene. Ácidos graxos poliinsaturados, proteínas e DNA são alvos vulneráveis para o ataque de O2(1Δg). Os endoperóxidos de derivados de naftaleno são muito úteis e versáteis como fontes limpas de O2(1Δg), uma vez que são quase quimicamente inertes. Por outro lado, o desenvolvimento de novas fontes de O2(1Δg) ainda é uma tarefa desafiadora. Os derivados de naftaleno são capazes de armazenar O2(1Δg) por reação de cicloadiação [4+2] e liberá-lo em temperaturas amenas, o que os torna muito adequados para uso em estudos biológicos. A síntese destes compostos está baseada em modificações nos substituintes ligados nas posições 1 e 4 da estrutura do naftaleno. Na primeira parte deste trabalho, a síntese de três endoperóxidos derivados do naftaleno solúveis em água foi realizada. DHPNO2 e NDPO2 foram preparados de acordo com métodos similares descritos na literatura. A síntese de um novo endoperóxido dicatiônico derivado do naftaleno (NBTEO2) foi desenvolvida, contendo dois grupos de cloreto de amônio quaternário nas posições 1,4 do anel aromático. O intermediário chave na síntese dos três endoperóxidos é o BBMN, o qual foi preparado a partir da bromação radicalar do 1,4-dimetilnaftaleno. Nossos resultados têm indicado que este composto dicatiônico pode ser uma fonte química de O2(1Δg) em potencial, e pode ser explorado em estudos com mitocôndrias, onde o papel biológico de O2(1Δg) é investigado. A segunda parte deste trabalho foi dedicada a investigar a geração de O2(1Δg) através das reações entre hidroperóxidos de lipídeos (ácido oleico, linoleico e colesterol), hidroperóxidos orgânicos (cumeno e t-butila), bem como peróxido de hidrogênio com NO2+, utilizando o composto NO2BF4. Evidências da geração de O2(1Δg) foram obtidas através de medidas de emissão de luz na região do infravermelho próximo, no comprimento de onda de 1270 nm. Além disso, a prova inequívoca da presença de O2(1Δg) foi demonstrada através da caracterização espectral direta da emissão de luz no infravermelho próximo. O uso de azida de sódio como captador físico de O2(1Δg), juntamente com as medidas da quimiluminescência, contribuíram para identificar a geração desta espécie na reação entre hidroperóxidos de lipídeos e NO2BF4. Embora seja uma abordagem química, nossos resultados adicionaram informações importantes sobre a peroxidação lipídica, principalmente quando espécies reativas de nitrogênio estão envolvidas. O O2(1Δg) poderia ser gerado como um subproduto da peroxidação lipídica em condições onde espécies reativas de nitrogênio interagem com hidroperóxidos lipídicos. Isto pode contribuir para um melhor entendimento deste evento complexo com implicações fisiológicas ou fisiopatológicas. / Singlet molecular oxygen [O2(1Δg)], an excited species, plays an important role in chemical and biological systems. It is a powerfull electrophile, reacting with electron rich molecules through [2+2] cycloadditions, [4+2] cycloadditions and ene reactions. Polyunsaturated fatty acids, proteins and DNA are vulnerable targets for O2(1Δg) reaction. Naphthalene derivatives endoperoxides are very useful and versatile as a clean source of O2(1Δg), once they are almost chemically inert. On the other hand, developing new sources of O2(1Δg) are still a challenging task. Naphthalene derivatives are able to trap O2(1Δg) by [4+2] cycloaddition and release it in mild temperatures, which make them very suitable for biological studies. The synthesis of these compounds is based on modifications in substituents bonded in 1,4 positions of nafhthalene backbone. In the first part of present work, the synthesis of three water soluble naphthalene derivatives endoperoxides was performed. DHPNO2, NDPO2 were prepared according to similar methods described in the literature. A new di-cationic naphthalene derivative endoperoxide (NBTEO2) synthesis was developed, containing two quaternary ammonium chloride groups in 1,4-positions of aromatic ring. The key intermediate: for the synthesis of the three endoperoxides is the compound BBMN, which was prepared from radicalar bromination of 1,4-dimethylnaphthalene. Our results have indicated that this di-cationic compound can be a potential chemical source of O2(1Δg) and may be explored in mitochondrial studies where O2(1Δg) biological role is investigated. The second part of this work is dedicated to the investigation of generation of O2(1Δg) through reaction of lipid hydroperoxides (oleic acid, linoleic acids and cholesterol), organic hydroperoxides (cumene and t-butyl), as well as hydrogen peroxide with NO2+, using the compound NO2BF4. Evidences of generation of O2(1Δg) were obtained recording the monomol light emission measurement in near infrared region at wavelength of 1270 nm. Moreover, the proof of the presence of O2(1Δg) was unequivocally demonstrated by the direct spectral characterization of near-infrared light emission. The use of sodium azide as a physical quencher of O2(1Δg), associated to chemiluminescence measurements, contributed to identify the generation of this species in the reaction of lipid hydroperoxides and NO2BF4. Although, it is a chemical approach, our results add important information about lipid peroxidation, mainly when reactive species of nitrogen are involved. O2(1Δg) might be generate as a byproduct of lipid peroxidation, in conditions where reactive nitrogen species interact with lipid hydroperoxides. This might contribute to a better understand of this complex event and physiological or physiopathological implications

Les technologies VLSI (« Very large Scale Integration ») font partie de notre quotidien et nos besoins en miniaturisation sont croissants. La densification des transistors occasionne non seulement des difficultés à localiser les défauts dits « hard » apparaissant durant les phases de développement (débug) ou de vieillissement, mais aussi l’apparition de comportements non fonctionnels purs du composant liées à des défauts de conception. Les techniques abordées dans ce document sont destinées à sonder les circuits microélectroniques à l’aide d’un outil appelé émission de lumière dynamique (Time Resolved Imaging - TRI) à la recherche de comportements anormaux au niveau des timings et des patterns en jeu dans les structures. Afin d’aller plus loin, cet instrument permet également la visualisation thermographique en temps résolue de phénomènes thermiques transitoires au sein d’un composant. / VLSI ("Very Large Scale Integration") technologies are part of our daily lives and our miniaturization needs are increasing. The densification of transistors not only means trouble locating the so-called "hard defects" occurring during the development phases (debug) or aging, but also the appearance of pure non-functional behaviors related to component design flaws. Techniques discussed in this document are intended to probe the microelectronic circuits using a tool called dynamic light emission (Time Resolved Imaging - TRI) in search of abnormal behavior in terms of timings and patterns involved in structures. To go further, this instrument also allows viewing thermographic time resolved thermal transients within a component.

[ES] Uno de los retos más importantes de la sociedad actual es la obtención de energía de forma sostenible, limpia y eficiente. Por ello, gran parte de la investigación actual en el campo de la química y la ciencia de los materiales centra sus esfuerzos en la búsqueda y estudio de nuevas generaciones de materiales que permitan una transición energética desde el modelo energético tradicional hacia un modelo más sostenible. En este contexto, las propiedades eléctricas de los materiales, relacionadas con la generación y transformación de energía, juegan un papel esencial. En esta tesis se estudian dos tipos de materiales híbridos con distinta estructura y composición, pero que combinan excelentes propiedades eléctricas y ópticas. Por una parte, los clústeres octaédricos de molibdeno, ya conocidos desde hace décadas, han demostrado ser excelentes materiales en catálisis. En los últimos tiempos, la investigación alrededor de este material se ha centrado en el estudio de sus propiedades ópticas y electrónicas y sus aplicaciones en sensores y dispositivos emisores de luz. Por otra parte, las perovskitas híbridas halogenadas son ampliamente conocidas en el campo de la generación energética por sus elevadas eficiencias, movilidad de cargas y alta eficiencia de emisión de luz. Se han estudiado dos estructuras de perovskita híbrida halogenada: una 3D, cuyas propiedades son ampliamente conocidas, y otra con estructura multidimensional 2D-3D, donde el carácter laminar le confiere una mejora en la estabilidad. Con el propósito de comprender mejor su interacción luz-materia, en los trabajos desarrollados en la presente tesis, se han realizado mediciones optoelectrónicas a nivel monocristalino. Esto incluye un análisis combinando de medidas de emisión, fotocolección y transporte de carga. Además, se ha investigado su comportamiento como cavidad resonante, así como sus propiedades como generador de energía. Por lo tanto, se ha corroborado que los materiales objeto de estudio, presentan unas propiedades que les confieren diferentes posibilidades de aplicación en diversos ámbitos dentro del campo de la generación energética. / [CA] Un dels reptes més importants de la societat actual és obtenir energia de forma sostenible, neta i eficient. Per això, gran part de la investigació actual en el camp de la química i la ciència dels materials centra els seus esforços en la cerca i l'estudi de noves generacions de materials que permeten una transició energètica des del model energètic tradicional cap a un model més sostenible. En aquest context, les propietats elèctriques dels materials, relacionades amb la generació i la transformació d'energia juguen un paper essencial. En aquesta tesi s'estudien dos tipus de materials híbrids amb diferent estructura i composició, però que combinen propietats elèctriques i òptiques excel·lents. D'una banda, els clústers octaèdrics de molibdè, ja coneguts des de fa dècades, han demostrat ser materials idonis en catàlisi. De fet, en els darrers temps, la recerca al voltant d'aquest material s'ha centrat en l'estudi de les propietats òptiques i electròniques i les aplicacions en sensors i dispositius emissors de llum. D'altra banda, les perovskites híbrides halogenades són àmpliament conegudes al camp de la generació energètica per les seues elevades eficiències, mobilitat de càrregues i alta eficiència d'emissió de llum. S'han estudiat dues estructures de perovskita híbrida halogenada: una de 3D, les propietats de la qual són àmpliament conegudes, i una altra amb estructura multidimensional 2D-3D, el caràcter laminar de la qual li confereix una millora en l'estabilitat. Amb el propòsit de comprendre millor la seua interacció llum-matèria, en els treballs desenvolupats en aquesta tesi, s'han realitzat mesuraments optoelectrònics a nivell monocristal·lí. Això inclou una anàlisi que combina mesures d'emissió, fotocol·lecció i transport de càrrega. A més, s'ha investigat el seu comportament com a cavitat ressonant, així com les seues propietats com a generador d'energia. Per tant, s'ha corroborat que els materials objecte d'estudi presenten unes propietats que els confereixen diferents possibilitats d'aplicació en diversos àmbits dins del camp de la generació energètica. / [EN] One of the most important challenges of today's society is obtaining energy in a sustainable, clean, and efficient way. For this reason, much of the current research in the field of chemistry and materials science focuses its efforts on the search and study of new generations of materials that allow an energy transition from the traditional energy model to a more sustainable model. In this context, the electrical properties of materials, related to the generation and transformation of energy, play an essential role. In this thesis, two types of hybrid materials with different structure and composition, but which combine excellent electrical and optical properties, are studied. On the one hand, octahedral molybdenum clusters have been known for decades and have proven to be excellent materials in catalysis. In fact, in recent times, research around this material has focused on the study of its optical and electronic properties and its applications in sensors and light-emitting devices. On the other hand, halogenated hybrid perovskites are widely known in the field of energy generation for their high efficiencies, charge mobility and high light emission efficiency. Two halogenated hybrid perovskite structures were studied: one 3D, whose properties are widely known, and another with a 2D-3D multidimensional structure, where the laminar character confers an improvement in stability. To better understand its light-matter interaction, in the work developed in this thesis, optoelectronic measurements have been carried out at the monocrystalline level. This includes a combined analysis of emission, photocollection and charge transport measurements. In addition, its behavior as a resonant cavity has been investigated, as well as its properties as an energy generator. Therefore, it has been confirmed that the materials under study have properties that give them different application possibilities in various areas within the field of energy generation. / Segura Sanchis, E. (2024). Propiedades ópticas y eléctricas de monocristales de materiales híbridos [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/202755