Dans la première partie de cette thèse, nous tirons parti du concept de nano-antenne optique afind'apporter une solution innovante au problème d'interprétation de la microscopie champ procheoptique (SNOM). En effet, il est connu que certaines nano-antennes développent des réponsesoptiques dipolaires. Dans cette thèse nous démontrons comment l’utilisation d’une nano-ouverturepapillon (nano-antenne dipolaire), à l’extrémité d’une pointe SNOM, permet de détecter et collecteruniquement une seule composante du champ proche électrique. Ce résultat est démontré d’unpoint de vue théorique par l’utilisation de simulation FDTD (Finite Difference Time Domain) et d’unpoint de vue expérimental par la caractérisation, par cette pointe innovante, d´échantillonsdiélectriques (réseaux, cristaux photoniques) et métalliques (milieux désordonnés plasmoniques).Dans une deuxième partie, nous démontrons comment la sonde développée dans la premièrepartie, peut être utilisée comme détecteur du signal émis par un nano-émetteurs (NE) unique. Il estétudié dans cette partie l’effet de couplage entre ces deux objets. Dans un premier temps, après ladescription complète des grandeurs caractéristiques d’un NE, nous démontrons théoriquementl’effet de la pointe sur la réduction du temps de vie de l’état excité et l’augmentation de lafluorescence d’un NE, en régime saturé et non saturé. Puis dans un deuxième temps nousdémontrons expérimentalement comment cette sonde réduit le temps de vie de l’état excité deboites quantiques placées à son extrémité, en comparaison de pointes SNOM plus conventionnellestelle que la pointe diélectrique et la pointe à ouverture circulaire. / In the first part of this manuscript, we use in our advantage the concept of optical nano-antennas, toget new solutions on the interpretation problems of scanning near-field optical microscope (SNOM)images. Indeed, it is known that some of the developed nano-antennas can express dipolarbehaviours. In this manuscript, we show how a bowtie nano-aperture (dipolar nano-antenna)embedded at the apex of a SNOM probe, can be used to detect and collect only one component ofthe electric near-field. This result is demonstrated as well theoretically, by the use of FDTD (FiniteDifference Time Domain) codes, as experimentally, by the characterisation with this tip, of dielectricsamples (diffraction grating and photonic crystals) and metallic ones (random plasmonic medium).In a second part, we show how the tip previously described, can be used as a detector of the signalfrom single emitter (SE). We study in this part the coupling and interactions between those twoobjects. After a full description of a two level system characteristics, we show theoretically the effectof our probe on the reduction of the excited state life time and the enhancement of thefluorescence of the SE, in both regime, saturated and non-saturated. Then we describeexperimentally how our special tip reduces the excited state life time of quantum dots placed at theapex of it, respect to more conventional SNOM probes as the dielectric and the circular apertureones.

In this work, homojunction interfacial workfunction internal photoemission (HIWIP) detectors based on GaAs, and heterojunction interfacial workfunction internal photoemission (HEIWIP) detectors based mainly on the Gallium Arsenide/Aluminum Gallium Arsenide material system are presented. Design principles of HIWIP and HEIWIP detectors, such as free carrier absorption, photocarrier generation, photoemission, and responsivity, are discussed in detail. Results of p-type HIWIPs based on GaAs material are presented. Homojunction detectors based on p-type GaAs were found to limit their operating wavelength range. This is mainly due to band depletion arising through carrier transitions from the heavy/light hole bands to the split off band. Designing n-type GaAs HIWIP detectors is difficult as it is strenuous to control their workfunction. Heterojunction detectors based on Gallium Arsenide/Aluminum Gallium Arsenide material system will allow tuning their threshold wavelength by adjusting the alloy composition of the Aluminum Gallium Arsenide/Gallium Arsenide barrier, while keeping a fixed doping density in the emitter. The detectors covered in this work operate from 1 to 128 micron (300 to 2.3 THz). Enhancement of detector response using resonance cavity architecture is demonstrated. Threshold wavelength extension of HEIWIPs by varying the Al composition of the barrier was investigated. The threshold limit of approximately 3.3 THz (92 micron), due to a practical Al fraction limit of approximately 0.005, can be overcome by replacing GaAs emitters in Gallium Arsenide/Aluminum Gallium Arsenide HEIWIPs with Aluminum Gallium Arsenide/Gallium Arsenide emitters. As the initial step, terahertz absorption for 1 micron-thick Be-doped Aluminum Gallium Arsenide epilayers (with different Al fraction and doping density) grown on GaAs substrates was measured. The absorption probability of the epilayers was derived from these absorption measurements. Based on the terahertz absorption results, an Aluminum Gallium Arsenide/Gallium Arsenide HEIWIP detector was designed and the extension of threshold frequency (f0) to 2.3 THz was successfully demonstrated. In a different study, switching in Gallium Arsenide/Aluminum Gallium Arsenide heterostructures from a tunneling dominated low conductance branch to a thermal emission dominated high conductance branch was investigated. This bistability leads to neuron-like voltage pulses observed in some heterostructure devices. The bias field that initiates the switching was determined from an iterative method that uses feedback information, such as carrier drift velocity and electron temperature, from hot carrier transport. The bias voltage needed to switch the device was found to decrease with the increasing device temperature.

No description available.

Tailored fluoropolymers remain the leading choice for a wide variety of advanced high-performance applications, including electronic/optical and energy conversion, owing to their unique blend of complementary high-performance properties. Amorphous semi-fluorinated polymers exhibit improved solubility and melt processability when compared to traditional perfluoropolymers. A leading class of semi-fluorinated aryl ether polymers includes perfluorocyclobutyl (PFCB), perfluorocycloalkenyl (PFCA), and fluoroarylene vinylene ether (FAVE) polymers. Monomers containing aromatic trifluorovinyl ethers (TFVE) are used to synthesize PFCB polymers via radical-mediated [2+2] cyclodimerization. On the other hand, FAVE and PFCA polymers are polymerized via base-mediated nucleophilic addition/elimination of bisphenols with TFVE monomers and decafluorocyclohexene respectively. The use of different monomer cores (aromatic, aliphatic, contorted, and renewable) should help to develop general structure/property relationships for this versatile and expanding approach to semi-fluorinated aryl ether polymers. The enchainment of polycyclic aromatic hydrocarbon (PAH) cores with functional fluorocarbon groups (or segments) recently afforded a new class of semi- fluorinated polymers in the continuing quest for novel organic materials for potential applications in optoelectronic, gas-separation, and advanced composites. Chapter 2 details the incorporation of commercially available acenaphthenequinone was achieved to afford PFCB aryl ether polymers with excellent solubility, high thermal stability, and film-forming capability. Chapter 3 represents base-promoted nucleophilic addition/elimination of commercial bisphenols with TFVE-triphenylene monomers affording FAVE aryl ether polymers possessing excellent solution processability, high thermal stability and photostability. In addition, triphenylene-enchained FAVE polymers exhibit extreme thermal-oxidative photostability and emit blue light after heating in air at 250 °C for 24 h. Further, time-dependent density functional theory (TD-DFT) computations were performed to understand electronic polymer structures. In one case, post-polymerization Scholl coupling converted the central triphenylene core to afford a hexabenzocoronene containing semi-fluorinated polymer with new optoelectronic properties. Chapter 4 demonstrates synthesis and characterization of renewable semi-fluorinated polymers obtained using aliphatic diol isosorbide. This renewable diol readily polymerizes with bis-TFVE derivatives of bisphenol A and 6F to provide high molecular weight thermoplastics exhibiting excellent solubility and tough, transparent film-forming capability. Finally, Chapter 5 presents synthesis of TFVE enchained corannulene which gave blue-light emission and outstanding processability. Synthesis and characterization, including the new materials' optical, thermal, and electronic properties, is presented.

<p dir="ltr">This thesis is about the exciting discovery of a new kind of single photon emitter that<br>is suspected to occur at the interface of silicon nitride SixNy and silicon dioxide SiO2 after<br>being rapidly annealed. Since SixNy is one of the most developed platforms for integrated<br>photonics the discovery of a native emitter in this platform opened up the possibility for<br>seamless integration of these single photon emitters with photonic circuitry for the first<br>time. This seamless integration was demonstrated as is shown in Chapter 3 by creating the<br>emitters and then patterning the SixNy layer into a waveguide. This work demonstrated for<br>the first time the coupling of such single photon emitters with on-chip integrated photonics.<br>However, the integration approach demonstrated was based on the stochastic integration of<br>emitters which limits the efficiency of the devices and the possible types of devices that can<br>be designed. This is why the next stage of research focused on the development of a site-<br>controlled process for creating these single photon emitters. Remarkably, it was found that<br>if the SixNy and SiO2 are nanostructured into nanopillars and then annealed then a single<br>photon emitter forms over 65% of the time within the nanopillar! Due to the lithography<br>defined nature of this process for creating the single photon emitters the first multi-mask<br>integration process was also developed and demonstrated. This fabrication process was used<br>to demonstrate the integration of several thousand single photon emitters with complex<br>integrated photonic structures such as topology optimized couplers. These developments<br>has generated a great deal of excitement due to the inherent scalability of the approach and<br>it’s obvious applications for the development of very large scale integrated (VLSI) on-chip<br>quantum photonic systems.</p>

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Ocorrem anualmente aproximadamente 600.000 mortes de crianças com até cinco anos, no mundo. Pneumonia é a principal causa e mais de 50 por cento destas mortes são atribuídas à poluição do ar. Ela ainda é responsável pelo aumento do risco de infecções respiratórias, asma, condições neonatais adversas e anomalias congênitas. A poluição do ar também afeta o desenvolvimento cognitivo de crianças e induz o desenvolvimento de doenças crônicas na idade adulta. Entre 70 e 80 por cento da poluição do ar em nações em desenvolvimento são de origem veicular. Objetivando definir critérios baseados em medições com sensoriamento remoto para identificação de veículos automotores leves do ciclo Otto com elevadas emissões de monóxido de carbono, hidrocarbonetos ou óxido nítrico, foram utilizados os dados secundários gerados pela Remote Sensing do Brasil Ltda dos quais foram selecionados 179.142 veículos em uso da frota circulante da cidade de São Paulo com medições completas dos índices de emissão dos poluentes monóxido de carbono (CO), hidrocarbonetos (HC) e óxido nítrico (NO) e ainda velocidade e aceleração do veículo quando da medição e inclinação da pista no local escolhido para as medições. Foram ajustados modelos estatísticos da classe Generalised Additive Models for Location, Scale and Shape (GAMLSS) visando testar a influência do Tipo de Combustível, da Potência Específica do Veículo (VSP) e das Fases do Programa de Controle da Poluição do Ar por Veículos Automotores (Proconve) sobre as emissões de CO, HC e NO, medidos usando o Remote Sensing Device (RSD). As emissões foram então conceitualmente subdivididas em dois grupos: veículos com emissões normais e com emissões anormais, isso para os diversos poluentes em veículos das Fases L3, L4 e L5 que são as fases de interesse para o gerenciamento da qualidade do ar. Variáveis latentes foram definidas para indicarem as distribuições dos veículos em relação a esses grupos e Fases. O algoritmo Expectation-Maximization (EM) foi empregado para identificação dos parâmetros das distribuições. Para determinação dos valores associados aos veículos com elevadas emissões de determinado poluente e fase do Proconve, foi empregado o percentil 98 por cento da distribuição ajustada para os veículos dos grupos com emissões normais. Assim sendo, o Erro de Tipo I foi fixado em 2 por cento sendo que esse percentual foi estabelecido considerando o Erro de Tipo II, de apontar o veículo como tendo emissão normal quando na realidade trata-se de um high emitter. Através desta abordagem foram determinados os valores indicativos de veículos com elevadas emissões segundo o poluente e a Fase do Proconve. Os resultados apontaram decréscimo nas emissões de CO e de HC segundo as Fases do Proconve. Para o NO, o comportamento das emissões não acompanhou as reduções impostas pelas Fases do Proconve. Foi constatado que os veículos de 2005 a 2009, movidos exclusivamente a gasool, foram os que apresentaram as maiores emissões de NO. Diversos possíveis fatores causadores deste comportamento diferenciado do NO foram discutidos neste trabalho. Os dados de qualidade do ar detectaram aumento significativo nas concentrações ambientais de Óxidos de Nitrogênio (NOx) em 2007, quando foi monitorado este parâmetro no período de inverno, o que pode indicar a influência dos high emitters, mas necessita de estudos mais aprofundados para confirmação da causa deste comportamento. / Approximately 600,000 deaths occur worldwide annually for children up to five years of age. Pneumonia is the leading cause and more than 50 per cent of these deaths are attributed to air pollution. It is still responsible for increased risk of respiratory infections, asthma, adverse neonatal conditions and congenital anomalies. Air pollution also affects the cognitive development of children and induces future development of chronic diseases in adulthood. In order to define criteria based on remote sensing measurements to identify Otto cycle light duty vehicles (LDV) with high emissions of carbon monoxide, hydrocarbons or nitric oxide it was used secondary data produced by Remote Sensing do Brasil Ltda, from which 179,142 inuse vehicles were selected, that belongs to the city of São Paulos current fleet. All those vehicles had complete measurements of emission of carbon monoxide (CO), hydrocarbons (HC) and nitric oxide (NO), and also speed and acceleration of the vehicle during measurements, and slope of the track at the place chosen for the measurements. Statistical models of the Generalized Additive Models for Location, Scale and Shape (GAMLSS) class were adjusted to test the influence of fuel type, Vehicle Specific Power (VSP) and of the Brazilian Vehicle Emission Control Program [Proconve] phases on CO, HC and NO emissions, measured using Remote Sensing Device (RSD). The emissions were then conceptually subdivided into two groups: vehicles with normal and abnormal emission, for the various pollutants in vehicles of L3, L4 and L5 phases of Proconve, which were of interest for the air quality management. Latent variables were defined to indicate the distribution of vehicles in relation to those groups and phases. The algorithm Expectation Maximization (EM) was employed to identify all parameters of the distributions. We use the 98 per cent percentiles of the statistical distribution set, for vehicles of groups with normal emissions to determine the limit values for vehicles with high emissions of pollutants and Proconve Phase. Therefore, the Type I Error was set at 2 per cent and this percentage was established considering the Type II Error to point the vehicle as having normal emission when in fact it is a high emitter. Through this approach, the indicative values of vehicles with high emissions according to the pollutant and the Proconve Phase were determined. Results of emissions measured with the RSD technique indicated a decrease in CO and HC emissions according to the Proconve Phase. For the NO, the emissions behavior did not follow the reductions imposed by the Proconve Phases. It was found that newer vehicles year model from 2005 to 2009 exclusively gasohol-powered vehicles, were the ones that presented the highest NO emissions. Several possible causative factors of this differential behavior of NO were discussed in this study. A significant increase in the environmental concentrations of Nitrogen Oxides (NOx) was detected in 2007, when this parameter was monitored in the winter period. This may indicate the influence of the high emitter vehicles, but it requires a more in-depth cause-effect study for confirmation of this behavior.

Elektrische und magnetische Emitter können zur Erforschung unterschiedlicher plasmonischer Nanostrukturen genutzt werden. Indem wir die Änderung der Abstrahldynamik und in der Lebensdauer bestimmen, detektieren wir die photonische lokale Zustandsdichte. Diese Zustandsdichte, die eine Eigenschaft der Umgebung ist, ermöglicht uns nicht nur Rückschlüsse auf die elektronischen und andere physikalische Eigenschaften dieser zu treffen sondern auch die allgemeinen Eigenschaften der plasmonischen Nanostruktur im Bezug auf Licht-Materie Kopplung zu bestimmen. Eine starke Licht-Materie-Kopplung ist für die zukünftige Anwendung im Bereich der Quantentechnologien wichtig. Wenn Emitter hierbei mit plasmonischen Nanostrukturen koppeln, fokussieren letztere nicht nur das emittierte Lichts an der Oberfläche im Subwellenlängenbereich sondern ermöglichen durch die Feldüberhöhung an der Oberfläche auch eine starke Licht-Materie-Kopplung. In der Arbeit konzentrieren wir uns auf zwei grundlegend unterschiedliche plasmonische Systeme: zunächst untersuchen wir analytisch den Einfluss von Graphen auf elektrische und magnetische Emitter und diskutieren dann die Lebensdaueränderungen und Strahlungsdynamiken in der Nähe von Silber- und Goldnanostrukturen. Im ersten Teil der Arbeit analysieren wir den Einfluss von Graphen mit einer Bandlücke auf den Emitter und zeigen Möglichkeiten zur experimentellen Bestimmung der Bandlücke auf. Im zweiten Teil modellieren wir die Propagation elektromagnetischer Felder im dreidimensionalen Raum mit Hilfe der Diskontinuierlichen Galerkin Zeitraum Methode mit erweiterten Funktionalitäten. Diese verwenden wir sowohl zur theoretischen Modellierung des ersten dreidimensionalen Fluoreszenlebensdauerabbildungsmikroskopie mit einem einzelnen Quantenemitter als auch zur selbstkonsistent Beschreibung von Emittern in der Nähe eines Goldpentamers. Die Kombination der Studien betont die Stärke von Emittern elektrische, optische und magnetische Eigenschaften zu detektieren. / Electric and magnetic emitters can be used to probe different plasmonic nanostructures. By determining the modification of the radiation dynamics and the lifetimes, we can measure the photonic local density of states. This, being a property of the enviroment, does not only allow us to draw conclusions regarding the electronic and other physical properties of the latter but also regarding the general light-matter coupling properties of the plasmonic nanostructure. A strong light-matter coupling is important for future applications in quantum technology. If emitters couple specifically to plasmonic nanostructure, the latter do not only focus the emitted light at the sub-wavelength scale at the surface of the structure but also allow for such a strong light-matter coupling due to the field enhancement at the surface. In this work, we focus on two different basic plasmonic systems: first, we study analytically the influence of graphene on electric and magnetic emitters, and second we discuss lifetime modifications and radiation dynamics close to silver and gold nanostructures. In the first part of this work, we specifically focus on the influence of graphene exhibiting a finite band gap on the emitter. In the second part, we model the propagation of electromagnetic fields in three-dimensional space making use of the discontinuous Galerkin time-domain method with extended functionalities. This framework we apply to model the first three-dimensional scanning-probe fluorescence-lifetime imaging microscopy by use of a single quantum-emitter as well as for a self-consistent description of emitters in the proximity of a gold pentamer. The combination of these studies stress that the strength of emitters lies in the detection of electronic, optical and magnetic properties.

Ocorrem anualmente aproximadamente 600.000 mortes de crianças com até cinco anos, no mundo. Pneumonia é a principal causa e mais de 50 por cento destas mortes são atribuídas à poluição do ar. Ela ainda é responsável pelo aumento do risco de infecções respiratórias, asma, condições neonatais adversas e anomalias congênitas. A poluição do ar também afeta o desenvolvimento cognitivo de crianças e induz o desenvolvimento de doenças crônicas na idade adulta. Entre 70 e 80 por cento da poluição do ar em nações em desenvolvimento são de origem veicular. Objetivando definir critérios baseados em medições com sensoriamento remoto para identificação de veículos automotores leves do ciclo Otto com elevadas emissões de monóxido de carbono, hidrocarbonetos ou óxido nítrico, foram utilizados os dados secundários gerados pela Remote Sensing do Brasil Ltda dos quais foram selecionados 179.142 veículos em uso da frota circulante da cidade de São Paulo com medições completas dos índices de emissão dos poluentes monóxido de carbono (CO), hidrocarbonetos (HC) e óxido nítrico (NO) e ainda velocidade e aceleração do veículo quando da medição e inclinação da pista no local escolhido para as medições. Foram ajustados modelos estatísticos da classe Generalised Additive Models for Location, Scale and Shape (GAMLSS) visando testar a influência do Tipo de Combustível, da Potência Específica do Veículo (VSP) e das Fases do Programa de Controle da Poluição do Ar por Veículos Automotores (Proconve) sobre as emissões de CO, HC e NO, medidos usando o Remote Sensing Device (RSD). As emissões foram então conceitualmente subdivididas em dois grupos: veículos com emissões normais e com emissões anormais, isso para os diversos poluentes em veículos das Fases L3, L4 e L5 que são as fases de interesse para o gerenciamento da qualidade do ar. Variáveis latentes foram definidas para indicarem as distribuições dos veículos em relação a esses grupos e Fases. O algoritmo Expectation-Maximization (EM) foi empregado para identificação dos parâmetros das distribuições. Para determinação dos valores associados aos veículos com elevadas emissões de determinado poluente e fase do Proconve, foi empregado o percentil 98 por cento da distribuição ajustada para os veículos dos grupos com emissões normais. Assim sendo, o Erro de Tipo I foi fixado em 2 por cento sendo que esse percentual foi estabelecido considerando o Erro de Tipo II, de apontar o veículo como tendo emissão normal quando na realidade trata-se de um high emitter. Através desta abordagem foram determinados os valores indicativos de veículos com elevadas emissões segundo o poluente e a Fase do Proconve. Os resultados apontaram decréscimo nas emissões de CO e de HC segundo as Fases do Proconve. Para o NO, o comportamento das emissões não acompanhou as reduções impostas pelas Fases do Proconve. Foi constatado que os veículos de 2005 a 2009, movidos exclusivamente a gasool, foram os que apresentaram as maiores emissões de NO. Diversos possíveis fatores causadores deste comportamento diferenciado do NO foram discutidos neste trabalho. Os dados de qualidade do ar detectaram aumento significativo nas concentrações ambientais de Óxidos de Nitrogênio (NOx) em 2007, quando foi monitorado este parâmetro no período de inverno, o que pode indicar a influência dos high emitters, mas necessita de estudos mais aprofundados para confirmação da causa deste comportamento. / Approximately 600,000 deaths occur worldwide annually for children up to five years of age. Pneumonia is the leading cause and more than 50 per cent of these deaths are attributed to air pollution. It is still responsible for increased risk of respiratory infections, asthma, adverse neonatal conditions and congenital anomalies. Air pollution also affects the cognitive development of children and induces future development of chronic diseases in adulthood. In order to define criteria based on remote sensing measurements to identify Otto cycle light duty vehicles (LDV) with high emissions of carbon monoxide, hydrocarbons or nitric oxide it was used secondary data produced by Remote Sensing do Brasil Ltda, from which 179,142 inuse vehicles were selected, that belongs to the city of São Paulos current fleet. All those vehicles had complete measurements of emission of carbon monoxide (CO), hydrocarbons (HC) and nitric oxide (NO), and also speed and acceleration of the vehicle during measurements, and slope of the track at the place chosen for the measurements. Statistical models of the Generalized Additive Models for Location, Scale and Shape (GAMLSS) class were adjusted to test the influence of fuel type, Vehicle Specific Power (VSP) and of the Brazilian Vehicle Emission Control Program [Proconve] phases on CO, HC and NO emissions, measured using Remote Sensing Device (RSD). The emissions were then conceptually subdivided into two groups: vehicles with normal and abnormal emission, for the various pollutants in vehicles of L3, L4 and L5 phases of Proconve, which were of interest for the air quality management. Latent variables were defined to indicate the distribution of vehicles in relation to those groups and phases. The algorithm Expectation Maximization (EM) was employed to identify all parameters of the distributions. We use the 98 per cent percentiles of the statistical distribution set, for vehicles of groups with normal emissions to determine the limit values for vehicles with high emissions of pollutants and Proconve Phase. Therefore, the Type I Error was set at 2 per cent and this percentage was established considering the Type II Error to point the vehicle as having normal emission when in fact it is a high emitter. Through this approach, the indicative values of vehicles with high emissions according to the pollutant and the Proconve Phase were determined. Results of emissions measured with the RSD technique indicated a decrease in CO and HC emissions according to the Proconve Phase. For the NO, the emissions behavior did not follow the reductions imposed by the Proconve Phases. It was found that newer vehicles year model from 2005 to 2009 exclusively gasohol-powered vehicles, were the ones that presented the highest NO emissions. Several possible causative factors of this differential behavior of NO were discussed in this study. A significant increase in the environmental concentrations of Nitrogen Oxides (NOx) was detected in 2007, when this parameter was monitored in the winter period. This may indicate the influence of the high emitter vehicles, but it requires a more in-depth cause-effect study for confirmation of this behavior.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal