The solid-state mesoscopic solar cells (sMSCs) have been developed as a promising alternative technology to the conventional photovoltaics. However, the device performance suffers from the low hole-mobilities and the incomplete pore filling of the hole transport materials (HTMs) into the mesoporous electrodes. A variety of HTMs and different preparation methods have been studied to overcome these limitations. There are two types of sMSCs included in this doctoral thesis, namely solid-state dye-sensitized solar cells (sDSCs) and organometallic halide perovskite based solar cells. Two different types of HTMs, namely the small molecule organic HTM spiro-OMeTAD and the conjugated polymer HTM P3HT, were compared in sDSCs. The photo-induced absorption spectroscopy (PIA) spectra and spectroelectrochemical data suggested that the dye-dye hole conduction occurs in the absence of HTM and appears to be of significant importance to the contribution of hole transport. The PIA measurements and transient absorption spectroscopy (TAS) indicated that the oxidized dye was efficiently regenerated by a small molecule organic HTM TPAA due to its excellent pore filling. The conducting polymer P3HT was employed as a co-HTM to transfer the holes away from TPAA to prohibit the charge carrier recombination and to improve the hole transport. An alternative small molecule organic HTM, MeO-TPD, was found to outperform spiro-OMeTAD in sDSCs due to its more efficient pore filling and higher hole-mobility. Moreover, an initial light soaking treatment was observed to significantly improve the device performance due to a mechanism of Li+ ion migration towards the TiO2 surface. In order to overcome the infiltration difficulty of conducting polymer HTMs, a state-of-the-art method to perform in-situ photoelectrochemical polymerization (PEP) in an aqueous micellar solution of bis-EDOT monomer was developed as an environmental-friendly alternative pathway with scale-up potential for constructing efficient sDSCs with polymer HTMs. Three different types of HTMs, namely DEH, spiro-OMeTAD and P3HT, were used to investigate the influence of HTMs on the charge recombination in CH3NH3PbI3 perovskite based sMSCs. The photovoltage decay measurements indicate that the electron lifetime (τn) of these devices decreases by one order of magnitude in the sequence τspiro-OMeTAD > τP3HT > τDEH.

Etwa die Hälfte aller Solarzellen weltweit wird aus blockerstarrtem Silizium hergestellt. Derartige Blöcke weisen in ihren Außenbereichen eine verringerte Diffusionslänge der Minoritätsladungsträger auf. Um die Ursache dafür im Fall des bodennahen Bereichs zu bestimmen wurden zwei Spezialblöcke (ein Block mit reduzierter Bor-Dotierung und ein Block mit Phosphor-Dotierung) - u. a. mittels DLTS und FTIR - auf Kristalldefekte untersucht. Zusätzlich zu Dotierelementen (B, P, Al, As) wurden im Bodenbereich folgende Defekte nachgewiesen: <u>Metalle</u>: Fe, Cr <u>Sauerstoffhaltige Defekte</u>: Interstitieller Sauerstoff, Thermische Donatoren (TD), O1, O2 <u>Stickstoffhaltige Defekte</u>: NN-Paar, NNO-Komplex, Shallow Thermal Donors (STD) <u>Ausgedehnte Defekte</u>: Versetzungen, Ausscheidungen, Korngrenzen. Die Verteilung der flachen Donatoren (P, TD, STD, As) und Akzeptoren (B, Al) bestimmt den Widerstandsverlauf im bodennahen Bereich des Phosphor dotierten Spezialblocks. Das dortige Diffusionslängenprofil kann im Rahmen der Shockley-Read-Hall-Statistik erst durch eine Erhöhung des Minoritätseinfangquerschnitts für das Cr-Niveau (Faktor 5) bzw. für das STD-Niveau (Faktor 10) nachgezeichnet werden. Eisen, Versetzungen und Korngrenzen haben hier keinen wesentlichen Einfluss. In den untersten Millimetern des Spezialblocks müssen weitere Defekte hinzukommen, die die Diffusionslänge zusätzlich reduzieren; Thermische Donatoren und O1 und eventuell Ausscheidungen kommen dazu in Frage. Die sinngemäße Übertragung der Konzentrationsverläufe aus den beiden Spezialblöcken auf einen Block mit einer produktionsüblichen Dotierung ([B]≈10^{<small>16</small>}/cm^{<small>3</small>}) ergibt, dass in diesem Fall verschiedene Defekte (TD, STD, CrB und FeB) einen Beitrag zur Diffusionslängenreduktion im bodennahen Blockbereich liefern.

This master thesis presents the development of a 100 W LED driver, suitable for outdoor and street lighting. In order to match the driver and LED features, special functionalities are added to the electronic system. To obtain a long lifetime, electrolytic capacitor are exchanged by film capacitor, with longer useful lifetime. However, this practice outcome in higher bus voltage ripple, which have to be compensated in the LED current control stage, named as power control stage. To achieve special functionalities, the proposed driver is designed to operate with universal input voltage and dimming capability, being the entire driver control implement in a digital way, increasing significantly the LED driver flexibility. After the literature review, which aimed to evaluate the characteristics of the LED driver topology structure, the two independent stage topology is selected. The buckboost converter operating in discontinuous conduction mode is employed on the power factor correction stage. The power control stage is composed by the DC/DC LLC resonant converter. Once the LED driver topology is defined, each converter is designed, following by the small signal modeling and the control system design. Experimental results of the driver operating with a reduced bus voltage capacitance (25 μF), are presented for a universal input voltage (85 – 265 VRMS) and different dimming levels (100% − 30%). A high power factor (> 0,94) and a medium to high efficiency (> 82%) is noticed in whole operation points, as well as, a reduced flicker (< 10%), being in accordance with the recent released IEEE Std 1789-2015 and IEC61000-3-2 Class C. / Este trabalho apresenta o desenvolvimento de um driver para o acionamento de um módulo de LEDs de 100 W, destinado a iluminação de exteriores ou iluminação pública. De forma a compatibilizar as características do LED com o driver, diferentes funcionalidades e condições de operação são adicionadas ao sistema eletrônico desenvolvido. Para alcançar longa vida útil, o driver desenvolvido substituiu os capacitores eletrolíticos por capacitores de filme. No entanto, essa prática resulta em maiores ondulações da tensão de barramento, as quais são compensadas pelo estágio de controle da corrente dos LEDs. De modo a aumentar as funcionalidades do driver, o mesmo opera com tensão de entrada universal e controle da intensidade luminosa, sendo o sistema de controle do driver implementado de forma digital, aumentando consideravelmente sua flexibilidade. Após revisão da literatura, a qual objetivou avaliar as características das estruturas e topologias empregadas em drivers para LEDs, seleciona-se a estrutura de dois estágios independentes. O conversor buck-boost operando no modo de condução descontínuo de corrente é empregado no estágio de correção do fator de potência. Para o estágio de controle da corrente dos LEDs, utiliza-se o conversor CC/CC meia ponte ressonante LLC. Definida a estrutura topológica, bem como os conversores utilizados, o projeto dos elementos é desenvolvido, seguido da modelagem dinâmica e do projeto do sistema de controle de cada estágio. Resultados experimentais do driver com reduzida capacitância de barramento (25 μF) mostram a sua operação com tensão de entrada universal (85 – 265 VRMS) e controle de intensidade luminosa (100% − 30%). Verificou-se um alto fator de potência (> 0,94) em toda a faixa de operação, rendimento média-alto (> 82%), bem como reduzida modulação de intensidade luminosa (< 10%), estando em conformidade com a IEEE Std 1789-2015 e a IEC61000-3-2 Classe C.

La travail présente traite du développement de diodes organiques électroluminescentes(OLEDs) a haute luminance pour des applications dans des micro écrans. Ces dispositifs sontbases sur des substrats silicium utilisent la technologie CMOS. Le présent ouvrage met en avantles efforts développe afin de réduire la dérive en tension et ma décroissance lumineuse enopération des dispositifs lumineux.Dans la première partie de l’étude, des OLEDs vertes haute luminance fonctionnant àbasse tension sont développes. L’empilement organique a émission vers le haut comprenant unémetteur fluorescent vert entre des couches de blocage de charges et des couches de transportdopées. Les effets de différentes structures de dispositifs, des configurations de l’empilement etdes matériaux organiques sur les performances initiales et en opération sont reportés ici.Dans la deuxième partie de l’étude, le développement de dispositifs OLED hybrides pourmicro écrans couleurs est présenté. Les structures hybrides comprennent une couche detransport de trous photosensible et traitable par solution (X-HTL) et d’une OLED blancheréalisée par évaporation sous vide. Cette méthode permet la génération de couleur directe, ellepermet ainsi d’obtenir de très bonnes efficacités et un contrôle aisé de la couleur émise parsimple modification de l’épaisseur de X-HTL. / The present work reports the development of high luminance organic light emitting diodes(OLEDs) device stacks for microdisplay applications. The devices are based on siliconcomplementary metal-oxide semiconductor (CMOS) backplane. In the present treatise effortsare particularly focused on reducing the luminance decay and the voltage drift during deviceoperation.In the first part of this study, high brightness and low operating voltage green OLEDs arereported. The top emitting device stack comprises of fluorescent green emitter accompanied bycharge blocking layers and doped charge transport layers. The effect of different devicestructures, configurations and organic materials on the initial and lifetime performance of thedevice is presented.In the second part of the study, device development of hybrid OLED stacks for high luminancefull color microdisplays is reported. The hybrid devices comprise of a solution processed andphotocrosslinkable hole transport layer (X-HTL) and an evaporated white OLED stack. Thismethod allows direct primary color generation with relatively high efficiency and offers ease ofcolor tunability by controlling the thickness of the X-HTL.

Made available in DSpace on 2010-04-20T20:47:57Z (GMT). No. of bitstreams: 3 86570.pdf.jpg: 22231 bytes, checksum: 34de2608e8e6e4e2dae8a7f653d5cd30 (MD5) 86570.pdf.txt: 243371 bytes, checksum: c5f0fa80eb08a9e86c0a1326c93f043a (MD5) 86570.pdf: 1102343 bytes, checksum: f361654fc4f109360f6de9a92dbc70e9 (MD5) Previous issue date: 2006-03-06T00:00:00Z / Este estudo no setor de telefonia celular adapta o modelo de investimento de marketing de Rust, Lemon & Zeithaml (2004) fornecendo um método de avaliação de investimento em áreas estratégicas de marketing (value, brand e relationship equity). Aplicado às operadoras de telefonia celular do estado de São Paulo (Vivo, Claro e TIM), o modelo permite calcular a probabilidade de um cliente mudar da operadora atual para uma concorrente, e verificar se a contribuição marginal advinda de uma ação mercadológica ultrapassa ou não seu custo de capital. Finalmente, através da aplicação do modelo obtém-se uma estimativa do customer equity atual das três operadoras de telefonia celular estudadas. / This study proposes an adaptation to the mobile telephone sector of the Rust Lemon & Zeithaml (2004) model of marketing investment. The model provides a method for the evaluation of investments in strategic marketing areas (value, brand and relationship equity). Applied to São Paulo State cellular telephone companies (Vivo, Claro and TIM), the model allows the estimation of a customer probability of change from the present operator to a competitor; and the assessment of a marketing initiative contribution, verifying if it exceeds its cost of capital. Finally, through the application of model, an estimate of customer equity is calculated for the three studied cellular telephone operators.

Dans l’industrie, les fabricants tendent à limiter la lubrification conventionnelle lors de l’usinage et s’orientent de plus en plus vers la microlubrification (MQL : Minimum Quantity Lubrication) pour des raisons économiques, écologiques et pour respecter la santé des opérateurs. Une très faible quantité de lubrifiant de faible pression nécessite une conception optimale des canaux internes de l’outil afin de limiter les pertes de charges et avoir les avantages de la microlubrification. Premièrement, une revue bibliographique introduit l’étude en présentant les avantages qu’induit le passage à la microlubrification. Par la suite, quelques conceptions d’outils avec une lubrification interne qui vise la face de coupe ou la face de dépouille de la plaquette sont passées en revue. / In machining industry, manufacturers tend to limit conventional lubrication and are moving increasingly towards Minimum Quantity Lubrication (MQL) for economic and ecological reasons, and with a view to safeguarding operator health and safety. A very small amount of lubricant at low pressure requires optimized design of the tools internal channels in order to minimize pressure drops and gain benefit from MQL. First, a literature review introduces the study by presenting the benefits induced by switching to MQL. Thereafter, some tool designs with internal lubrication for rake face or flank face lubrication are presented.

Ce travail de thèse s’inscrit dans la continuité des activités de recherche du laboratoire GREAH sur les problématiques de la gestion d’énergie électrique et de l’amélioration de la qualité énergétique des systèmes de production aux énergies renouvelables. En effet, le couplage de plusieurs sources de natures différentes entraîne des problématiques de dimensionnement, de qualité d’énergie et de la durée de vie des éléments interconnectés. La démarche scientifique repose sur la caractérisation de l'évolution des résistances et des capacités des cellules de batteries LFP/supercondensateurs en fonction des contraintes électriques et thermiques, suivi de la modélisation du vieillissement accéléré des cellules. Nous proposons dans ce mémoire de thèse des améliorations de la réponse dynamique d’un bateau fluvial à propulsion électrique par l’hybridation des batteries LFP et des supercondensateurs. Nous proposons également une approche électrothermique pour la caractérisation et la modélisation multi-physique du vieillissement des batteries et supercondensateurs en utilisant des contraintes combinées de la température et de la fréquence des ondulations du courant de charge/décharge des cellules. Les données expérimentales collectées ont permis d'établir des modèles des supercondensateurs et des batteries dédiés aux systèmes multi-sources incluant des sources d’énergie renouvelable (éoliens et hydroliens). Les modèles développés se révèlent très précis par rapport aux résultats expérimentaux. Ils permettent une bonne description du phénomène de vieillissement des batteries LFP/supercondensateurs dû aux opérations de charge/décharge avec un courant continu fluctuant combiné à une température variable. / This thesis work is a continuation of the research activities of the GREAH laboratory on the issues of the management of electrical energy and improving the energy quality of production systems for renewable energy. Indeed, the coupling of several different nature sources entails the problems of dimension, quality of energy and the lifetime of the interconnected elements. The scientific approach is based on the characterization of the evolution of the resistances and capacitances of the batteries/supercapacitors cells according to the electrical and thermal constraints, followed by the modeling of accelerated cells aging. In this thesis, we propose improvements to the dynamic response of an electric propulsion fluvial boat by using the hybrid system of lithium-batteries and supercapacitors. We also propose an electrothermal approach for the multi-physical characterization and modeling of the batteries and supercapacitors aging, using combined constraints of the temperature and frequency of the DC current ripples. The experimental data has been collected to establish models of batteries and supercapacitors dedicated to multi-source systems including renewable energy sources (wind and tidal turbines). The results of the developed models shown high accuracy compared with experimental results. These models illustrated a good description of the aging phenomenon of batteries/ supercapacitors due to charging/discharging operations with a fluctuating continuous current combined with a variable temperature.

Rieck & Nedelman (1991) propuseram um modelo de regressão log-linear tendo como base a distribuição Birnbaum-Saunders (Birnbaum & Saunders, 1969a). O modelo proposto pelos autores vem sendo bastante explorado e tem se mostrado uma ótima alternativa a outros modelos propostos na literatura, como por exemplo, os modelos de regressão Weibull, gama e lognormal. No entanto, até o presente momento, não existe nenhum estudo tratando de refinamentos para as estatísticas da razão de verossimilhanças e escore nesta classe de modelos de regressão. Assim, um dos objetivos desta tese é obter um fator de correção de Bartlett para a estatística da razão de verossimilhanças e um fator de correção tipo-Bartlett para a estatística escore nesse modelo. Estes ajustes melhoram a aproximação da distribuição nula destas estatísticas pela distribuição qui-quadrado de referência. Adicionalmente, objetiva-se obter ajustes para a estatística da razão de verossimilhanças sinalizada. Tais ajustes melhoram a aproximação desta estatística pela distribuição normal padrão. Recentemente, uma nova estatística de teste foi proposta por Terrell (2002), a qual o autor denomina estatística gradiente. Esta estatística foi derivada a partir da estatística escore e da estatística de Wald modificada (Hayakawa & Puri, 1985). A combinação daquelas duas estatísticas resulta em uma estatística muito simples de ser calculada, não envolvendo, por exemplo, nenhum cálculo matricial como produto e inversa de matrizes. Esta estatística foi recentemente citada por Rao (2005): \"The suggestion by Terrell is attractive as it is simple to compute. It would be of interest to investigate the performance of the [gradient] statistic.\" Caminhando na direção da sugestão de Rao, outro objetivo da tese é obter uma expansão assintótica para a distribuição da estatística gradiente sob uma sequência de alternativas de Pitman convergindo para a hipótese nula a uma taxa de convergência de n^{-1/2} utilizando a metodologia desenvolvida por Peers (1971) e Hayakawa (1975). Em particular, mostramos que, até ordem n^{-1/2}, a estatística gradiente segue distribuição qui-quadrado central sob a hipótese nula e distribuição qui-quadrado não central sob a hipótese alternativa. Também temos como objetivo comparar o poder local deste teste com o poder local dos testes da razão de verossimilhanças, de Wald e escore. Finalmente, aplicaremos a expansão assintótica derivada na tese em algumas classes particulares de modelos. / The Birnbaum-Saunders regression model is commonly used in reliability studies.We address the issue of performing inference in this class of models when the number of observations is small. Our simulation results suggest that the likelihood ratio and score tests tend to be liberal when the sample size is small. We derive Bartlett and Bartlett-type correction factors which reduce the size distortion of the tests. Additionally, we also consider modified signed log-likelihood ratio statistics in this class of models. Finally, the asymptotic expansion of the distribution of the gradient test statistic is derived for a composite hypothesis under a sequence of Pitman alternative hypotheses converging to the null hypothesis at rate n^{-1/2}, n being the sample size. Comparisons of the local powers of the gradient, likelihood ratio, Wald and score tests reveal no uniform superiority property.

Consider life testing of J-component series systems that are subjected to stress levels that are steeper than that at normal usage condition. The objective of performing such life tests, commonly known as Accelerated Life Testing (ALT) in the literature, is to collect observations on system failure times within a limited time frame. The accelerated observations are then used to infer on the component and system reliability metrics at usage stress. In this thesis, the existing literature is first extended by considering the general case of K stress variables, as opposed to the usual consideration of a single stress variable. Next, a general model assuming that the component log-lifetimes belong to an arbitrary location-scale family of distributions, is formulated. The location parameters are assumed to depend on the stress variables through a general stress translation function, while the scale parameters are assumed to be independent of the stress variables. This formulation covers the standard lifetime distributions as well as well-known stress translation functions as special cases. Bayesian methodologies are then developed for four special cases of the proposed general model, viz., exponentials, Weibulls with equal shape parameter, Weibulls with distinct shape parameters and log-normals with distinct scale parameters. For exponential and Weibull models, the priors on lifetime parameters are assumed to be log-concave and independent of each other. The resulting univariate conditional posterior of each lifetime parameter given the rest, is shown to be log-concave. This facilitates Gibbs sampling from the joint posterior of lifetime parameters. Propriety of the joint posteriors with Laplacian uniform priors on stress coefficients are also proved under a suitable set of sufficient conditions. For the log-normal model, the observed data is first augmented with log-lifetimes of un-failed components to form complete data. A Gibbs sampling scheme is then developed to generate observations from the joint posterior of lifetime parameters, through the augmented data and a conjugate prior for the complete data. In all four cases, Bayesian predictive inference techniques are used to study component and system reliability metrics at usage stress. Though this thesis mainly deals with Bayesian inference of accelerated data of series systems, maximum likelihood analysis for the log-normal component lifetimes is also performed via an expectation-maximization (EM) algorithm and bootstrap, which are not available in the literature. The last part of this thesis deals with construction of optimal Bayesian designs for accelerated life tests of J-component series systems under Type-I censoring scheme. Optimal ALT plans for a single stress variable are obtained using two different Bayesian D-optimality criteria for exponentially distributed component lives. A detailed sensitivity analysis is carried out to investigate the effect of different planning inputs on the optimal designs as well.

Ce travail s'inscrit dans le cadre d'études de structures nucléaires réalisées en utilisant des réactions de fission induites par neutrons froids. Il décrit successivement les résultats d'une étude sur des noyaux ayant un nombre de neutrons N=50-60, sur le développement d'un marqueur d'événements de fission et enfin sur la production de l'isomère Pt-195m. Chacun des différents sous-thèmes trouve son origine dans la campagne EXILL qui s'est déroulée en 2012-2013 et durant laquelle un spectromètre de grande efficacité pour la détection des rayonnements γ (EXOGAM) a été utilisé auprès du réacteur à haut flux de neutrons de l'Institut Laue-Langevin (ILL). Dans la première partie de cette thèse, les noyaux d'intérêt ont été produits par fission induites par des neutrons sur les cibles fissiles U-235 et Pu-241. Des méthodes de spectroscopie γ ont été appliquées pour l'identification des fragments de fission, l'attribution des transitions γ à un noyau et l'analyse des durées de vie moyenne des états excités. L'analyse des durées de vie moyenne des états excités dans la plage de quelques picosecondes à quelques nanosecondes a été réalisée en utilisant deux méthodes complémentaires. Dans les deux cas, il s'agit de réaliser un spectre en temps construit à partir de la coincidence entre une transition qui alimente le niveau mesuré et une transition qui le désexcite. Les durées de vie moyenne pour les noyaux Kr-92, Kr-93 et Zr-101 sont présentées. Dans la seconde partie, les premiers résultats du développement d'un nouveau détecteur pour la discrimination des fragments de fission sont présentés. Ce marqueur d'événements de fission est destiné à être utilisé sur le spectromètre FIssion Prompt Product γ-ray Spectrometer (FIPPS) de l'ILL. Dans le cadre de cette étude, deux conceptions de détecteurs différentes, basées sur un scintillateur en plastique solide et un scintillateur liquide organique, ont été testées. Dans la troisième partie, la possibilité de la population spécifique de l'isomère de spin dans Pt-195 est examinée au regard particulièrement de son utilisation en tant que radio-isotope en médecine nucléaire. Une telle activation spécifique pourrait être réalisée grâce à l'existence d'états excités dont la structure permettrait une population ciblée dans le cas de l'utilisation de réactions de photo-excitation. La recherche de tels états a été initiée lors d'une expérience de capture de neutrons à EXILL dans laquelle des états potentiels ont été identifiés. L'activation de l'isomère par ces états a ensuite été testée avec des réactions photonucléaires à l'aide du faisceau haute intensité disponible auprès de l'installation γ HIGS de TUNL (Triangle Universities Nuclear Laboratory, Duke, USA). / Within the scope of atomic nuclear structure studies with neutron-induced reactions, this work presents the results of a fission fragment study in the N=50-60 region, the development of a fission event tagger, and the production of the isomer Pt-195m. Each of the different sub-topics has its origin in the 2012/13 EXILL campaign, where nuclear structure studies were carried out with neutron-induced reactions, and explored with a γ-efficient detector array. In the first part of this thesis, the neutron-rich region around neutron number N=50-60 was investigated with neutron-induced fission reactions on the fissile targets U-235 and Pu-241. Gamma spectroscopy methods were applied for the identification of the respective fission fragments, the assignment of γ transitions, and the analysis of lifetimes of excited states. The slope fit method as well as the recently developed generalized centroid difference method were used for the analysis of lifetimes in the low picoseconds to sub-nanoseconds range. Lifetimes for the nuclei Kr-92, Kr-93 and Zr-101 are presented. In the second part, first results of the development of a new detector for the discrimination of fission fragments are presented. This fission event tagger is intended to be used at the FIssion Product Prompt γ-ray Spectrometer (FIPPS) at the Institut Laue-Langevin. Within the scope of this study, two different detector designs, based on a solid plastic scintillator and an organic liquid scintillator, respectively, were tested. In the third part the possibility of the specific population of the spin-isomer in Pt-195 is discussed with special regard to its use as radioisotope in nuclear medicine. Such a specific activation could be realized via certain “doorway states” in photo-excitation reactions. The search for these doorway states was initiated within a neutron capture experiment at EXILL where potential states were found. The activation of the isomer via these states was tested afterwards with photonuclear reactions using the high intense γ-beam HIGS of the TUNL facility.