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Structure, morphology and performance relationships of organic photovoltaic devices : the block copolymer approachDeribew, Dargie Hailu 14 July 2013 (has links)
Ce travail se focalise sur l’étude de cellules solaires organiques modèles basées sur le mélange de poly(3-hexylthiophène) (P3HT) et de l'ester méthylique de l'acide [6,6]-phényl C61 butyrique (PCBM). La corrélation entre la morphologie de la couche active, les paramètres de mises en œuvre et le rendement photovoltaïque a été soigneusement étudiée afin d’obtenir l’optimisation de l’efficacité de tels dispositifs. Une méthode originale pour contrôler la séparation de phases dans ces mélanges a été proposée et consiste à l'intégration de copolymères blocs comme additifs. Trois copolymères séquencés ont été utilisés en tant qu’agents de nanostructuration et/ou d'agents de nucléation. Il a notamment été montré que l'incorporation de P3HT-b-PI permet l'augmentation du nombre de cristallites de P3HT tout en limitant l’agglomération du PCBM. D'autre part, l'incorporation de P3HT-b-P4VP dans les mélanges de P3HT:PCBM a permis de contrôler l'orientation des cristallites de P3HT, améliorant par ce fait le transport de charge dans les dispositifs. / This work investigates organic solar cells made of a blend of polymeric materials based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as model system. The correlation between the photovoltaic active layer morphology and the performance of the organic solar cell is thoroughly investigated. The chosen method for controlling phase separation in the polymeric blends is to incorporate block copolymers as additives. Three systematically selected block copolymers were used as nanostructuring and/or nucleating agents. Indeed, the incorporation of P3HT-b-PI induces the increase in the number of P3HT crystallites as well as suppresses the growth of PCBM aggregates. On the other hand, the incorporation of P3HT-b-P4VP into P3HT:PCBM decreases the crystallization of P3HT but increases its face-on orientation, a requirement for an enhanced charge transport in organic PV devices.
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Top-down Fabrication Technologies for High Quality III-V NanostructuresNaureen, Shagufta January 2013 (has links)
III-V nanostructures have attracted substantial research effort due to their interesting physical properties and their applications in new generation of ultrafast and high efficiency nanoscale electronic and photonic components. The advances in nanofabrication methods including growth/synthesis have opened up new possibilities of realizing one dimensional (1D) nanostructures as building blocks of future nanoscale devices. For processing of semiconductor nanostructure devices, simplicity, cost effectiveness, and device efficiency are key factors. A number of methods are being pursued to fabricate high quality III-V nanopillar/nanowires, quantum dots and nano disks. Further, high optical quality nanostructures in these materials together with precise control of shapes, sizes and array geometries make them attractive for a wide range of optoelectronic/photonic devices. This thesis work is focused on top-down approaches for fabrication of high optical quality nanostructures in III-V materials. Dense and uniform arrays of nanopillars are fabricated by dry etching using self-assembly of colloidal SiO2 particles for masking. The physico-chemistry of etching and the effect of etch-mask parameters are investigated to control the shape, aspect ratios and spatial coverage of the nanopillar arrays. The optimization of etch parameters and the utilization of erosion of etch masks is evaluated to obtain desired pillar shapes from cylindrical to conical. Using this fabrication method, high quality nanopillar arrays were realized in several InP-based and GaAs-based structures, including quantum wells and multilayer heterostructures. Optical properties of these pillars are investigated using different optical spectroscopic techniques. These nanopillars, single and in arrays, show excellent photoluminescence (PL) at room temperature and the measured PL line-widths are comparable to the as-grown wafer, indicating the high quality of the fabricated nanostructures. The substrate-free InP nanopillars have carrier life times similar to reference epitaxial layers, yet an another indicator of high material quality. InGaAs layer, beneath the pillars is shown to provide several useful functions. It effectively blocks the PL from the InP substrate, serves as a sacrificial layer for generation of free pillars, and as a “detector” in cathodoluminescence (CL) measurements. Diffusion lengths independently determined by time resolved photoluminescence (TRPL) and CL measurements are consistent, and carrier feeding to low bandgap InGaAs layer is evidenced by CL data. Total reflectivity measurements show that nanopillar arrays provide broadband antireflection making them good candidates for photovoltaic applications. A novel post etch, sulfur-oleylamine (S-OA) based chemical process is developed to etch III-V materials with monolayer precision, in an inverse epitaxial manner along with simultaneous surface passivation. The process is applied to push the limits of top-down fabrication and InP-based high optical quality nanowires with aspect ratios more than 50, and nanostructures with new topologies (nanowire meshes and in-plane wires) are demonstrated. The optimized process technique is used to fabricate nanopillars in InP-based multilayers (InP/InGaAsP/InP and InP/InGaAs/InP). Such multilayer nanopillars are not only attractive for broad-band absorption in solar cells, but are also ideal to generate high optical quality nanodisks of these materials. Finally, the utility of a soft stamping technique to transfer free nanopillars/wires and nanodisks onto Si substrate is demonstrated. These nanostructures transferred onto Si with controlled densities, from low to high, could provide a new route for material integration on Si. / <p>QC 20130205</p>
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Contribution à l'étude de la fiabilité des MOSFETs en carbure de silicium / Study of silicon carbide MOSFETs reliabilitySantini, Thomas 25 March 2016 (has links)
Ces dernières années ont vu apparaître sur le marché les premiers transistors de puissance de type MOSFET en carbure de silicium. Ce type de composant est particulièrement adapté à la réalisation d’équipement électrique à haut rendement et capable de fonctionner à haute température. Néanmoins, la question de la fiabilité doit être posée avant de pouvoir envisager la mise en œuvre de ces composants dans des applications aéronautiques ou spatiales. Les mécanismes de défaillance liés à l’oxyde de grille ont pendant longtemps retardé la mise sur le marché des transistors à grille isolée en carbure de silicium. Cette étude s’attache donc à estimer la durée de vie des MOSFET SiC de 1ére génération. Dans un premier temps, le mécanisme connu sous le nom de Time Dependent Dielectric Breakdown(TDDB) a été étudié au travers de résultats expérimentaux issus de la bibliographie. Notre analyse nous a permis de justifier de l’emploi d’une loi de Weibull pour modéliser la distribution des temps à défaillance issue de ces tests. Les résultats nous ont également permis de confirmer l’amélioration significative de la fiabilité de ces structures vis-à-vis de ce mécanisme. Dans un second temps, l’impact du mécanisme d’instabilité de la tension de seuil sur la fiabilité a été quantifié au travers de tests de vieillissement de type HTGB. Les données de dégradation ainsi collectées ont été modélisées à l’aide d’un processus gamma non-homogène, qui nous a permis de prendre en compte la variabilité entre les composants testés dans des conditions identiques et de proposer des facteurs d’accélération en tension et en température pour ce mécanisme. Enfin, ces travaux ont permis d’ouvrir la voie à la mise en œuvre d’outils de pronostic de la durée de vie résiduelle pour les équipements électriques. / Recent years have seen SiC MOSFET reach the industrial market. This type of device is particularly adapted to the design of power electronics equipment with high efficiency and high reliability capable to operate in high ambient temperature. Nevertheless the question of the SiC MOSFET reliability has to be addressed prior to considering the implementation of such devices in an aeronautic application. The failure mechanisms linked to the gate oxide of the SiC MOSFET have for a long time prevented the introduction of the device. In this manuscript we propose to study the reliability of the first generation of SiC MOSFET. First, the mechanism known as the Time–Dependent Dielectric Breakdown is studied through experimental results extracted from literature. Our study shows the successful application of a Weibull law to model the time-to-failure distribution extracted from the accelerated tests. The results show also a significant improvement of the SiC MOSFET structure with respect to this phenomenon. In a second step, the impact of the threshold voltage instability is quantified through accelerated tests known as High Temperature Gate Bias. The collected degradation data are modeled using a non-homogeneous Gamma process. This approach allows taking into account the variability between devices tested under the same conditions. Acceleration factors have been proposed with respect to temperature and gate voltage. Eventually the study delivers a primary estimation of the remaining useful lifetime of the SiC MOSFET in a typical aeronautic application.
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Spolehlivost bezolovnatých pájek a vybrané způsoby odhadu jejich životnosti / Reliability of Lead-free Solders and the Selected Methods to Estimate its LifetimeŠvecová, Olga January 2012 (has links)
The doctoral thesis is focused on reliability of lead-free solder SAC 305. Knowledge in the field of fatigue models used in determining the lifetime of solder joints are observed in this thesis. Also such methods of predicting reliability as numerically-analytical methods or reliability experimental tests are mentioned. Practical results of reliability measurement are presented. Experimental data served as the foundation for determining empirical coefficients for the fatigue model based on deformation induced by creep of the solder, which was implemented in the ANSYS environment. Results from different methods were compared and conclusions discussing the suitability of the presented prediction methods are formulated.
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Integrated multibody dynamics and fatigue models for predicting the fatigue life of poly-V ribbed beltsElmaraghi, Omar A. 05 1900 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / Belt-drives are used in many applications such as industrial machines, washing machines, and accessory drives for automobiles and other vehicles. Multibody dynamics/finite element numerical models have become an effective way to predict the dynamic response of belt-drives. In this thesis, a high fidelity numerical model was built using a multibody dynamics/finite element code to simulate a belt-drive. The belt-drive transmits power from a turbine of a Rankin cycle (that uses the exhaust waste heat of the internal combustion engine as heat source) to the crank shaft of the engine. The code uses a time-accurate explicit numerical integration technique to solve the multibody dynamics differential equations. The belt was modeled using three-node beam elements to account for the belt axial and bending stiffness/damping, while the pulleys, shafts and tensioner body were modeled as rigid bodies. The penalty technique was used to model normal contact between the belt and the pulleys. An asperity-based friction model was used to approximate Coulomb friction between the belt and the pulleys. The dynamic response predicted using the model was validated by comparing it to experimental results supplied by Cummins Inc. A parameter sensitivity study was performed to evaluate the change in response due to change in various belt-drive parameters. A fatigue model was developed to predict the belt fatigue life using output from the explicit finite element code including normal and tangential forces between the belt and the pulleys and belt tension. The belt fatigue life was evaluated for alternative belt-drive configurations in order to find the configuration with the longest life.
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Extension de l'approche par la courbe maitresse de la prédiction des durées de vie de réseaux d'indice complexes inscrits par UV dans les fibres / Extension of the master-curve approach for lifetimes predictions of complex componants based on fiber bragg gratings written by uv exposureCostes, Sylvain 04 June 2013 (has links)
L’objectif principal de cette thèse était d’examiner dans quelle mesure il est possible d’étendre l’approche de la courbe maîtresse à des composants complexes afin de déterminer des conditions de déverminage et de réaliser une prédiction de durée de vie en fonction de ces conditions de déverminage. Nous avons considéré la stabilité d’un réseau dit élémentaire (réseau carré, à pas constant et droit) puis le problème de la stabilité (selon des critères spécifiques) des composants complexes: les CDC et les monofiltres GFF. Cette thèse a permis de décrire de façon rigoureuse, puis d'utiliser le cadre de travail VAREPA pour résoudre des problèmes issus de l'industrie de télécoms. A cet effet, des séries d’études de vieillissement accéléré sur des réseaux simples et complexes ont été menées. Un protocole de mesure permettant de déterminer les incertitudes de mesure a été mis au point afin de déterminer de façon fiable des intervalles de confiance sur les prédictions de durée de vie.Nous avons étudié les cinétiques de croissance des réseaux inscrits dans une fibre dédiée à l’inscription des CDC (Coreactive). Cette étude nous a permis de montrer que la réaction prédominante à l’origine des changements d’indice de réfraction est activée par une absorption à 1 photon. D’autre part, nous avons étendu le cadre de travail utilisé pour prédire l’effacement des réseaux (VAREPA) afin de rendre compte de leurs cinétiques d’inscription. Puis nous avons cherché à déterminer les conditions de passivation et à prédire la durée de vie des réseaux déverminés en présence d’hydrogène résiduelle (procédé industriel actuel). Pour cela, nous avons établi la courbe maîtresse de réseaux photoinscrits non déverminés puis nous avons validé les conditions de déverminage et les prédictions de durée de vie en construisant une nouvelle courbe maîtresse sur des réseaux déverminés.Nous avons étudié la stabilité thermique des réseaux inscrits dans une fibre hydrogénée dédiée aux futurs monofiltres GFF dans des conditions d’inscription similaires à celles de ces composants. Nous avons utilisé les courbes maîtresses établies à partir des réseaux élémentaires (mais apodisés) simplement dégazés « à froid » (ici 2jours à 50°C puis 2 jours à 110°C). Puis, nous avons fait vieillir le profil d’indice (cœur et gaine) d’un monofiltre GFF. Puis, nous avons recalculé la réponse spectrale de ce filtre vieilli (e.g. 30jours à 200°C) et nous l’avons comparé à des mesures expérimentales. Cette approche reste générale et permet de changer les conditions de déverminage au besoin. Cette étude nous a permis de mettre en évidence que la stabilité des variations d’indice photo-induites dans le cœur dépend peu de l’amplitude initiale de la modulation pour des valeurs comprises entre quelques 10-5 et 10-3. Du fait de la présence d’une gaine optique fortement photosensible (car fortement dopée en Ge), nous avons établi les courbes maîtresses des variations d’indice photo-inscrites dans le cœur et la gaine optique pour des valeurs allant jusque 10-3 dans le cœur et 3.10-3 dans la gaine. Nous avons ainsi obtenu des courbes maîtresses présentant le même k0 (fréquence d'essai, i.e facteur pré exponentiel) mais dont la forme est légèrement différente. La stabilité des variations d’indice est meilleure dans le cœur (moins dopé en Ge) que dans la gaine photosensible. Dans un second temps, nous avons cherché à déterminer les conditions de passivation et à prédire la durée de vie des réseaux déverminés à partir des réseaux de Bragg qualifiés d’élémentaires. Pour la première fois à notre connaissance, nous avons validé de façon fiable les conditions de passivation et les prédictions de durée de vie en construisant une nouvelle courbe maîtresse sur des monofiltres GFF préalablement déverminés. Conformément à la théorie, cette courbe maîtresse présente le même k0 et une forme similaire à celle établie au moyen de réseaux non déverminés, ce qui valide la fiabilité de nos prédictions. / The main objective of this thesis was to investigate how it is possible to extend the master curveapproach to complex components, in order to calculate annealing conditions and giving a life timeprediction according those annealing conditions. We studied the stability of a simple Bragg grating (noapodisation, constant pitch, no tilt). Then, we have been able to study the problem of the stability(according to specific criteria) of complex components: CDC and GFF monofilters. This thesis allowed toshow precisely what is the VAREPA framework and how to apply it to optical telecommunicationsproblems. To give an answer to the question of the possibility of extending the master curve approach tocomplex components, series of accelerate aging studies have been carried out. For this purpose, ameasurement protocol including the determination of the measurement uncertainty was developed. Thisprotocol allow, to determine confidence intervals on the life time prediction.We studied the kinetics of photo induced index growth in the optical fiber dedicated forfabrication of CDC (Coreactive). This study allowed us to demonstrate that the predominant reaction atthe origin of changes in refractive index is activated by a one photon absorption. On the other hand wehave extended the VEREPA framework used to predict the Bragg gratings erasure to take into account thegrowing kinetics. In a second step we tried to calculate annealing conditions in the presence of residualmolecular hydrogen and associated Bragg grating life time prediction. For that purpose we established themaster curve of photo-induced Bragg gratings without annealing, then we validated the annealingconditions and lifetime predictions by building a new master curve from aging of annealed Bragg gratings(in presence of residual hydrogen).We studied the thermal stability of hydrogenated fiber Bragg gratings dedicated to futuremonofiltres GFF in similar conditions to those components. We used master curves from basic Bragggratings (ie no apodisation, constant pitch, no tilt) simply out-gazed at "cold" temperature (here 2 days at50 ° C and 2 days at 110 ° C). Then the aging of the index profile of a GFF monofilter have beensimulated (index profile of the core and of the cladding, each of them having a different master curve).For that purpose the profile have been separated into 35 "basic" filters. Then the spectral response of thisaged monofilter (e.g. 30 days at 200°C) have been calculated and compared with experimentalmeasurements. The advantage of this approach is that it is general and allow to change the annealingconditions if needed. Firstly, this study allowed to highlight that the stability of photo-induced indexchanges in the core depend little on the initial amplitude modulation for values between several 10-5 and10-3. Secondly, due to the presence of a highly sensitive optical cladding (and therefore highly Ge doped),Master curves, of photo-induced index change in the core and the cladding have been established forvalues ranging up to 10-3 in the core and 3.10-3 in the cladding. Master Curves with the same k0 havebeen obtained but the elbow and the slopes are different. Stability of index variations in the core is better(less Ge doped) than in the photosensitive cladding. In a second step, from the basic Bragg gratings, theannealing conditions and the lifetime have been determined. For the first time to our knowledge, thereliably of the annealing conditions and the life time predictions have been validated by building a newmaster curve on annealed GFF monofilters. According to the theory, this master curve show the same k0as the one determined using non-annealed gratings. More beyond the elbow, the two curves are same,which validates the reliability of our predictions.
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"Não linearidades ópticas em azocompostos" / Optical nonlinearities in azocompoundsBoni, Leonardo de 10 December 2004 (has links)
Neste trabalho, são estudadas as alterações das propriedades ópticas lineares e não lineares de soluções de azocompostos devidas aos mecanismos de isomerização e às alterações das propriedades estruturais com a temperatura. A dependência da transição pipi* com a estrutura linear dos azocompostos é notada já nas medidas dos espectros de absorção em função da temperatura para o isômero trans. Através do conhecimento dos níveis de energia e dos tempos de relaxação via isomerização, foi possível obter a dinâmica entre os isômeros cis e trans. As medidas não lineares forneceram propriedades interessantes associadas aos estados de energia dos compostos. Por exemplo, através de experimentos de varredura-z e de excitação e prova, foi possível ver que os azocompostos apresentam uma alta transparência quando excitados, a qual desaparece com o término da isomerização. Medidas em função do comprimento de onda mostraram que a transparência observada está presente em toda a banda pipi* e não ocorre na banda npi* . Também foi observado que o tempo de isomerização muda de acordo com o comprimento de onda de excitação, o que pode estar relacionado com a superposição das duas bandas. Os resultados obtidos em femtossegundos foram essenciais para descrever o processo dinâmico de fotoisomerização, observado, por completo, através de medidas com varredura-Z em picossegundos e nanossegundos. Essas medidas forneceram os valores das seções de choque dos isômeros cis, que são difíceis de serem quantificadas devido ao curto tempo de vida desse isômero. Além dos resultados ressonantes, foram feitos experimentos de absorção de dois fótons em femtossegundos usando a técnica de varredura-Z. Esses estudos mostraram a dependência das seções de choque de absorção de dois fótons com características estruturais das moléculas, tais como comprimento de conjugação, grupos push-pull e planaridade. Os resultados ressonantes e não ressonantes obtidos em femtossegundos serviram de base para a calibração da técnica de varredura-Z com pulsos de luz branca. Essa técnica se mostrou adequada para a obtenção dos espectros das não linearidades ópticas ressonantes e não ressonantes em uma única medição (de 5 minutos), diminuindo assim flutuações do laser durante o experimento. / This work reports on the temperature dependence of linear and nonlinear properties of azocompounds solutions due to isomerization mechanisms. The dependence of pipi* transitions on the linear structure of azocompounds is already noticeble in the measurements of absorption spectra as function of the temperature for the trans isomer. Knowing the energy levels and the relaxation times through isomerization, it was possible to obtain the exchange dynamics between cis and trans conformations. Nonlinear measurements provided interesting properties associated with the energy levels of de compounds. For exemple, through Z-scan and pumpprobe experiments, it was possible to verify that azocompounds present a high transparency when excited and that this transparency disapears when the izomerization ends. The wavelength change has shown that the observed transparency is present along the complete pipi* band, but not in the npi* band. It was also observed that the isomerization time changes with the exciting wavelength, which may be related to the superposition of both bands. The results obained with femtoseconds pulses were essential to completily describe the photoisomerization process observed with Z-scan measurements using picoseconds and nanoseconds pulses. These measurements provided values of the crosssection of the cis conformation, which are difficult to be quantified due to the short lifetime of this isomer. Besides ressonant results, experiments of two-photon absorption in the femtosecond regime using the Z-scan technique were made. These studies shown the dependence of the two photons absorption cross-section on structural features of molecules such as conjugation length, push-pull groups and planarity. The ressonant and nonressonant results obteined with femtoseconds have provide the calibration of the Z-scan technique with white light pulses. This technique has been found able to obtain the spectra of ressonat and nonressonant nonlinearities in a single measurement (about 5 minutes), diminishing laser fluctuation during the experiment.
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顧客生命週期價值分析之實地實證研究-以某銀行信用卡部門為例陳怡君 Unknown Date (has links)
要創造顧客價值,首先需瞭解顧客。顧客是企業最重要的資產,企業應掌握該資產之性質與經濟意涵。本研究自此觀點出發,對個案公司之顧客資產提出四大問題:1.可能長期/短期往來客戶分辨及探討可能長期往來客戶是否一定是好客戶2.各區隔客戶的主要消費型態3.各區隔顧客與企業之獲利關係4.各區隔顧客之理財型態。本研究藉由此四大問題,串連時間、獲利與經濟行為構面進行分析與探討。本研究之資料取自某銀行信用卡部門二年期之月顧客資料。
本研究之發現說明如下:
1.以獲利與時間兩構面為區隔,發現長期往來之客戶不一定是好客戶。可能短期往來客戶亦有極佳之獲利潛能,但可能因為企業未能滿足需求或客戶有交換使用各家信用卡之行為、預算分配情況的影響,致使此類客戶未能成為忠實客戶,管理當局應深入調查這些顧客的行為,以利策略之擬定。
2.各區隔間有鮮明之行為特質。各區隔之所注重的消費層次不同,關心的議題可能不同,因此企業在行銷上注重的層面理應不同。
3.大多數之客群對獲利有顯著貢獻,顯示出大多數客戶是具有潛在利潤的客戶。
4.「一般交易需求者」為個案銀行之主要客戶,屬於極少拖欠帳款,或者是有支出預算之消費者,銀行只能自手續費獲利,因此,日常營運成本可能是關心重點,企業應力求成為此類顧客的主要銀行。 / Customer valuation is becoming a critical element in strategy development. It is built on the notation that the customer is the primary asset of the firm. The firm has a protfolio of customer assets that should be analyzed economically to determine their value to the firm. The four issues in this study relate to (1) identifying possible long-lived or short-lived customers and if those possible long-lived customers are necessarily profitable customers or not; (2) investigating consuming behavior of each segment; (3) understanding the profit relationship between the firm and customers; (4) establising financing behavior of each segment. This study is based on a monthly data from a large retail bank for two years.
Bellows are the illustation of the empirical findings in this study:
1. Duration and customer profitability are two good dimensions of segmentation. Long-lived customers are not necessarily profitable customers. Short-lived customers have great potential in profitability, too. The firm may not fulfill their needs. Those customers may be butterflies, i.e., they like to use different banks’credit cards. On the other hand, some customers may have budget for their spending. The firm must investigate this phenomenon deeply, so as to plan their marketing strategy.
2. Each segment concerns about different issues because they have distintive consuming behavior. So, the firm must have different marketing strategies for each segment.
3. There is positive association between customers and the firm's profitability in most of the segments. This reveals that most customers are profitable.
4. Tansistors are the domain customer type of the firm. They usually pay bills in time. Maybe, they have spending budget. The firm receives transation fees only. Under this condition, operation excellence is the key point. The firm must pay great efforts to become the domain bank of their customers.
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Der Einfluss jugendlicher Sozialisationserfahrungen auf ausgewählte Aspekte der politischen Identität im Erwachsenenalter / The impact of socialization during adolescence on selected aspects of adult political identityMays, Anja 04 February 2008 (has links)
No description available.
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"Não linearidades ópticas em azocompostos" / Optical nonlinearities in azocompoundsLeonardo de Boni 10 December 2004 (has links)
Neste trabalho, são estudadas as alterações das propriedades ópticas lineares e não lineares de soluções de azocompostos devidas aos mecanismos de isomerização e às alterações das propriedades estruturais com a temperatura. A dependência da transição pipi* com a estrutura linear dos azocompostos é notada já nas medidas dos espectros de absorção em função da temperatura para o isômero trans. Através do conhecimento dos níveis de energia e dos tempos de relaxação via isomerização, foi possível obter a dinâmica entre os isômeros cis e trans. As medidas não lineares forneceram propriedades interessantes associadas aos estados de energia dos compostos. Por exemplo, através de experimentos de varredura-z e de excitação e prova, foi possível ver que os azocompostos apresentam uma alta transparência quando excitados, a qual desaparece com o término da isomerização. Medidas em função do comprimento de onda mostraram que a transparência observada está presente em toda a banda pipi* e não ocorre na banda npi* . Também foi observado que o tempo de isomerização muda de acordo com o comprimento de onda de excitação, o que pode estar relacionado com a superposição das duas bandas. Os resultados obtidos em femtossegundos foram essenciais para descrever o processo dinâmico de fotoisomerização, observado, por completo, através de medidas com varredura-Z em picossegundos e nanossegundos. Essas medidas forneceram os valores das seções de choque dos isômeros cis, que são difíceis de serem quantificadas devido ao curto tempo de vida desse isômero. Além dos resultados ressonantes, foram feitos experimentos de absorção de dois fótons em femtossegundos usando a técnica de varredura-Z. Esses estudos mostraram a dependência das seções de choque de absorção de dois fótons com características estruturais das moléculas, tais como comprimento de conjugação, grupos push-pull e planaridade. Os resultados ressonantes e não ressonantes obtidos em femtossegundos serviram de base para a calibração da técnica de varredura-Z com pulsos de luz branca. Essa técnica se mostrou adequada para a obtenção dos espectros das não linearidades ópticas ressonantes e não ressonantes em uma única medição (de 5 minutos), diminuindo assim flutuações do laser durante o experimento. / This work reports on the temperature dependence of linear and nonlinear properties of azocompounds solutions due to isomerization mechanisms. The dependence of pipi* transitions on the linear structure of azocompounds is already noticeble in the measurements of absorption spectra as function of the temperature for the trans isomer. Knowing the energy levels and the relaxation times through isomerization, it was possible to obtain the exchange dynamics between cis and trans conformations. Nonlinear measurements provided interesting properties associated with the energy levels of de compounds. For exemple, through Z-scan and pumpprobe experiments, it was possible to verify that azocompounds present a high transparency when excited and that this transparency disapears when the izomerization ends. The wavelength change has shown that the observed transparency is present along the complete pipi* band, but not in the npi* band. It was also observed that the isomerization time changes with the exciting wavelength, which may be related to the superposition of both bands. The results obained with femtoseconds pulses were essential to completily describe the photoisomerization process observed with Z-scan measurements using picoseconds and nanoseconds pulses. These measurements provided values of the crosssection of the cis conformation, which are difficult to be quantified due to the short lifetime of this isomer. Besides ressonant results, experiments of two-photon absorption in the femtosecond regime using the Z-scan technique were made. These studies shown the dependence of the two photons absorption cross-section on structural features of molecules such as conjugation length, push-pull groups and planarity. The ressonant and nonressonant results obteined with femtoseconds have provide the calibration of the Z-scan technique with white light pulses. This technique has been found able to obtain the spectra of ressonat and nonressonant nonlinearities in a single measurement (about 5 minutes), diminishing laser fluctuation during the experiment.
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