La durée de vie des porteurs minoritaires est l'un des principaux paramètres mesurés dans les semi-conducteurs et la décroissance de photoconductivité (PCD) l'une des méthodes les plus largement utilisées pour ce type de mesure. Aujourd'hui, grâce aux divers équipements automatisés, la mesure de durée de vie est devenue une caractérisation de routine qui permet de juger de la qualité d'un matériau dans tous les secteurs utilisant les semi-conducteurs. Cependant, l'utilisation de micro- et nano-matériaux dans l'industrie du photovoltaïque et de la microélectronique requière l'adaptation des techniques existantes (PCD, photoluminescence etc.). En effet, avec la réduction des dimensions (couches ultraminces telles que les couches épitaxiées, couches SOI « silicon on insulator », et nanostructures), l'influence de la surface (états d'interfaces, pièges, etc.) devient prépondérante. La présence des substrats utilisés pour les croissances ou report de couche de ces différentes structures perturbe également les mesures. Ceci rend difficile l'adaptation des méthodes de mesure de durée de vie classiques comme, par exemple, le déclin de photoconductivité. Au cours de cette thèse nous nous sommes attachés à adapter des techniques de caractérisation de durée de vie à des matériaux de faibles dimensions. Nous avons tout d'abord caractérisé des échantillons massifs et des couches épitaxiées d'une épaisseur de l'ordre de la dizaine de micromètres. Nous avons proposé une technique qui consiste à déterminer simultanément la durée de vie en volume et la vitesse de recombinaison en surface des porteurs minoritaires dans d'une couche épitaxiée, à partir de la mesure de l'intensité de photoluminescence. La méthode développée consiste à calculer le rapport de l'intensité de photoluminescence (RPL) mesurée à différentes longueurs d'onde et pour différentes puissances d'excitation. Ces rapports RPL expérimentaux sont ensuite comparés aux rapports RPL simulés, ce qui permet d'évaluer la vitesse de recombinaison en surface et le temps de vie en volume. Nous avons ensuite étudié des couches semi-conductrices ultraminces de l'ordre de la centaine de nanomètres dans des structures de type SOI (silicon on insulator). Après un rappel des méthodes de fabrication et de quelques-unes des utilisations, nous avons analysé les méthodes électriques existantes permettant de déterminer la qualité des substrats SOI. Cela nous a amené à proposer une nouvelle méthode de caractérisation apportant des solutions aux limitations de ces techniques. Cette méthode se base sur une mesure courant-tension sous obscurité et sous éclairement en configuration PSEUDO-MOSFET où le substrat de la structure SOI sert de grille du transistor et deux pointes déposées sur le film de silicium servent de source et drain. Nous avons appliqué cette nouvelle méthode de caractérisation de la durée de vie des porteurs de charge à un substrat SOI et avec l'aide de la simulation numérique, nous avons pu expliquer les phénomènes de recombinaison aux interfaces et extraire les paramètres associés. Enfin, la dernière partie de ce travail de thèse concerne l'étude des nanofils pour des applications photovoltaïques. Dans les nanofils, le rapport surface sur volume augmente considérablement ce qui entraîne une diminution de la durée de vie effective due à l'augmentation de l'influence des surfaces. Le fonctionnement des cellules solaires à base de nanofils que nous avons étudiées est très dépendant de la qualité des interfaces. Nous avons analysé ces cellules grâce à la méthode RRT (« Reverse Recovery Transient ») basée sur la proportionnalité qui existe entre la quantité de charges stockées dans les régions neutres des jonctions pn polarisées et la durée de vie des porteurs minoritaires. Ce type de structure étant assez complexe, nous avons utilisé des simulations numériques pour analyser les phénomènes de recombinaison au sein de la cellule solaire et extraire les densités de défauts aux interfaces. / The minority carrier lifetime is one of the main parameters used to analyse the semiconductors quality and photoconductivity decay (PCD) is one of the most widely used lifetime characterization method. Thanks to the variety of automated equipment that has developed, lifetime measurement has become a routine technique to assess the quality of semiconductors. However, the micro and nano materials used in the photovoltaic and microelectronics industry require an adaptation of the existing methods (PCD, photoluminescence etc.). Indeed, with reduced dimensions (epitaxial layers, SOI “Silicon on Insulator”, nanostructures and nanowires), the influence of the surface (interface states density, traps, etc.) becomes predominant. The presence of the substrates used for the material growth or for the layer transfer can also influence the measures. Consequently traditional methods of lifetime measurement are difficult to apply to low dimensional materials. This thesis is focused on the measurement of minority carrier lifetime in micro and nano materials (bulk, epitaxial layer, silicon on insulator and nanowires) with a special emphasis on the adaptation of the characterization tools to the material thickness. We have studied first bulk samples and epitaxial layers (with thicknesses around 50µm) by photoluminescence. We have developed a method to determine simultaneously the bulk lifetime and the surface recombination velocity using room temperature photoluminescence measurement. The procedure consists in measuring the photoluminescence intensity ratio at different incident laser wavelengths and power. These photoluminescence ratios are then compared with analytical simulations, which allow us to evaluate the surface recombination velocity and the bulk lifetime. We have then investigated SOI (Silicon on insulator) structures with ultrathin semiconductor layers of the order of 100 nanometers. After a brief description of the manufacturing methods and of some of their uses, we have analyzed the existing electrical methods used to evaluate the quality of SOI substrates. This led us to propose a new characterization method to overcome the limitations of these techniques. This method is based on a current-voltage measurement in the dark and under illumination called PSEUDO-MOSFET (the substrate of the SOI structure serves as the transistor gate and the two contact points deposited on the silicon film are used as the source and drain). We applied this new method to characterize the lifetime of a SOI substrate and with the help of numerical simulation, we were able to explain the recombination mechanism associated with interfaces and extract the parameters. Finally, the last chapter concerns the study of nanowires for photovoltaic applications. In the nanowires, the surface to volume ratio greatly increases leading to a decrease of the effective lifetime due to the increased influence of the surfaces. In this chapter, we have studied the minority carrier lifetime in core-shell nanowire-based solar cells under dark conditions with a purely electrical approach called reverse recovery transient (RRT). This method is based on storage time measurement which depends essentially on the amount of stored charges in the biased junction and can be used to calculate the minority carrier lifetime. Numerical simulations have also been done to explain the measurements and to validate the theory and the hypotheses used for parameter extraction.

Orientador: Fernando Galembeck / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-24T05:29:50Z (GMT). No. of bitstreams: 1 Burgo_ThiagoAugustodeLima_D.pdf: 54614783 bytes, checksum: 04e6b01b521de52d69d91a83d891d034 (MD5) Previous issue date: 2013 / Resumo: A triboeletrização de polímeros gera domínios macroscópicos de carga positiva e negativa, verificando a geometria fractal de mosaicos de carga previamente detectados por microscopia de sonda elétrica. Utilizando métodos analíticos adequados (espectroscopia de perda de energia de elétrons, microespectroscopia infravermelho/Raman e carbonização/colorimetria) e cálculos teóricos, espécies positivas foram identificadas como hidrocarbocátions e espécies negativas como fluorocarbânions. A triboeletrização de PTFE com PE é entendida como segue: a ruptura homolítica mecanoquímica da cadeia é seguida por transferência eletrônica dos radicais livres de hidrocarbonetos para os radicais mais eletronegativos do fluorocarbono. Os íons gerados pelos fragmentos de cadeia sofrem auto-ordenamento de acordo com a teoria de Flory- Huggins, formando os padrões macroscópicos observados experimentalmente. Estes resultados mostram que a triboeletrização só pode ser compreendida considerando os eventos químicos complexos provocados por ação mecânica, acoplados a conceitos bem estabelecidos pela físico-química. Além disso, o atrito entre superfícies dielétricas produz padrões de carga fixos e estáveis que contribuem para interações eletrostáticas entre superfícies. Medidas de coeficiente de resistência de rolamento de esferas de vidro sobre PTFE triboeletrizado, bem como de atrito estático de pellets de polietileno e imagens de microscopia de força lateral, mostraram que as forças de atrito aumentam muitas vezes em superfícies triboeletrizadas, nas quais as contribuições das interações eletrostáticas podem suplantar todas outras contribuições. Estes resultados são explicados considerando um mecanismo segundo o qual a indução de carga por uma superfície triboeletrizada no contato com outra superfície dissipa energia durante o atrito, sugerindo novas abordagens para controlar atrito em interfaces pelo controle da formação de tribocargas / Abstract: Tribocharged polymers display macroscopically patterned positive and negative domains, verifying the fractal geometry of electrostatic mosaics previously detected by electric probe microscopy. Using suitable analytical techniques (electron energy-loss spectral imaging, infrared/Raman microspectrophotometry and carbonization/colorimetry) and theoretical calculations, the positive species were identified as hydrocarbocations and the negative species as fluorocarbanions. A comprehensive model is presented for PTFE tribocharging with PE: mechanochemical chain homolytic rupture is followed by electron transfer from hydrocarbon free radicals to the more electronegative fluorocarbon radicals. Polymer ions self-assemble according to Flory-Huggins theory, thus forming the experimentally observed macroscopic patterns. These results show that tribocharging can only be understood by considering the complex chemical events triggered by mechanical action, coupled to well-established physicochemical concepts. Also, friction between dielectric surfaces produces patterns of fixed, stable electric charges that in turn contribute electrostatic components to surface interactions between the contacting solids. The coefficient of rolling resistance of glass beads on tribocharged PTFE was measured, as well as the static friction coefficient of polyethylene pellets on PTFE and friction force on the scanning probe during lateral-force microscopy imaging. Results show that friction coefficients may increase many-fold on tribocharged surfaces and the contribution of electrostatic interactions may supersede all other contributions to friction. These results are explained considering a mechanism according to which charge induction by an electrified surface on a contacting body accounts for energy dissipation during friction suggesting new approaches to control friction coefficients, by controlling tribocharge formation / Doutorado / Físico-Química / Doutor em Ciências

When an electromagnetic wave illuminates metal nanostructure under right circumstances, it can couple to the motion of electrons and thus give rise to so-called LSPR. When these collective oscillations non-radiatively decay, they excite charge carriers that can have, for a short moment of time, highly non-thermal energy distribution. These so-called "hot" electrons and holes can then take part in photochemical applications, e.g. in reactions on photoactive electrodes where hot electrons act as catalysts. Gold nanoparticles seem to be a good candidate for fabrication of such electrodes because they exhibit resonantly enhanced absorption due to plasmon excitation in the visible and near infrared spectral range, which could make the solar energy harvesting more efficient. In this work we present electrohemical experiments that should help to clarify the underlying principles of photochemical reactions involving hot electrons. Our model system consists of indium tin oxide electrodes covered with tungsten disulphide nanotubes that were previously decorated by gold nanoparticles. By comparing the results of chronoamperometric measurements on individual components of this system it was shown that excitation of plasmonic nanoparticles indeed leads to photocurrents and that electrochemical methods can serve as a valuable tool for analysis of photochemical reactions catalyzed by hot electrons.

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Das fundamentale Verständnis von Ladungsträgern in molekularen Halbleitern, die typischerweise als Polaronen bezeichnet werden, ist unverzichtbar, wenn es um das Design besonders leistungsfähiger (opto)elektronischer Bauelemente geht. Die vorliegende Arbeit hat zum Ziel ein umfangreiches Bild der Energetik von Polaronen in organischen Halbleitern zu erhalten. Zunächst geht es darum einen Probenaufbau zu finden, der es nicht nur ermöglicht Ladungsträger zu generieren, sondern auch ihre elektronische Struktur unter Verwendung von komplementären Photoemissionstechniken – Rötngen-, Ultraviolett- und inverse Photoelektronenspektroskopie - aufzuklären. Das Probenkonzept basiert darauf, dass molekulare Filme, die eine niedrigere Ionisierungsenergie als die Austrittsarbeit des zugrunde liegenden Substrates aufweisen, Fermi-level Pinning zeigen. In diesem Fall wären die höchsten besetzten Zustände der neutralen molekularen Schicht energetisch oberhalb des Substrat-Fermi-Levels angeordnet, wodurch zum Erhalt des elektronischen Gleichgewichts die Notwendigkeit für einen Ladungstransfer gegeben ist. Da die starke elektronische Kopplung zwischen Molekülen und Metallen die spektrale Information der Überschussladungsträger verändern könnte, wird die Metalloberfläche durch eine ultradünne Zwischenschicht passiviert. Die Ergebnisse zeigen, dass es durch die vorliegende starke on-site Coulomb Repulsion zur Aufspaltung des höchsten besetzen molekularen Niveaus in ein besetztes und ein unbesetztes Sub-niveau kommt. Dies widerspricht der seit Jahren etablierten Vorstellung von einem einfach besetzten Niveau in der Bandlücke des neutralen molekularen Halbleiters. Unter zusätzlicher Berücksichtigung der inter-site Coulomb Repulsion zwischen Molekülionen und neutralen Molekülen, sowie der Energieniveau Verbiegung kann schließlich ein vollständiges Bild entwickelt werden, das die etablierte Vorstellung der Energieniveaus von Ladungsträgern in molekularen Halbleitern ersetzen soll. / Understanding the nature of charge carriers in molecular semiconductors, typically termed "polarons", is indispensable for rational material design targeting future superior (opto-)electronic device performance. The present work addresses this fundamental issue to derive a comprehensive picture of polarons in organic semiconductors. Conceptual work is dedicated to identifying a sample structure, which allows both, deliberately generating charged molecules and applying the complementary photoemission techniques X-ray, ultraviolet and inverse photoelectron spectroscopy in order to assess the polaron energetics. The sample concept is based on the fact that molecular layers exhibiting an ionization energy lower than the work function of the supporting substrate show Fermi-level pinning. There, as the substrate Fermi-level is moved into the occupied density of states of the molecular adsorbate, electron transfer occurs from the molecules to the substrate. Because strong electron coupling between molecules and eg. metal surfaces might mask or alter the spectral information of excess charge carriers, such interaction needs to be inhibited by implementation of an ultrathin passivating interlayer. The comprehensive results provide evidence that the highest occupied molecular orbital level is split into an upper unoccupied and a lower occupied sub-level due to strong on-site Coulomb interaction. This finding is in marked contrast to what has been assumed for decades, where a singly occupied level was proposed to lie within the gap of the neutral molecular semiconductor. Moreover, taking into account the inter-site Coulomb interaction between molecular cations and surrounding neutral molecules, as well as energy-level bending, finally, a complete picture of the energetics associated with polarons in molecular semiconductors could be derived, which aims at replacing common perceptions.

Die vorliegende Dissertation befasst sich mit der ramanspektroskopischen Charakterisierung von Galliumnitrid (GaN). Der Zusammenhang zwischen Waferkrümmung und mechanischer Restspannungen wird diskutiert. Mit Hilfe konfokaler Mikro-Ramanmessungen wurden Dotierprofile nachgewiesen sowie die Ladungsträgerkonzentration und -beweglichkeit ermittelt. Sämtliche Ramantensorelemente von wz-GaN wurden erstmals durch die Anwendung verschiedener Streugeometrien bestimmt. Eine neu entwickelte Vorwärtsstreuanordnung ermöglichte die Beobachtung von Phonon-Polaritonen. Es konnte gezeigt werden, dass von der theoretischen und experimentellen Betrachtung der Ramanstreuintensitäten dieser Elementaranregungen eindeutig das Vorzeichen der Faust-Henry-Koeffizienten von wz-GaN abgeleitet werden kann. Im Rahmen dieser Arbeit wurden alle Faust-Henry-Koeffizienten für GaN experimentell bestimmt. / This thesis focuses on special aspects of the Raman spectroscopical characterization of wurtzite gallium nitride (wz-GaN). The correlation between wafer curvature and residual stress is discussed. By means of confocal micro-Raman measurements doping profiles were detected as well as the density and mobility of free charge carriers were deduced. All Raman scattering cross sections of wz-GaN were determined the first time using different scattering configurations. A novel method for near-forward scattering was developed in order to observe phonon polaritons with pure symmetry. It is shown that the theoretical and experimental consideration of the Raman scattering efficiency of these elementary excitations allow for determining the sign of the Faust-Henry coefficients of wz-GaN unambiguously. The Faust-Henry coefficients of GaN were deduced from Raman scattering efficiencies of corresponding TO and LO phonons.

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