Current leakage in GaN thin films limits reliable device fabrication. A variety of Ga and N rich MBE GaN thin films grown by Rf, NH3, and Rf+ NH3, are examined with electrical measurements on NiIAu Schottky diodes and CAFM. Current-voltage (IV) mechanisms will identify conduction mechanisms on diodes, and CAFM measurements will investigate the microstructure of conduction in GaN thin films. With CAFM, enhanced conduction has been shown to decorate some extended defects and surface features, while CAFM spectroscopy on a MODFET structure indicates a correlation between extended defects and field conduction behavior at room temperature. A remedy for poor conduction characteristics is presented in molten KOH etching, as evidenced by CAFM measurements, Schottky diodes, and MODFET's. The aim of this study is to identify anomalous conduction mechanisms, the likely cause of anomalous conduction, and a method for improving the conduction characteristics. Keywords: 111-Nitride, 111-V, Gallium Nitride, GaN, Electrical Properties, Conduction, Conductivity, Mobility, Hall Measurements, Resistivity, Schottky Diode, Modulation Doped Field Effect Transistor (MODFET), Conductive Atomic Force Microscopy (AFM), Defects, Molten Potassium Hydroxide (KOH) etching, Silvaco, Atlas, and Illumination.

Dans les dernières années nombre de matériaux lamellaires à dimensions réduites ont démontré des propriétés optiques remarquables. Cependant, la plupart des études ont porté sur le système parfait et le rôle des défauts en tant que centres optiques actifs restent encore largement inexploré. Le nitrure de bore hexagonal (h-BN) est l'un des candidats les plus prometteurs pour les dispositifs émetteurs de lumière dans la région de l’UV lointain, présentant une forte émission excitonique à 5,8 eV. Cependant, émission n’apparaît uniquement que dans des monocristaux très purs qui peuvent difficilement être obtenus que par des procédés de synthèse complexes. Les échantillons ordinaires de h-BN présentent des spectres d'émission plus complexes qui ont été généralement été attribuée à la présence de défauts structuraux. Malgré un grand nombre d'études expérimentales jusqu'à présent il n'a pas été possible d'attribuer cette émission additionnelle à des défauts structuraux bien définis. Nous abordons ici cette question fondamentale en adoptant une approche théorique et expérimentale combinant une technique de cathodoluminescence nanométriquement résolu avec une caractérisation structural résolu atomiquement par microscopie électronique a transmission et de l'état de l'art de simulations excitoniques. Très récemment, l'équipe d'Orsay a mis au point un système de détection de cathodoluminescence intégré au sein d'un microscope électronique à transmission à balayage. Cette expérience unique est maintenant en mesure de fournir des spectres d'émission complet avec une résolution aussi faible que quelques dizaines de MeV associés à une taille de sonde électronique du nanomètre. Une image hyper-spectrale cathodoluminescence peut donc être enregistrée en parallèle avec une image HAADF. La cathodoluminescence résolu au nanomètre sur quelques-couche chimiquement exfoliée de h-BN a montré que les spectres d'émission sont fortement inhomogènes dans les feuillets individuels. Les pics d'émission à proximité de l'exciton libre apparaissent dans des régions étendues. Les examens complémentaires par microscopie électronique à transmission à haute résolution permettent d'associer ces raies d'émission avec des défauts étendue dans le cristal tels que les défauts d'empilement et les plis des facetter. Au moyen de calculs ab-initio dans le cadre de la « Many Body perturbation theory » (GW) et l'équation de Bethe-Salpeter nous fournissons une description détaillée de la structure électronique et la réponse spectroscopique du nitrure de bore hexagonal en présence de défaut d’empilements. En particulier, nous montrons un bon accord avec les résultats expérimentaux, les excitons supplémentaires sont associées à des changements de symétrie locaux qui se produisent par des fautes d'empilement dans le cristal. Ce résultat sera ensuite étendu à des nanotubes de BN à parois multiples. Des émissions supplémentaires qui apparaissent à l'intérieur du gap présentent une localisation spatiale élevée, typiquement inférieure à 100 nm, et par conséquent ils peuvent être liés à des défauts ponctuels individuels. Lorsqu’ils sont adressés individuellement à travers une sonde électronique très ciblé, ils pourraient avoir un caractère d’émetteur de photon unique. Cette hypothèse a été récemment confirmée par des expériences combinant notre système de cathodoluminescence avec un interféromètre Handburry-Brown et Twiss (HBT). / Within the latest years number of layered materials at reduced dimensions have demonstrated remarkable optical properties. However most studies focused on perfect system and the role of defects as optical active centers remain still largely unexplored. Hexagonal boron nitride (h-BN) is one of the most promising candidates for light emitting devices in the far UV region, presenting a single strong excitonic emission at 5.8 eV. However, a single line appears only in extremely pure mono-crystals that can hardly be obtained only though complex synthesis processes. Common h-BN samples present more complex emission spectra that have been generally attributed to the presence of structural defects. Despite a large number of experimental studies up to now it was not possible to attribute specific emission features to well identify defective structures. Here we address this fundamental question by adopting a theoretical and experimental approach combining few nanometer resolved cathodoluminescence techniques with high resolution transmission electron microscopy images and state of the art quantum mechanical simulations. Very recently, the Orsay team has developed a cathodoluminescence detection system integrated within a scanning transmission electron microscope. This unique experimental set up is now able to provide full emission spectra with a resolution as low as few tens of meV associated with an electron probe size of one nanometer. A cathodoluminescence hyper-spectral image can thus be recorded in parallel with an HAADF image. Nanometric resolved cathodoluminescence on few-layer chemically exfoliated h-BN crystals have shown that emission spectra are strongly inhomogeneous within individual flakes. Emission peaks close to the free exciton appear in extended regions. Complementary investigations through high resolution transmission electron microscopy allow to associate these emission lines with extended crystal deformation such as stacking faults and folds of the planes. By means of ab-initio calculations in the framework of Many Body Perturbation Theory (GW) approximation and Bethe-Salpeter equation) we provide an in-depth description of the electronic structure and spectroscopic response of bulk hexagonal boron nitride in the presence of extended morphological modifications. In particular we show that, in a good agreement with the experimental results, additional excitons are associated to local symmetry changes occurring at crystal stacking faults. These result will then be extended to faceted multiwalled BN nanotubes, they display additional emission at the same energy as characterized within the flakes.

Neste trabalho estudamos as propriedades físicas das impurezas de elementos de terra rara (TR) nos cristais de GaN, nas estruturas cristalinas zincblenda e wurtzita, e de ZnO. Para tal, consideramos as impurezas de Eu, Gd, Tb, Dy, Ho, Er e Tm substitucionais no sítio do cátion (Ga ou Zn), pois esta posição é mais estável do que no sítio do ânion (N ou O). As investigações foram efetuadas através de simulações computacionais baseadas em métodos de primeiros princípios dentro do formalismo da teoria do funcional da densidade e utilizando o método FP-LAPW (Full Potential Linear Augmented Plane Waves), implementado no código computacional WIEN2k, dentro do esquema de supercélula, com relaxações atômicas tratadas de modo apropriado. No tratamento dos estados de valência 3d (Ga ou Zn) e 4f dos átomos de TR foi introduzida uma correção local de Hubbard, para levar em conta efeitos de alta correlação eletrônica. Inicialmente, estudamos as propriedades eletrônicas e estruturais dos elementos de TR em suas fases metálicas. Estes resultados serviram para validar a metodologia de obtenção dos valores dos parâmetros U de Hubbard de modo autoconsistente, pois para este grupo de materiais existem resultados experimentais. Comparando a localização e o desdobramento entre os estados ocupados e desocupados relacionados aos orbitais 4f, em relação ao nível de Fermi dos sistemas, obteve-se uma ótima concordância. Nossos resultados para os sistemas dopados, utilizando a correção do potencial U de Hubbard, mostram que a suas descrições estão adequadas. Somente com a introdução da correção é possível localizar corretamente, em relação ao topo da banda de valência, os estados ocupados e desocupados relacionados aos orbitais 4f. Estes resultados estão de acordo com esquemas propostos na literatura, mostrando que o estado de oxidação das impurezas de TR é trivalente e que, em geral, em ambos sistemas cristalinos, não há a introdução de níveis de energia na região do gap dos materiais. Nosso estudo da correção do potencial U de Hubbard, obtido autoconsistemente, na teoria do funcional da densidade, mostra que seus valores não são universais, dependendo do estado de carga e do ambiente em que o átomo está inserido. Mais ainda, mostra que o procedimento adotado é totalmente apropriado para descrever a correlação eletrônica dos elétrons 4f. / In this work we studied the physical properties of rare earth (RE) impurities in GaN, in the zincblend and the wurtzite crystal structures, and in ZnO. Eu, Gd, Tb, Dy, Ho, Er and Tm substitutional impurities in the cation site (Ga or Zn) were considered, since this position is more stable than anion site (N or O). The investigations were carried out by computational simulations using ab initio methods, based on the density functional theory and the FP-LAPW (Full Potential Linear Augmented Plane Waves) method, as implemented in the WIEN2k code, considering the supercell approach and atomic relaxations. The 3d-Ga or 3d-Zn and the 4f-RE valence states were treated with the introduction of on-site Hubbard correction, in order to correctly describe the strongly correlated electrons. First, the electronic and structural properties of RE metallic systems were investigated and the results were compared with available experimental data, showing a good agreement. Those results helped to identify the appropriate procedure to compute the Hubbard U potential. This procedure should also provide a reliable description about the electronic properties of RE elements as impurities in semiconductors. Then, we have computed the properties of substitutional RE impurities in the cation site using the same methodology and procedures. The Hubbard U potential was necessary to correctly describe the position of the 4f occupied and unoccupied states, related to the valence band top. These results are in agreement with proposed electronic properties of RE doped GaN and ZnO found in the literature. The RE impurities oxidation states are in general trivalent in both crystal systems and introduce no energy levels in the gap region. Our Hubbard U potential correction, obtained in a self-consistent way, depends on the considered element and the neighborhood, and it is not an universal parameter. Moreover, our investigation shows that the adopted procedure is totally appropriate to describe the electronic correlation of the 4f electrons.

Os aços inoxidáveis duplex são materiais com um excelente desempenho, devido às suas sobressalentes propriedades mecânicas e excelente resistência à corrosão. Uma composição química adequada e microestrutura balanceada são as responsáveis por esta combinação de propriedades. No entanto, são estes mesmos fatores que os fazem especialmente susceptíveis à precipitação de fases intermetálicas, com efeitos maléficos no seu desempenho. Durante os ciclos térmicos de uma soldagem multipasse, a precipitação de intermetálicos é crítica. Foi desenvolvido um método para simular os ciclos térmicos de uma solda multipasse. Usando este método, foi estudada a precipitação de nitreto de cromo e fase sigma na zona afetada pelo calor submetida a temperaturas abaixo de 950°C dos aços inoxidáveis duplex UNS S31803 e S32550. Foram estudadas energias de soldagem na faixa de 0,4 a 1,0 kJ/mm. Foi determinada mediante extração de precipitados, seguida de difração de raios X na câmara de Debye-Scherrer e microscopia eletrônica de transmissão, a precipitação de nitreto de cromo para energias de soldagem de 0,4 a 1,0 kJ/mm e de fase sigma para energias de soldagem de 0,6-1,0 KJ/mm, no UNS S32550. Já o UNS S31803 não apresentou precipitação alguma para as energias de soldagem estudadas. Baseando-se nos resultados verifica-se que durante uma soldagem multipasse o UNS S31803 é menos propenso que o UNS S32550 à precipitação de intermetálicos na zona afetada pelo calor submetida a temperaturas abaixo de 950°C. / Duplex stainless steels belong to a group of high performance stainless steels regarding to corrosion and mechanical properties. These achievements are related to a suitable chemical composition and a balanced microstructure. During welding thermal cycles the microstructure changes and, consequently, corrosion and mechanical properties might be impaired due to a precipitation of intermetallic phases. This precipitation is an issue to be addressed for multipass welding. It was developed a method for simulate the multipass welding thermal cycles. Using this method chromium nitride and sigma phase precipitation was studied in a simulated heat affected zone of multipass welding (three passes) of UNS S31803 and UNS S32550 duplex stainless steels with different heat inputs (0,4 to 1,0 kJ/mm). The HAZ simulated region was below 950°C maximum temperature. Microstructural characterization of simulated samples showed discontinuous films of a precipitated phase at ferrite/ferrite grain boundaries and ferrite/austenite interfaces were observed only in a UNS S32550 duplex grade for all heat inputs simulated. This suggests that sigma phase and chromium nitride precipitation took place during sample thermocycling. X-ray diffraction in a Debye-Scherrer chamber of extracted precipitates and electron diffraction by TEM confirmed the presence of chromium nitrides for all range of heat input studied and sigma phase for heat input above 0,6 kJ/mm. On the other hand, microstructural analysis of UNS S31803 simulated samples did not present precipitation of intermetallic phases in the tested temperature range of HAZ. Based on these results, UNS S31803 is more resistant than UNS S32550 to intermetallic phases precipitation in multipass welding.

O nitreto de alumínio (AlN) apresenta elevada condutividade térmica, além de um conjunto de propriedades físicas, que o torna um excelente candidato a substituir a alumina (Al2O3) e a berília (BeO) na fabricação de dispositivos eletrônicos de alta performance. A rota de fabricação do AlN com elevada condutividade térmica está estabelecida na literatura, sendo o Y2O3 e o CaO os aditivos de sinterização mais usados. No entanto, observou-se que os estudos sobre esta cerâmica esclarecem parcialmente os mecanismos envolvidos na sua sinterização. Assim, este trabalho tem como objetivo geral estudar os possíveis mecanismos envolvidos na sinterização do AlN, tendo como objetivo específico estudar a influência do teor de CaCO3 e CaO na densificação do AlN. O comportamento de densificação do AlN com 0,5%, 1%, 2%, 4% e 8% em peso de CaO, adicionado na forma de CaCO3 e CaO calcinado, foi estudado por sinterizações em dilatômetro e em forno com elemento resistivo de tungstênio entre 1100ºC e 2000ºC. Os corpos sinterizados foram analisados por microscopia eletrônica de varredura, microanálise por espectrometria por dispersão de energia, difratometria de Raios X e análise química por espectrometria de emissão atômica por plasma de acoplamento induzido. Os resultados experimentais mostraram que não ocorreu variações significativas nos comportamentos de densificação das amostras de AlN com adição de CaCO3 e CaO entre 1100ºC e 1800ºC, desde que as comparações sejam feitas em relação aos respectivos teores equivalentes de CaO. A adição de pequenas quantidades de ambos os aditivos, ou seja, de 0,5% em teor equivalente de CaO, aumentou de forma significativa a sinterabilidade do AlN. O aumento do teor de ambos os aditivos causou a formação de segundas fases de aluminato de cálcio mais ricas em CaO entre 1300ºC e 1600ºC, o que era esperado. Entretanto, acima desta faixa de temperatura, observou-se uma tendência de formar a fase CA, independente do teor e tipo de aditivo usado, mostrando que a fase CA é mais estável em altas temperaturas no AlN do que as demais fases de aluminato de cálcio previstas no sistema CaO – Al2O3. Em geral, a densificação das amostras de AlN com adição de CaCO3 e CaO foi influenciada pela rota de evolução das segundas fases, quantidade de fase líquida e a formação de poros grandes. A formação de fases ricas em CaO (C3A e C12A7) promoveu a formação de fase líquida em baixas temperaturas, o que causou uma rápida densificação inicial das amostras de AlN com 2% a 8% de CaO, com ambos os aditivos, abaixo de 1600ºC. O aumento do teor de aditivo também favoreceu a densificação destas amostras devido à maior quantidade de fase líquida formada, porém, causou a formação de uma elevada quantidade poros grandes. As amostras de AlN com 0,5% e 1% de CaO, com ambos os aditivos, apresentaram menor quantidade de poros grandes, porém, apresentaram fases mais ricas em Al2O3 (CA2 e CA6), as quais fundem em mais alta temperatura. Assim, somente acima de 1600ºC estas amostras apresentaram rápida densificação devido à formação de fase líquida e à baixa fração de poros grandes. Por outro lado, as amostras com 2% a 8% em teor equivalente de CaO apresentaram lenta densificação devido à dificuldade de eliminação dos poros grandes, mesmo sinterizando em altas temperaturas (>1800ºC). De maneira geral, os poros grandes foram sendo eliminados da microestrutura em decorrência do crescimento de grão, que ocorreu principalmente durante a sinterização assistida por fase líquida. / Aluminum nitride (AlN) presents high thermal conductivity, beyond several physical properties, that make it an excellent candidate to substitute alumina (Al2O3) and the berylia (BeO) in the manufacturing of high performance electronic devices. The route of production of AlN with high thermal conductivity is established in literature, with Y2O3 and CaO the most used sintering additives. However, the studies on this ceramics clarify only partially the mechanisms involved in its sintering. The general aim of this work was to study the possible mechanisms related in the sintering of AlN. The specific objective was to understanding the influence of the amount of CaCO3 and CaO in the densification of AlN. The densification behavior of AlN with 0.5%, 1%, 2%, 4%, and 8% in weight of CaO, added as CaCO3 and calcined CaO, was studied by sintering both in dilatometer and in an oven with tungsten resistive elements between 1100ºC and 2000ºC. The sintered bodies were analyzed by scanning electronic microscopy, microanalysis by energy dispersive spectrometry, X-ray difratometry, and chemical analysis by ICP-AES. The same general tendencies in densification were observed in samples with CaCO3 and calcined CaO between 1100ºC and 1800ºC. The addition of small amounts of both additives (0.5% CaO) strongly enhanced the sinterability of AlN. With increasing amount of both additives, calcium aluminates richer in CaO were formed between 1300ºC and 1600ºC, as expected. However, above this temperature range, it was observed the tendency of the formation of CA phase, independent of the additive type and content, showing that the CA phase is more stable in high temperatures in AlN than the others calcium aluminates predicted by CaO - Al2O3 system. As a rule, the densification of the AlN samples with CaCO3 and calcined CaO additions was influenced by the second-phase evolution path, liquid phase content, and the formation of large pores. The formation of CaO rich phases (C3A and C12A7) promoted the formation of liquid phase in low temperatures, which caused a fast initial densification of the AlN samples with 2% to 8% CaO, with both additives, below 1600ºC. The increasing additive content also favored the densification of theses samples by the formation of a higher amount of liquid phase, but it caused the formation of higher fractions of large pores. The AlN samples with 0.5% and 1% CaO, with both additives, presented lower fractions of large pores, however they presented Al2O3 rich aluminate phases (CA2 and CA6), which melt at higher temperatures. Thus, only above 1600ºC these samples presented rapid densification because of the formation of liquid phase and the low fraction of large pores. On the other hand, the samples with 2% to 8% CaO presented slow densification because of the difficult of the elimination of the large pores, even sintering at high temperatures (> 1800ºC). The large pores were gradually eliminated from the microstructure as a consequence of grain growth, which occurred mainly during the liquid phase sintering.

Foram realizados ensaios tribológicos de deslizamento do par Si3N4-Al2O3, lubrificado com água, na configuração esfera contra disco, sendo a esfera de nitreto de silício e o disco de alumina para investigar a influência da velocidade de deslizamento, da carga aplicada e da temperatura no coeficiente de atrito. As esferas de nitreto de silício e os discos de alumina foram caracterizados determinando-se: densidades, dureza Vickers, módulo de elasticidade e tenacidade à fratura. Os ensaios foram realizados com rugosidade inicial nos discos de Rrms = 352 nm. O regime de ultra baixo coeficiente de atrito (UBCA, &#956; < 0,01) foi atingido após um período de running-in de aproximadamente uma hora e o coeficiente de atrito ficou na faixa de &#956; = 0,008 a &#956; = 0,002. Os resultados mostraram que este sistema deslizante tem características hidrodinâmicas, pois o coeficiente de atrito diminuiu com o aumento da velocidade de deslizamento. Uma variação suave da carga aplicada fez com que o coeficiente de atrito permanecesse no regime de UBCA, com a carga aplicada variando de 54 N até 94 N. Em temperaturas menores ou iguais a 11°C o sistema não atingiu o regime de UBCA e o coeficiente de atrito final ficou da ordem de centésimos. Foi observado o fenômeno de UBCA em temperaturas de 30 e 40°C. No entanto, nestas temperaturas, a baixa viscosidade da água não deveria permitir que o sistema atingisse o regime de UBCA. A análise dos dados possibilitou inferir que durante o regime de UBCA o sistema desliza num regime de lubrificação mista, sendo lubrificação hidrodinâmica, devido ao filme de água, somada a lubrificação limite, devido às camadas hidratadas formadas nas superfícies das cerâmicas. Os resultados mostraram que a temperatura influencia no desgaste das cerâmicas. A determinação do volume desgastado possibilitou observar que durante os ensaios a alumina sofre menos desgaste que o nitreto de silício e que o desgaste de ambas cerâmicas aumenta com o aumento da temperatura. / Tribological tests were conducted in a ball on disk setup, using water as lubricant. Were used a silicon nitride ball and alumina disk. The tests were conducted to investigate the effects of sliding speed, applied load and temperature on friction coefficient. The silicon nitride balls and alumina disks were characterized by determining density, Vickers hardness, elastic modulus and fracture toughness. The tests were conducted with initial roughness on the disk surface of 352 nm. The ultra low friction coefficient regime (ULFC, &#956; < 0.01) was reached after a running-in period of approximately one hour and the friction coefficient remains in the range of &#956; = 0.008 a &#956; = 0.002 during this steady state regime. The results showed that this sliding system has hydrodynamic characteristics, because the friction coefficient decreased with increasing of the sliding speed. With an smooth variation of the applied load the system remained in the ULFC regime, when the applied load varied from 54 N up to 94 N. At temperatures below or equal to 11°C the system did not reach the ULFC regime and the final friction coefficient was the order of hundredths. We observed the ULFC phenomenon at temperatures of 30 and 40°C. However, at these temperatures, the water viscosity is low and should not allow the system to reach the ULFC regime. The data analysis allowed infer that during the ULFC regime the system slides with a mixed lubrication regime, hydrodynamic plus limitrofe, the first due to water film and the second due to the hydrated layer formed on the ceramics surfaces. The results showed a influences of temperature in the ceramics wear. The results of the worn volume allowed to observe that during the tests alumina suffers less wear than the silicon nitride, and the ceramics wear increases with increasing temperature.

Im Rahmen dieser Arbeit werden Untersuchungen der Spinrelaxation in epitaktischen GaN-Schichten mit unterschiedlichen Donatorkonzentrationen und Versetzungsdichten mit Hilfe spin- und zeitaufgelöster differentieller Reflektanzspektroskopie präsentiert. Dabei wurden die optischen Anregungsbedingungen sehr sorgfältig gewählt. Neben der genauen Abstimmung der Anregungsenergie, unterstützt durch die Modellierung der differentiellen Reflektanz, wurden insbesondere spektral schmale Laserpulse verwendet. Diese erlauben eine selektive Anregung der untersuchten Übergänge. Es wurden Spinlebensdauern von 30 bis 170~ps bei tiefen Temperaturen für das freie A-Exziton bestimmt. In der Nähe des Metall-Isolator-Übergangs ließ sich eine langsamere Spinrelaxation als für schwächer dotierte Proben nachweisen. Die längsten beobachteten Spinrelaxationszeiten zeigen freistehende GaN-Schichten hoher Materialqualität mit sehr geringen Versetzungsdichten. In der Literatur besteht eine kategorische Unterteilung der Ergebnisse in lange elektronische Spinlebensdauern bis in den Nanosekundenbereich, erhalten mit Kerr-Messungen, und extrem kurze exzitonische Spinrelaxation in Reflektanz-Experimenten im (Sub-)Pikosenkundenbereich. Dieses Bild wird hier nicht bestätigt. Die beobachteten Spinrelaxationszeiten liegen eineinhalb bis zweieinhalb Größenordnungen über Ergebnissen, von denen bisher mit der hier verwendeten Methode berichtet wurde. Es wird gezeigt, dass die Beobachtungen extrem kurzer Spinrelaxationszeiten an anderer Stelle eine Folge der optischen Anregungsbedingungen sind. Die Verwendung sehr kurzer und damit spektral breiter Laserpulse, die eine selektive Exziton-Anregung verbieten, führt zu einem deutlich anderen zeitlichen Verhalten und stark verfälschten Ergebnissen. Diese Beobachtung löst den scheinbaren Widerspruch zwischen den beiden Ergebnisgruppen in der Literatur auf und bildet die Grundlage für weiterführende Untersuchungen. / In this work, an investigation of spin relaxation in GaN epitaxial layers with different doping concentrations and dislocation densities is presented. The measurements were carried out by the means of spin- and time-resolved differential reflectance spectroscopy. The conditions of optical excitation were chosen with special care. In particular, spectrally narrow laser pulses were used to achieve selective excitation of the examined transitions in addition to the precise adjustment of the excitation energy, supported by the modeling of the differential reflectance. The spin relaxation times obtained for the free A exciton at low temperatures are in the range of 30 to 170 ps. In the proximity of the metal insulator transition, a slower spin relaxation was observed than for lower doping concentrations. The longest spin relaxation times were found in high quality, free-standing GaN layers with very low dislocation densities. Existing results in the literature can be strictly grouped into long electronic spin lifetimes of up to a few nanoseconds, obtained with Kerr rotation, and extremely short spin relaxation in the (sub)picosecond range, measured with reflectance experiments. This picture cannot be confirmed here. The spin relaxation times observed here lie 1.5 to 2.5 orders of magnitude above the values previously reported using the same experimental method. It is shown that the instances of extremely fast spin relaxation are caused by the properties of the optical excitation. The use of ultra-short and thus spectrally broad laser pulses, which prohibits the selective excitation of excitons, leads to a significantly different temporal behavior and strongly distorted results. This finding elucidates the apparent conflict between the two groups of results and forms the basis for further investigations.

In der vorliegenden Arbeit werden verschiedene Aspekte des Einflusses von Lokalisation, Unordnung und Polarisationsfeldern auf Elektron-Loch Zustände in Quantengräben (QWs von engl. quantum wells) aus Halbleitern mit großer Bandlücke theoretisch untersucht. Unter Verwendung eines Schwerpunktseparationsansatzes wird das Verhalten von QW Exzitonen und Biexzitonen im Grenzfall schwacher Lokalisation beschrieben. Es zeigt sich, daß die Lokalisationsenergie des Biexzitons mehr als doppelt so groß ist wie die des Exzitons. Dies wird verursacht durch ein universelles Gesetz der Lokalisation in schwachen zwei-dimensionalen Potentialen, welches lediglich durch das "Potentialvolumen" und die Masse des lokalisierten Teilchens bestimmt wird. Ein einfaches Modell des QW Biexzitons wird entwickelt, dessen Ergebnisse gut mit jenen übereinstimmen, die man mit Hilfe eines aufwendigeren numerischen Modells erhält. Der Grenzfall starker Lokalisation von QW Exzitonen und höheren Exzitonenkomplexen wird mittels einer Dichtefunktionalrechnung untersucht. Es wird gezeigt, daß Zustände bis mindestens zum X4 in den nm-großen Potentialminima lokalisieren können, die durch Phasenseparation in (In,Ga)N/GaN QWs enstehen. Es wird das Übergangsspektrum des sukzessiven Zerfalls eines lokalisierten X4 berechnet. Auf Grundlage der selbstkonsistenten Lösung von Poisson- und Schrödinger-Gleichung wird der Einfluß des Probendesigns von (In,Ga)N/GaN QW-Strukturen auf den makroskopischen Verlauf des Polarisationsfeldes in Wachstumsrichtung und somit auf optische Übergangsenergie und Oszillatorstärke systematisch untersucht. Besondere Bedeutung kommt dabei der Abschirmung der Felder durch Raumladungszonen zu. Es wird gezeigt, daß die Position des QW bezüglich einer ausgedehnten Oberflächen-Verarmungszone - die in n-dotierten, Ga-polarisierten Proben auftritt - erheblichen Einfluß auf Übergangsenergie und Oszillatorstärke hat. Durch die räumliche Variation der Polarisationsfeldstärke in dieser Verarmungszone kann das optische Übergangsspektrum eines Mehrfach-QW Schultern oder mehrere Maxima aufweisen. Indium Oberflächen-Segregation ruft eine Blauverschiebung der Übergangsenergie hervor, die bis zu einem Drittel der vom Polarisationsfeld verursachten quantum confined Stark-Verschiebung kompensiert. Diese Blauverschiebung wird von einer Verringerung des Elektron-Loch Überlapps begleitet. Die Polarisationsfelder in (In,Ga)N/GaN Mehrfach-QWs verschmieren das stufenförmige Einteilchen-Absorptionsspektrum. Durch die Aufhebung der näherungsweisen Diagonalität von Inter-Subband Übergängen und durch die Miniband-Dispersion in höheren, gekoppelten Zuständen haben diese Felder, neben dem Beitrag von Potentialfluktuationen, einen entscheidenden Einfluß auf die Form des Absorptionsspektrums. Ein in der Literatur diskutierter Mechanismus, der allein durch Polarisationsfelder eine Verbreiterung optischer Spektren hervorruft, kann nicht bestätigt werden. Unter Annahme einer unkorrelierten Zusammensetzung von (In,Ga)N und einer lateral korrelierten Grenzflächenrauhigkeit von einer Monolage in jeder Grenzfläche zeigt die spektrale Breite des Exzitonen-Schwerpunktpotentials eine Verschmälerung mit zunehmendem Feld. Diese wird verursacht durch das Eindringen der Teilchen in die binären Barrieren und durch ein vergrößertes Exzitonenvolumen. Im Fall einer langreichweitigen Grenzfächenrauhigkeit findet man eine Aufspaltung des Spektrums in einzelne Linien. / In this thesis, various aspects of the influence of localization, disorder, and polarization fields on electron-hole states in wide-gap semiconductor quantum wells (QWs) are investigated theoretically. A theoretical treatment of quantum well exciton and biexciton states in the limit of weak localization is presented, using a center-of-mass separation ansatz. It shows that the localization energy of the biexciton is more than twice as large as that of the exciton due to the universal behaviour of localization in weak two-dimensional potentials which is ruled only by the potential "volume" and the mass of the localized particle. A useful simple model of the QW biexciton wavefunction is developed which provides good agreement with the results obtained with an extensive numerical solution. The limit of strong localization of QW excitons and higher exciton complexes is investigated with a density functional calculation. It is demonstrated that states at least up to X4 may localize in nm-scale potential boxes caused by indium phase separation in (In,Ga)N/GaN QWs. The transition spectrum of the successive recombination of a localized X4 is calculated. A systematic investigation of the influence of the sample design of (In,Ga)N/GaN QW structures on optical transition energy and oscillator strength reveals the importance of space charge layers with regard to screening of polarization fields along the QW-axis. Based on a self-consistent solution of the Schrödinger-Poisson equations, the overall situation of the macroscopic spontaneous and piezoelectric polarization fields is discussed in dependence on various substantial sample parameters. It is found that the position of a QW in the sample with respect to an extended surface depletion layer - which is shown to exist in n-type Ga-face grown material - severely affects transition energy and electron-hole overlap. Due to the spatial variation of the field strength in this surface depletion layer, the optical transition spectrum of a Ga-face grown multiple-QW can display shoulders or even a multiple-peak structure. Indium surface segregation results in a blueshift of the transition energy compensating up to one third of the quantum confined Stark shift produced by the polarization field. This blueshift is accompanied by a decrease of the electron-hole overlap. Polarization fields in (In,Ga)N/GaN multiple-QWs result in a smoothing of the step-like single-particle absorption spectrum. Apart from the contribution of compositional fluctuations, the fields have significant influence on the shape of the spectrum via the abrogation of the nearly diagonality of inter-subband transitions and via the mini-band dispersion of higher coupled states in case of a periodic structure. A line broadening-mechanism due to polarization fields in (In,Ga)N/GaN QWs, as sometimes discussed in literature, could not be confirmed. Assuming uncorrelated (In,Ga)N alloy and in-plane-correlated interface roughness of one monolayer in each interface, the calculation of the spectral width of the QW exciton center-of-mass potential yields a narrowing with increasing average field. This is a result of the penetration of the carriers into the barriers and of an increasing exciton volume. In case of a long-range interface roughness, a splitting of the spectrum into individual lines can be predicted.

Die Polarität ist ein kritisches Thema für das III-Nitrid-Materialsystem, das sich auf die Qualität und Eigenschaften von epitaktischen Schichten, sowie auf die Leistungfähigkeit von auf Nitrid-Materialien basierenden Bauelementen auswirkt. Das Verständnis der elementaren Mechanismen, die für die Ausbildung von Metall- oder Stickstoffpolarität der Schichten bei Abscheidung auf unpolarem Substrat verantwortlich sind, fehlt jedoch. Die bestehenden Konzepte basieren auf empirischen Beobachtungen und sind teilweise widersprüchlich. Einer der Hauptgründe dafür ist der Mangel an präzisen Charakterisierungsmethoden, die eine lokale Bestimmung der Polarität und atomarer Struktur von Schichten erlauben, als die wesentlichen Konzepte der Polaritätskontrolle aufgestellt wurden. In dieser Arbeit entwickeln wir ein Konzept der Polaritätskontrolle in AlN- und GaN-Schichten, welche mittels metallorganische Gasphasenepitaxie (MOVPE) auf Saphirsubstraten gewachsen sind. Die Polarität der Schichten wird mit Hilfe von aberrationskorrigierter Hochauflösungstransmissionselektronenmikroskopie und Z-Kontrastabbildung (Ordnungszahlkontrast) im Rastertransmissionselektronenmikroskop untersucht. Die Auswertung der experimentellen Untersuchungen ergibt Erkenntnisse bezüglich folgender Themen: (i) zum Mechanismus, der die Polaritätsauswahl steuert; (ii) zur Beziehung zwischen Saphir-Oberflächennitridierung und Al-polaren Domänen in ansonsten N-polaren AlN-Schichten; (iii) zur Möglichkeit des kontrollierten Wechsel von N- hin zu Al-polaren Schichten durch ein Sauerstofftempern. Das Verständnis dieser Mechanismen, durch die die Polarität bestimmt wird, eröffnet die Möglichkeit der gezielten Manipulierung der Polarität und Polaritätsabfolge in Nitridschichten und kann einen Hinweis zum Verständnis der Polaritätskontrolle in anderen Materialsystemen (z. B. Oxiden) geben. / Polarity is a critical issue for III-nitrides material system that has an impact on the quality and properties of epitaxial films and the performance of nitride-based devices. But the understanding of the elementary mechanisms that are responsible for establishing metal or nitrogen polarity of the films grown on nonpolar substrate is lacking. The existing concepts are based on empirical observations and contain ambiguous results. One of the main reasons for that is the lack of precise characterization tools, allowing localized determination of polarity and atomic structure of layers, at the time, when main concepts for polarity control were established. In this work we develop a concept of polarity control in AlN and GaN layers grown by metalorganic vapor phase epitaxy (MOVPE) on sapphire substrates. The polarity of the layers is studied by aberration corrected HRTEM and high resolution high-angle annular dark field (HAADF) scanning TEM. The analysis of the experimental investigations yields the following principal results about: (i) the mechanism that governs polarity selection; (ii) the relation between sapphire surface nitridation and Al-polar domains in N-polar AlN films; (iii) the possibility of controlled switching the layers polarity from N to Al by oxygen annealing. The understanding of these mechanisms by which polarity is controlled opens up the possibility for polarity engineering in nitride films and can give a clue to understanding polarity control in other material systems (e.g. oxides). / La polarité est une question critique pour le système de matériaux III-nitrures, qui a un impact sur la qualité des films épitaxies et la performance des dispositifs à base de nitrure. Mais la compréhension des mécanismes élémentaires responsables de l'établissement de la polarité N ou métallique des films sur le substrat non-polaire manque. Les concepts existants sont basés sur des observations empiriques et contiennent des résultats ambigus. Une des raisons principales est le manque d'outils analytiques, permettant la détermination localisée de la polarité et de la structure atomique des couches à l'époque, lorsque les concepts de contrôle de la polarité ont été établis. Dans ce travail, nous développons un concept de contrôle de la polarité dans les couches AlN et GaN épitaxies sur substrat de saphir par EPVOM. La polarité des couches est étudiée par microscopie électronique en transmission (MET) haute résolution corrigée des aberrations et par microscope électronique à balayage en transmission en champ sombre (HAADF-STEM). L'analyse des investigations expérimentales donne les principaux résultats suivants : (i) le mécanisme qui régit la sélection de la polarité; (ii) la relation entre la nitruration de la surface et les domaines de polarité Al dans les films d'AlN N-polaire; (iii) possibilité d’inverser la polarité N de films d’AlN de polarité mixte en introduisant un recuit sous oxygène. La compréhension de mécanisme par lequel la polarité est contrôlée ouvre les possibilités d'une ingénierie de polarité dans les films de nitrure et peut donner une idée de la compréhension du contrôle de la polarité dans d'autres systèmes de matériaux (par exemple, les oxydes).

Diese Arbeit beschreibt die optische Charakterisierung mittels Photolumineszenzspektroskopie (PL) von Halbleiter-Nanodrähten (ND) im allgemeinen und einzelnen GaN-ND und GaN-ND-Ensembles im speziellen. ND werden oftmals als vielversprechende Bausteine zukünftiger, kleinster Bauele- mente bezeichnet. Diese Vision beruht insbesondere auf einigen attraktiven Eigenheiten, die ND im allgemeinen zugeschrieben werden. Im ersten Teil dieser Arbeit werden exemplarisch einige dieser Eigenschaften näher untersucht. So wird anhand von temperaturabhängigen PL-Messungen an Au- und selbstinduzierten GaAs/(Al,Ga)As-ND der Einfluss des Keimmaterials auf die PL der ND untersucht. Weiterhin werden die optischen Eigenschaften von ZnO-ND untersucht, die auf Si-, Saphir- und ZnO-Substraten gewachsen wurden. Die optische Charakterisierung von GaN-ND nimmt den Hauptteil dieser Arbeit ein. Die detaillierte Untersuchung einzelner GaN-ND und von GaN-ND-Ensembles zeigt die Relevanz des großen Oberflächen-zu-Volumen-Verhältnisses und dass jeder ND ganz eigene optische Eigenschaften aufweist. Die unerwartet starke Verbreiterung des strahlenden Übergangs donatorgebundener Exzitonen wird durch das vermehrte Auftreten von Oberflächendonatoren erklärt, deren statistische Relevanz durch PL-Messungen an einzelnen ausgestreuten und freistehenden GaN-ND nachgewiesen werden kann. Weiterhin wird der Einfluss elektrischer Felder auf die optischen Eigenschaften von GaN-ND ermittelt. Die Ein- und Auskopplung von Licht mit GaN ND wird mithilfe von Reflektanz- und Ramanmessungen bestimmt. Die zentralen Ergebnisse dieser Arbeit motivieren die Einführung eines Modells, dass die typischerweise nichtexponentielle Rekombinationsdynamik in ND-Ensemblen erklärt. Es basiert auf einer Verteilung der Rekombinationsraten. Vorläufige Ergebnisse dieses Modells beschreiben das nichtexponentielle Rekombinationdynamik in GaN ND-Ensemblen zufriedenstellend und erlauben eine Abschätzung ihrer internen Quanteneffizienz. / This thesis presents a detailed investigation of the optical properties of semiconductor nanowires (NWs) in general and single GaN NWs and GaN NW ensembles in particular by photoluminescence (PL) spectroscopy. NWs are often considered as potential building blocks for future nanometer-scaled devices. This vision is based on several attractive features that are generally ascribed to NWs. In the first part of the thesis, some of these features are examined using semiconductor NWs of different materials. On the basis of the temperature-dependent PL of Au- and self-assisted GaAs/(Al,Ga)As core-shell NWs, the influence of foreign catalyst particles on the optical properties of NWs is investigated. The effect of the substrate choice is studied by comparing the PL of ZnO NWs grown on Si, Sapphire, and ZnO substrates. The major part of this thesis discusses the optical properties of GaN NWs. The investigation of the PL of single GaN NWs and GaN NW ensembles reveals the significance of their large surface-to-volume ratio and that each NW exhibits its own individual recombination behavior. An unexpected broadening of the donor-bound exciton transition is explained by the abundant presence of surface donors in NWs. The existence and statistical relevance of these surface donors is confirmed by PL experiments of single GaN NWs which are either dispersed or free-standing. Furthermore, the influence of electric fields on the optical properties of GaN NWs is investigated and the coupling of light with GaN NWs is studied by reflectance and Raman measurements. The central results of this thesis motivate the introduction of a model that explains the typically observed nonexponential recombination dynamics in NW ensembles. It is based on a distribution of recombination rates. Preliminary simulations using this model describe the nonexponential decay of GaN NW ensembles satisfactorily and allow for an estimation of their internal quantum efficiency.