<p>During the last decade, AlGaN High Electron Mobility Transistors (HEMTs) have been intensively studied because their fundamental electrical properties make them attractive for highpower microwave device applications. Despite much progress, AlGaN HEMTs are far from fully understood and judged by the number of published papers the understanding of advanced structures is even poorer. This work is an exploration of the electrical and structural properties of advanced HEMT structure containing AlN exclusionlayer and double heterojunctions. These small modifications had great impact on the electrical properties.</p><p>In this work, AlGaN HEMT structures grown on SiC substrates by a hot-wall MOCVD have been characterized for their properties using optical microscopy, scanning electron microscopy, transmission electron microscopy, capacitance/voltage, eddy-current resistivity, and by homebuilt epi-thickness mapping equipment.</p><p>A high electron mobility of 1700 [cm2/Vs] was achieved in an AlN exclusion-layer HEMT. A similar electron mobility of 1650 [cm2/Vs] was achieved in a combination of a double heterojunction and exclusion-layer structure. The samples had approximately the same electron mobility but with a great difference: the exclusion-layer version gave a sheet carrier density of 1.58*1013 [electrons/cm2] while the combination of double heterojunction and exclusion-layer gave 1.07*1013 [electrons/cm2]. A second 2DEG was observed in most structures, but not all, but was not stable with time.</p><p>The structures we grew during this work were also simulated using a one-dimensional Poisson-Schrödinger solver and the simulated electron densities were in fairly good agreement with the experimentally obtained. III-nitride materials, the CVD concept, and the onedimensional solver are shortly explained.</p>

Efficiency droop is a critical issue for the Group III-nitride based light-emitting diodes (LEDs) to be competitive in the general lighting application. Carrier spill-over have been suggested as an origin of the efficiency droop, and an InAlN electron-blocking layer (EBL) is suggested as a replacement of the conventional AlGaN EBL for improved performance of LED. Optimum growth condition of InAlN layer was developed, and high quality InAlN layer was grown by using metalorganic chemical vapor deposition (MOCVD). A LED structure employing an InAlN EBL was grown and its efficiency droop performance was compared with a LED with an AlGaN EBL. Characterization results suggested that the InAlN EBL delivers more effective electron blocking over AlGaN EBL. Hole-injection performance of the InAlN EBL was examined by growing and testing a series of LEDs with different InAlN EBL thickness. Analysis results by using extended quantum efficiency model shows that further improvement in the performance of LED requires better hole-injection performance of the InAlN EBL. Advanced EBL structures such as strain-engineered InAlN EBL and compositionally-graded InAlN EBLs for the delivery of higher hole-injection efficiency were also grown and tested.

The objective of the research was to develop high quality GaN epitaxial growth on alternative substrates that could result in higher external quantum efficiency devices. Typical GaN growth on sapphire results in high defect materials, typically 10⁸⁻¹⁰cm⁻², due to a large difference in lattice mismatch and thermal expansion coefficient. Therefore, it is useful to study epitaxial growth on alternative substrates to sapphire such as ZnO which offers the possibility of lattice matched growth. High-quality metalorganic chemical vapor deposition (MOCVD) of GaN on ZnO substrate is hard to grow due to the thermal stability of ZnO, out-diffusion of Zn, and H₂back etching into the sample. Preliminary growths of GaN on bare ZnO substrates showed multiple cracks and peeling of the surface. A multi-buffer layer of LT-AlN/GaN was found to solve the cracking and peeling-off issues and demonstrated the first successful GaN growth on ZnO substrates. Good quality InGaN films were also grown showing indium compositions of 17-27% with no indium droplets or phase separation. ZnO was found to to sustain a higher strain state than sapphire, and thereby incorporating higher indium concentrations, as high as 43%, without phase separation, compared to the same growth on sapphire with only 32%. Si doping of InGaN layers, a known inducer for phase separation, did induce phase separation on sapphire growths, but not for growths on ZnO. This higher strain state for ZnO substrates was correlated to its perfect lattice match with InGaN at 18% indium concentration. Transmission electron microscopy results revealed reduction of threading dislocation and perfectly matched crystals at the GaN buffer/ZnO interface showing coherent growth of GaN on ZnO. However, Zn diffusion into the epilayer was an issue. Therefore, an atomic layer deposition of Al₂O₃was grown as a transition layer prior to GaN and InGaN growth by MOCVD. X-ray and PL showed distinct GaN peaks on Al₂O₃/ZnO layers demonstrating the first GaN films grown on Al₂O₃/ZnO. X-ray photoelectron spectroscopy showed a decrese in Zn diffusion into the epilayer, demonstrating that an ALD Al₂O₃layer was a promising transition layer for GaN growth on ZnO substrates by MOCVD.

In der vorliegenden Arbeit werden bi- und oligometallische Komplexe, die auf Bis(alkinyl)titanocen-Bausteinen (Metallorganische pi-Pinzetten) basieren, beschrieben. Dabei stehen Synthesestrategien und Untersuchungen zum Reaktionsverhalten sowie elektrochemische Eigenschaften der mehrkernigen Komplexe im Vordergrund. Bimetallische Ti-M-Systeme (M = Cu, Ag) können als Vorstufen zu höhernuklearen Spezies dienen. Die oligometallischen pi-Pinzetten-Komplexe sind entweder durch organische Ligandsysteme oder über anorganische Bausteine wie Halogenide oder Pseudohalogenide miteinander verknüpft. Über entsprechende Kupfer(I)- und Silber(I)-Pseudohalogenid-Komplexfragmente können Bis(akinyl)titanocen-M-Komplexe (M = Cu, Ag) mit bis zu neun Metallzentren in einer Verbindung realisiert werden. Je nach verbrückender Einheit werden dabei gewinkelte, lineare oder sternförmige Strukturen gebildet. Die gegenseitige elektrochemische Beeinflussung verschiedener Metallzentren in ausgewählten Komplexen wird cyclovoltammetrisch orientierend untersucht. Ein weiterer Schwerpunkt der vorliegenden Arbeit liegt in der Synthese und der Untersuchung thermischer Eigenschaften von Kupfer(I)-Alkin-Komplexen, die präparativ und finanziell mit moderatem Aufwand zugänglich sind. Über thermogravimetrische Untersuchungen können Rückschlüsse auf die Eignung solcher Verbindungen für den MOCVD-Prozeß getroffen werden.

Die vorliegende Arbeit befaßt sich mit neuartigen ein- und zweikernigen Komplexen basierend auf dem Phosphanbaustein P(C6H4CH2NMe2-2)3. Im Vordergrund steht dabei die Synthese sowie die Untersuchung des elektrochemischen Verhaltens dieser Verbindungen. Einkernige Verbindungen des Typs [P(C6H4CH2NMe2-2)3]MX (M = Cu, Ag; X = nicht-koordinierter, anorganischer Rest) dienen dabei als Ausgangsverbindungen zur Darstellung ein- und zweikerniger Komplexe mit s-Donorliganden. Die Verknüpfung zweier [P(C6H4CH2NMe2-2)3]M-Fragmente (M = Cu, Ag) erfolgt über bis(s-Donor)liganden. Mittels cyclovoltammetrischer Experimente wird die elektrochemische Beeinflussung der Metallzentren untereinander untersucht. Weiterhin befaßt sich diese Arbeit mit der Synthese sowie der Untersuchung der thermischen Eigenschaften Lewis-Basen-stabilisierter Kupfer(I)-b-Diketonate bzw. -Carboxylate. Durch die Wahl der Lewis-Base sowie des b-Diketonato- bzw. Carboxylato-Fragmentes ist es möglich, Einfluß auf die Eigenschaften der erhaltenen Komplexe zu nehmen. Thermogravimetrische Untersuchungen bzw. OMCVD-Versuche lassen Rückschlüsse auf die Eignung solcher Systeme zur Abscheidung elementaren Kupfers zu.

During the last decade, AlGaN High Electron Mobility Transistors (HEMTs) have been intensively studied because their fundamental electrical properties make them attractive for highpower microwave device applications. Despite much progress, AlGaN HEMTs are far from fully understood and judged by the number of published papers the understanding of advanced structures is even poorer. This work is an exploration of the electrical and structural properties of advanced HEMT structure containing AlN exclusionlayer and double heterojunctions. These small modifications had great impact on the electrical properties. In this work, AlGaN HEMT structures grown on SiC substrates by a hot-wall MOCVD have been characterized for their properties using optical microscopy, scanning electron microscopy, transmission electron microscopy, capacitance/voltage, eddy-current resistivity, and by homebuilt epi-thickness mapping equipment. A high electron mobility of 1700 [cm2/Vs] was achieved in an AlN exclusion-layer HEMT. A similar electron mobility of 1650 [cm2/Vs] was achieved in a combination of a double heterojunction and exclusion-layer structure. The samples had approximately the same electron mobility but with a great difference: the exclusion-layer version gave a sheet carrier density of 1.58*1013 [electrons/cm2] while the combination of double heterojunction and exclusion-layer gave 1.07*1013 [electrons/cm2]. A second 2DEG was observed in most structures, but not all, but was not stable with time. The structures we grew during this work were also simulated using a one-dimensional Poisson-Schrödinger solver and the simulated electron densities were in fairly good agreement with the experimentally obtained. III-nitride materials, the CVD concept, and the onedimensional solver are shortly explained.

L'objectif fondamental de cette étude est de montrer la faisabilité de l'élaboration des couches épaisses de zircone non dopée, en contrôlant la microstructure et l'état mécanique, par MOCVD et par Sol-Gel. Dans un premier temps, nous avons essayé d'optimiser les conditions de dépôt de MOCVD, en faisant varier ou en jouant sur les différents paramètres du procédé, conduisant à l'obtention des couches de ZrO2 micrométriques et denses. La stabilité de la phase quadratique de la zircone est conditionnée par la pression partielle en oxygène, la température du substrat ainsi que l'épaisseur du dépôt. La texture cristallographique de type {100} est obtenue pour les dépôts réalisés à une température de substrat T ≤ 850°C et pour de faibles pressions totales. Concernant l'état mécanique des couches de zircone, l'augmentation de l'épaisseur de la couche peut relaxer les contraintes résiduelles de tension au sein du dépôt. Ce phénomène s'accentue au-delà d'une épaisseur critique suite à la création des espacements entre les colonnes de croissance de la couche. Parallèllement, nous avons montré que la qualité des dépôts Sol-Gel est maitrisée par le choix du substrat, l'utilisation de " sols " vieillis, la multiplication du nombre de couches " spin-coating ", le mode de dépôt ainsi que la température de recuit. Certaines propriétés caractéristiques du dépôt telles que la cristallisation, la composition de phase et l'adhérence sont aisément contrôlées respectivement par l'âge du sol, la température de recuit et le coefficient de dilatation thermique associé au substrat utilisé. La microstructure (changement de phases, taille des cristallites, texture cristallographique) et les contraintes internes (thermiques et intrinsèques) ont été caractérisées. Le Sol-Gel présente l'avantage de proposer des couches de zircone très peu contraintes par rapport aux films obtenus par le procédé MOCVD. Quel que soit le procédé de dépôt, MOCVD et/ou Sol-Gel, l'élaboration des films de ZrO2 orientés demeure fonction de la température du traitement. La tentative d'élaborer des multicouches de zircone par un couplage MOCVD/Sol-Gel montre la possibilité de sélectionner des paramètres de dépôt propices à la fabrication d'un film présentant un état microstructural et mécanique contrôlé et voulu.

Les aciers ferritiques à faible teneur en chrome tel que le T/P91 sont largement utilisés dans les centrales de productions d’électricité pour leurs bonnes propriétés mécaniques et leur faible coefficient d’expansion thermique. Cependant, la demande croissante en énergie alliée à la nécessité de réduire les émissions de gaz à effet de serre, conduisent à envisager l’augmentation des conditions d’utilisation (température et pression) de ces matériaux. Des études ont montré qu’en modifiant la température de fonctionnement et la pression de vapeur d’eau de 538°C/18.5 MPa à 650°C/30 MPa, le rendement des centrales thermiques progressait d’environ 8%. Se pose alors la question de la tenue à la corrosion à haute température des aciers à 9% de chrome. Au cours de ces travaux, le comportement d’un acier ferritique/ martensitique à 9% de chrome a été étudié à 650°C sous air sec et sous vapeur d’eau de matière isotherme et en conditions de cyclage thermique. La prise de masse des échantillons renseigne sur la cinétique de la réaction d’oxydation et l’adhérence des couches d’oxydes formées. Les produits de corrosion ont été caractérisés par plusieurs techniques d’analyses dans l’optique de clairement identifiés les oxydes en présences et leurs mécanismes de formation. Des oxydes mixtes de fer et de chrome (Cr,Fe)2O3 sont dans un premier temps formés et assurent s’avèrent être temporairement protecteur. Pour des longs temps d’oxydation ou des températures supérieures à 650°C, la magnétite Fe3O4 et l’hématite Fe2O3 sont les principaux oxydes formés, montrant ainsi l’inadéquation des nuances à faible teneur en chrome pour une utilisation dans des conditions aussi drastiques. Dans l’optique d’augmenter la résistance à la corrosion à haute température de cet alliage, diverses solutions ont été envisagées tel que l’aluminisation par cémentation en caisse, les revêtements d’oxydes de terre rare par MOCVD, ou encore l’ajout d’éléments d’addition. Ces solutions ont été également testées à 650°C sous air sec et sous vapeur d’eau. / The improvement of high temperature oxidation resistance of low chromium content steels, such as T/P91, is of great interest in regards with their application in thermal power generating plants. Indeed, they possess good creep properties, and low thermal expansion coefficient. Important needs in energy together with environmental issues place power generation plants under constraints which lead to develop high efficiency systems. A usual way to increase the efficiency consists in increasing temperature and pressure parameters of the power generating plant. Studies has shown that the total efficiency of a plant increases by nearly 8 % when changing the steam parameters from 538°C/18.5 MPa to 650°C/30 MPa. Then, the problem of corrosion resistance of 9% chromium steel in those conditions is asked. In this work, the behavior of a ferritic / martensitic 9% chromium steel has been studied at 650°C in dry air and in water vapor containing environment in both isothermal and thermal cyclic conditions. The weight gain of samples provides information on the kinetics of the oxidation reaction and the adhesion of formed oxide scale. Corrosion products were characterized by several analytical techniques in order to identify oxides with accuracy and to understand their formation mechanisms. Mixed iron and chromium oxides (Cr, Fe) 2O3 are initially formed and provide temporary protection to the substrate. For long time exposure or temperatures above 650°C, magnetite, Fe3O4 and hematite Fe2O3 are the main oxides formed, highlighting the fact that low chromium steel are inappropriate for applications in such drastic conditions. In order to increase the high temperature corrosion resistance of this alloy, various solutions have been proposed as aluminizing by pack cementation, reactive element oxides coatings of by MOCVD, or addition of alloying elements in the steel composition. These solutions were then tested at 650 ° C in dry air and in water vapor environments.

No description available.

Group III-Nitrides (GaN, InN & AlN) are considered one of the most important class of semiconducting materials after Si and GaAs. The excellent optical and electrical properties of these nitrides result in numerous applications in lighting, lasers, and high-power/high-frequency devices. Due to the lack of cheap bulk III- Nitride substrates, GaN based devices have been developed on foreign substrates like Si, sapphire and SiC. These technologies have been predominantly developed on the so called Ga-polarity epitaxial stacks with growth in the [0001] direction of GaN. It is this orientation that grows most easily on sapphire by metal organic chemical vapor deposition (MOCVD), the most common combination of substrate and deposition method used thus far. The opposite [000¯1] or N-polar orientation, very different in properties due to the lack of an inversion centre, offers several ad- vantages that could be exploited for better electronic and optoelectronic devices. However, its growth is more challenging and needs better understanding. The aim of the work reported in this dissertation was a systematic investigation of the relation between the various growth parameters which control polarity, surface roughness and mosaicity of GaN on non-miscut sapphire (0001) wafers for power electronics and lighting applications, with emphasis on the realization of N-polar epitaxial layers. GaN is grown on sapphire (0001) in a two-step process, which involves the deposition of a thin low temperature GaN nucleation layer (NL) on surface modified sapphire followed by the growth of high temperature device quality GaN epitaxial layer. The processing technique used is MOCVD. Various processing methods for synthesis of GaN layers are described with particular em- phasis on MOCVD method. The effect of ex situ cleaning followed by an in situ cleaning on the surface morphology of sapphire (0001) wafers is discussed. The characterization tools used in this dissertation for studying the chemical bond nature of nitrided sapphire surface and microstructural evolution (morphological and structural) of GaN layers are described in detail. The effect of nitridation temperature (TN) on structural transformation of non- miscut sapphire (0001) surface has been explored. The structural evolution of nitrided layers at different stages of their process like as grown stage and thermal annealing stage is investigated systematically. The chemical bond environment information of the nitrided layers have been examined by x-ray photoelectron spectroscopy (XPS). It is found that high temperature nitridation (TN ≥ 800oC) results in an Al-N tetrahedral bond environment on sapphire surface. In contrast, low temperature nitridation (TN = 530oC) results in a complex Al-O-N environment on sapphire surfaces. Microstructural evolution of low temperature GaN NLs has been studied at every stage of processing by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Surface roughness evolution and island size distribution of NLs measured from AFM are discussed. It is found that NLs processed on sapphire wafers nitrided at (TN ≥ 800oC) showed strong wurtzite [0002] orientation with sub-nanometre surface roughness. In contrast, NLs processed at (TN = 530oC) showed zinc blende phase in the as grown stage with higher surface roughness, but acquired a greater degree of wurtzite [0002] orientation after thermal annealing prior to high temperature GaN growth. Polarity, surface quality and crystal quality of subsequently grown high temperature GaN epitaxial layers is described in relation to the structure of the trans- formed nitrided layers. Higher nitridation temperatures (TN ≥ 800oC) consistently yield N-polar GaN whereas lower nitridation temperatures (TN = 530oC) yield Ga-polar GaN. It is found that the relative O atom concentration levels in nitrided layers control the density of inversion domains in N-polar GaN. The effect of various growth parameters (NH3 flow rate, growth temperature, NL thickness) on surface morphology and mosaicity of both Ga & N-polar GaN layers is discussed in detail. We report device quality N-polar GaN epitaxial layers on non-miscut sapphire (0001) wafers by careful optimization of growth temperature. It is found that lower growth temperatures (800oC) are favorable for obtaining smooth N- polar GaN layers. In contrast, N-polar GaN layers grown at higher temperatures (1000 to 1080oC) are rough with hexagonal hillocks.