In der vorliegenden Arbeit werden zwei Enzymsysteme – Ni-haltige Kohlenmonoxid-Dehydrogenase (CODH) und [NiFe]-haltige Hydrogenase – strukturell untersucht. Im 1. Teil werden die Untersuchungen des ACDS-Komplexes aus A. fulgidus mittels Transmissionselektronenmikroskopie (Negativkontrastierung und der Kryo-Einbettung) geschildert. Die 3D-Rekonstruktion mit einer Auflösung von 29 Å wird de novo ermittelt und drei mögliche Positionen für die CODH-Untereinheit vorgeschlagen. Im 2. Teil wird die Röntgenkristallstrukturanalyse der CODH-Untereinheit des ACDS Komplexes aus A. fulgidus geschildert. Das Protein besteht aus α- und ε-Untereinheiten, die zusammen eine α2ε2-Stöchiometrie bilden (Afα2ε). Während die Gesamtstruktur von Afα2ε2 jener von M. barkeri (Mbα2ε2) ähnelt, führt der Austausch der koordinierenden Cys zu Asp und Glu zu einer Deletion des verbrückenden FeS-Zentrums. Die Rolle der ε-Untereinheit wird durch kinetische Studien untersucht. Die CO-abhängige FAD-Reduktionsaktivität von Afα2ε2 folgt einer Michaelis-Menten Kinetik. Die Mbα2ε2 hat ein ähnliches Kinetikverhalten. Im Gegensatz dazu weist die CODH-II von C. hydrogenoformans, die keine ε-Untereinheit hat, eine lineare Abhängigkeit der CO-abhängigen FAD-Reduktionsaktivität von Flavin auf. Diese Beobachtungen sind im Einklang mit der Annahme, dass die ε-Untereinheit ein Gerüst für die Flavinbindung bereitstellt. Der 3. Teil ist der F420-reduzierenden Hydrogenase aus M. barkeri (MbFRH) gewidmet. Die Struktur von MbFRH wird mittels Röntgenkristallographie bestimmt und ergibt eine dodekamerische Anordnung von ca. 1.2 MDa. Zusammen mit der etablierten Elektronenübertragungskette, beobachtet in FRH aus M. marburgensis, wird in MbFRH auch ein [2Fe2S]-Cluster und eine Fe-Stelle detektiert. Schließlich führen die schwingungsspektroskopischen Analysen zusammen mit der Röntgenkristallographie zu dem Schluss, dass MbFRH in einem bisher strukturell nicht charakterisierten, katalytisch aktiven Nia-S Zustand isoliert wird. / In this work, we structurally characterize two metal-based enzyme systems from archaea: Ni-containing CO dehydrogenase (CODH) and [NiFe] containing hydrogenase. In the first chapter we investigate, using transmission electron microscopy, the ACDS complex from A. fulgidus (AfACDS). The purified ACDS complex can be visualized as an intact globular protein particle by negative stain and vitrification techniques. The 3D reconstruction is determined de novo to 29 Å-resolution by single-particle analysis. We suggest three possible positions for the CODH subunit within ACDS by rigid-body fitting. In the second chapter we determine the X-ray crystal structure of the CODH subunit. The 220 kDa protein is composed of α- and ε-subunits that form a heterodimer with (α2ε2) stoichiometry (Afα2ε2). While the overall structure of Afα2ε2 resembles the previously reported structure of the α2ε2-subunit from M. barkeri (Mbα2ε2), the naturally-occurring exchange of the Cys to Asp and Glu results in a depletion of the bridging iron-sulfur cluster. The role of the ε-subunit is investigated by kinetics studies. CO-dependent FAD reduction activity of Afα2ε2 exhibits Michaelis-Menten type kinetics. The same kinetic type is demonstrated for the Mbα2ε2-subunit. In contrast, the ε-subunit lacking CODH-II from C. hydrogenoformans shows linear dependency between CO-dependent FAD reduction activity and flavin concentration. The data suggests that the ε-subunit provides a scaffold for the flavin binding. In the third chapter we study the F420-reducing hydrogenase from M. barkeri (MbFRH). Its structure is solved by X-ray crystallography, revealing a dodecameric arrangement of 1.2 MDa. Along with the established ET chain observed in FRH from M. marburgensis, one solvent-exposed [2Fe2S] cluster and an additional Fe metal site are detected. The combined approach of X-ray crystallography and vibrational spectroscopy reveals that MbFRH is isolated in the previously structurally uncharacterized Nia-S state.

Les aciers appelés ODS (pour Oxide Dispersion Strengthened), renforcés par une dispersion homogène de nano-oxydes, sont des matériaux de structure avancés pour les futurs réacteurs nucléaires de fusion et de fission. En effet ces nano-oxydes, à base d’Y et Ti, servent comme centres de recombinaison de défauts ponctuels et d'obstacles aux mouvements des dislocations, améliorant de ce fait leur résistance aux radiations et aux températures élevées. La fabrication conventionnelle des aciers ODS est réalisée par broyage mécanique suivi de traitements thermo-mécaniques, et ne permet pas facilement de comprendre les mécanismes physiques conduisant à la précipitation des nano-oxydes, ce qui serait potentiellement utile pour optimiser leur production. La cinétique de formation de ces nano-oxydes peut être étudiée en utilisant une technique alternative, à savoir la synthèse par faisceaux d’ions, qui présente de nombreux avantages, notamment le contrôle précis des paramètres expérimentaux et la possibilité de décorréler divers facteurs contribuant à la cinétique de précipitation. Au cours de cette thèse, cette technique a été utilisée pour étudier la coprécipitation d'ions métalliques (Y et/ou Ti) et d'oxygène implantés dans un alliage modèle Fe-Cr de composition proche de celle typique des aciers ODS commerciaux. Des ions de Y, Ti et O à basse énergie ont été implantés dans des échantillons d'alliage Fe10wt%Cr de haute pureté à température ambiante. Les échantillons implantés ont ensuite été recuits à diverses températures entre 600 à 1100°C pour favoriser la précipitation de nano-oxydes, conformément au principe de cette technique. La microscopie électronique à transmission a été utilisée pour caractériser la structure cristallographique et la composition chimique des nano-oxydes formés lors de trois séries d'expériences. Tout d'abord, l'implantation séquentielle d'ions Ti et O a été mise en œuvre. Un recuit ultérieur a révélé qu’il n’y avait pas de précipitation d'oxyde de titane jusqu’à des températures inférieures à 1000°C, mais la présence de nano-oxydes riches en chrome avec une structure hexagonale de type corundum, qui contiennent une certaine quantité de Ti à des températures suffisamment élevées. Ce n’est qu’après le recuit à 1100°C que des nano-oxydes d’un autre type à cœur enrichi en Ti et coquille enrichie en Cr ont également été observés. Deuxièmement, l'implantation séquentielle d’ions Y et O a entraîné la formation à 800°C de nano-oxydes probablement riches en yttrium. Le recuit à 1100°C a favorisé la croissance des particules identifiées comme étant des nano-oxydes d’yttrium avec une coquille enrichie en Cr. Enfin, une implantation ionique séquentielle de deux ions métalliques (Y et Ti) a été réalisée, suivie d'une implantation d’O. L'ordre d'implantation des ions métalliques s'est révélé crucial pour la précipitation de nano-oxydes lors du recuit ultérieur. Lors de la séquence avec une implantation de Ti en premier, une précipitation d'oxyde riche en chrome de structure corundum hexagonale a été observée, très similaire au cas de l'implantation d’ions Ti et O. En revanche, la séquence avec une implantation d’ions Y en premier a produit des nano-oxydes d'yttrium-titane qui possèdent une structure non identifiable. En résumé, l’étude a démontré la faisabilité de la formation de nano-oxydes de Y, Ti et (Y, Ti) par implantation ionique. La thèse présente la caractérisation détaillée de ces nano-oxydes, ainsi que certaines de leurs caractéristiques spécifiques, telles que la présence de relations d'orientation entre les nano-oxydes et la matrice FeCr, qui ont été observées même dans le cas de nano-oxydes de type corundum riches en Cr. Enfin, les résultats obtenus, combinées avec les données de la littérature, sont discutées pour une meilleure compréhension des mécanismes impliqués dans la formation des nano-oxydes dans les aciers ODS. / Oxide Dispersion Strengthened (ODS) steels, that is steels reinforced with a homogeneous distribution of (Y,Ti) oxide nano-particles, are advanced structural materials for nuclear applications. The oxide particles serve as point defect recombination centres and obstacles to dislocation motion thereby improving radiation resistance and high-temperature strength of these steels making them perfect candidate materials for future fusion and fission nuclear reactors. The conventional fabrication of ODS steels is achieved by mechanical alloying followed by thermomechanical heat treatments. This way of ODS steel production seems complicated to understand the physical mechanisms leading to the precipitation of nano-oxide particles. The kinetics of nanoparticle formation can be much better studied using an alternative technique of nanoparticle growth, namely Ion Beam Synthesis (IBS). This approach has many advantages including the precise control of experimental parameters and the ability to de-correlate various factors contributing to precipitation kinetics. A better knowledge gained in this way would be potentially helpful for optimization of ODS steel production routines. In the course of this PhD study, the IBS approach was applied to investigate the co-precipitation of metal (Y and/or Ti) and oxygen ions implanted into a model Fe-Cr alloy with the composition close to those typical for commercial ODS steels. Following the standard IBS schedule, consisting of ion implantation followed by high-temperature heat treatment, ions of Y, Ti and O at low energies were implanted into high-purity Fe10wt%Cr alloy samples at room temperature. The implanted samples were then annealed at various temperatures ranging from 600 to 1100°C to promote the precipitation of nano-oxide particles. A range of Transmission Electron Microscopy techniques were used to characterize the crystallographic structure and chemical composition of the nanoparticles. The study has been performed following three sets of experiments. First of all, the sequential implantation of Ti and O ions was implemented. Subsequent annealing at temperatures below 1000°C revealed that precipitation of titanium oxide was suppressed. Instead, chromium-rich nano-oxide particles with corundum hexagonal structure were found to precipitate. At sufficiently high temperatures these corundum particles were found to contain certain amount of Ti. Only after annealing at the highest temperature of 1100°C, particles of another type with Ti enriched core and Cr enriched shell were additionally fixed. Secondly, sequential Y and O ion implantation resulted in the formation of probable yttrium-rich oxides at 800°C. Annealing at 1100°C promoted their growth to larger sized yttria (Y₂O₃) particles with a Cr enriched shell. Finally, sequential ion implantation of both metal ions (Y and Ti) was performed, followed by O implantation. The order of metal ion implantation has been found to be crucial for subsequent oxide precipitation at the annealing stage. With the Ti implantation first in the sequence, the precipitation of corundum hexagonal chromium-rich oxide was observed, very similar to the case of Ti and O implantation. In contrast, implantation starting with Y produced yttrium-titanium oxide particles with unidentifiable structure. Summing up, the study has demonstrated the feasibility of the formation of Y, Ti and (Y,Ti) oxides by ion implantation. The thesis presents the detailed characterization of the nanoparticles, as well as the discovered specific features of precipitated particles, such as the presence of orientation relationships between the particles and the FeCr matrix, which was observed even for the case of Cr-rich corundum particles. Finally, the implications of the obtained results, in conjunction with the already known data from the existing literature, for the better understanding of the mechanisms involved in the formation of nano-oxide particles in ODS steels are discussed.

Der Einsatz nanostrukturierter Magnetmaterialien als Speicherschichten in Festplatten stellt ein vielversprechendes Konzept zur weiteren Erhöhung der erreichbaren Speicherdichten im Vergleich zu den heute eingesetzten granularen Medien dar. Für die Realisierung dieses Konzeptes ist eine detaillierte Kenntnis der Struktureigenschaften und deren Einfluss auf das magnetische Verhalten der einzusetzenden Schichten erforderlich. Für die vorliegende Arbeit wurden drei verschiedene magnetische Materialien ausgewählt und insbesondere mit elektronenmikroskopischen Methoden in struktureller Hinsicht untersucht. Dazu zählen ferromagnetische (FePt)(100-x)Cu(x) -Schichten, ferromagnetische [Co/Pt]n -Multilagen sowie ferrimagnetische Fe(100-x)Tb(x) -Schichten. Der Schwerpunkt der Untersuchungen lag dabei auf der Korrelation zwischen strukturellen und magnetischen Eigenschaften sowie im Einfluss der Nanostrukturierung auf das magnetische Verhalten der Schichten. In dieser Hinsicht wurden Aspekte der durch die Struktur bedingten magnetischen Anisotropie in Form von magnetokristalliner und Grenzflächenanisotropie betrachtet. Zudem wurde das Kopplungsverhalten zwischen einzelnen Strukturelementen in nanostrukturierten Schichten untersucht. Aufbauend auf die Untersuchung der drei genannten Materialien wurden [Co/Pt]n und Fe(100-x)Tb(x) ausgewählt zum Aufbau eines Systems mit zwei magnetischen Komponenten: Fe(80)Tb(20) / [Co/Pt]10. Die Untersuchungen konzentrierten sich dabei auf die Morphologie der Grenzfläche zwischen den beiden Bestandteilen und deren Einfluss auf den Exchange Bias, der in diesem System vorliegt.

[pt] A presente tese tem como objetivo estudar a estabilidade microestrutural da superliga 625 a base de Ni pelas suas propriedades mecânicas e suas várias aplicações na indústria, em três condições distintas: maciça (placa forjada industrialmente), partículas de pó precursora da peça 3D e uma peça produzida por impressão a laser (Deposição Direta de Metais - DMD). Amostras destas condições foram submetidas a tratamentos de solubilização e envelhecimento isotérmico a 650 graus Celsius e 750 graus Celsius durante 10 horas e 100 horas, de modo a promover fenômeno de precipitação e, assim, correlacionar com as propriedades mecânicas do material. A caracterização microestrutural foi realizada por microscopia ótica (MO), microscopia eletrônica de varredura (MEV), microscopia eletrônica de transmissão (MET) no modo convencional utilizando contraste de difração, na modalidade analítica de transmissão/varredura (STEM), e em alta resolução (HRTEM). Espectroscopias de raios X por dispersão em energia (EDS) e de perdas de energia de elétrons (EELS) foram utilizadas para analisar a composição local da matriz e das fases presentes. Foram realizados ensaios de microdureza para avaliar o efeito dos tratamentos térmicos. A análise microestrutural da amostra maciça na condição como recebida apresentou grãos equiaxiais com fases NbTiC e M6C. Com o tratamento térmico de solubilização a 1100 graus Celsius por 40 minutos houve uma dissolução parcial dos carbetos. O envelhecimento a 650 graus Celsius por 10 horas resultou em carbetos de NbTiC e um aumento da dureza em 5 porcento em relação a amostra como solubilizada. Entretanto no tratamento de envelhecimento a 100 horas ocorreu precipitação homogênea da fase gama aumentando a dureza do material em 45 porcento, se comparada à mesma como solubilizada. A liga maciça envelhecida a 750 graus Celsius por 10 horas apresentou os carbetos NbTiC e M23C6 nos contornos de grãos e dispersos na matriz. Já a liga maciça envelhecida por 100 horas a esta mesma temperatura, apresentou a fase δ dispersa na matriz. A análise microestrutural do pó precursor mostrou ser policristalino constituído predominantemente de grãos colunares da matriz austenítica. Análises das amostras produzidas por DMD como recebida revelou estrutura dendrítica com carbetos de Nb e fase Laves nas regiões interdendríticas. A solubilização das amostras DMD durante 40 minutos por 1100 graus Celsius e 1200 graus Celsius mostrou ser insuficientes para a dissolução dos precipitados. A fim de melhorar a difusão do Nb e a dissolução dos carbetos e da fase Laves, foi realizado o tratamento de solubilização a 1200 graus Celsius por 100 horas. Esta amostra tratada a 650 graus Celsius por 100 horas apresentou carbetos M23C6 precipitados nos contornos de grão e nas interfaces entre matriz CFC e a fase Laves. Entretanto, no envelhecimento a 750 graus Celsius durante 100 horas ocorreu à precipitação dos carbetos M23C6 e M6C nos contornos de grão e dispersos na matriz, aumentando assim a dureza do material em 18 porcento, se comparada à mesma como solubilizada. O aumento da microdureza em 12 porcento após o tratamento térmico está relacionado à precipitação dos carbetos nos contornos de grão e dispersos na matriz resultado dos tratamentos térmicos de envelhecimento. / [en] This thesis studies the microstructural stability of Ni-base Super alloy 625 for its mechanical properties and its varieties of applications in the industry, in three different conditions: bulk (industrially forged plate), precursor powder particles for 3D printing process and a sample produced by laser Direct Metal Deposition (DMD). Aiming at promoting precipitation processes and, therefore, correlate with the mechanical properties of the material, samples of these conditions were submitted to solution annealing and isothermal aging treatments at 650 Celsius degrees and 750 Celsius degrees for 10 hours and 100 hours. Characterization of the microstructure was performed by optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), in the conventional diffraction contrast mode, scanning/transmission (STEM) analytical mode, and high resolution microscopy (HRTEM). Energy dispersive X-ray spectrometry (EDXS) and electron energy loss spectroscopy (EELS) were used to analyze the local composition of the matrix and precipitated phases. Micro hardness measurements were performed to evaluate the effect of thermal treatments. The microstructural analysis of the bulk sample in the as-received condition showed an equiaxial grain structure with NbTiC and M6C precipitated phases. Solid solution treatment at 1100 Celsius degrees for 40 minutes allowed partial dissolution of the carbides. Aging at 650 Celsius degrees for 10 hours showed NbTiC carbides and a hardness increase of 5 percent compared to the as-solubilized sample. However, aging at this temperature for 100 hours promoted the homogeneous precipitation of the gama phase, thus increasing the material s hardness by 45 percent, when compared to it as solubilized. The bulk sample aged at 750 Celsius degrees for 10 hours showed grain boundary and homogeneous precipitation of NbTiC and M23C6 carbides. This sample condition upon aging at this temperature for 100 hours shows δ phase homogeneously precipitated in the matrix. The microstructural analysis of the precursor powder showed micrometer size individual particles as polycrystalline, consisting predominantly of columnar grains of the austenitic matrix. Analysis of samples produced by DMD in the as-received condition revealed dendritic microstructure with carbides of Nb and Laves phase in the interdendritic regions. The solution treatment of the DMD samples for 40 minutes at 1100 Celsius degrees and 1200 Celsius degrees proved to be insufficient for the dissolution of the precipitate. In order to enhance diffusion of Nb and so carbide and Laves phase dissolution, a solution anneal was carried out at 1200 Celsius degrees for 100 hours. This sample treated at 650 Celsius degrees for 100 hours showed M23C6 carbides precipitated at grain boundaries and also at the Laves phase/matrix interfaces. However, upon aging at 750 Celsius degrees for 100 hours the precipitation of M23C6 and M6C takes place at the grain boundary and in the austenitic matrix, thus increasing the material s hardness by 18 percent, when compared to it as solubilized. The increase of the hardness by 12 percent after the heat treatment is related to the precipitation of the carbides in the grain boundaries and dispersed in the matrix resulting from the aging thermal treatments.

Though ferroelectric HfO₂ thin films are now well characterized, little is currently known about their grain substructure. In particular, the formation of domain and phase boundaries requires investigation to better understand phase stabilization, switching, and phase interconversion. Here, scanning transmission electron microscopy is applied to investigate the atomic structure of boundaries in these materials. It is found that orthorhombic/orthorhombic domain walls and coherent orthorhombic/monoclinic interphase boundaries form throughout individual grains. The results inform how interphase boundaries can impose strain conditions that may be key to phase stabilization. Moreover, the atomic structure near interphase boundary walls suggests potential for their mobility under bias, which has been speculated to occur in perovskite morphotropic phase boundary systems by mechanisms similar to domain boundary motion.

D. Tech. (Department of Biotechnology and Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / The synthesis of Ag and Cu nanoparticles was carried out using the thermal decomposition method in the presence of oleylamine as a capping agent. This method was used because it can produce uniform and monodisperse nanoparticles with controlled size distribution. The nanoparticles synthesized under various conditions were characterized by transmission electron microscopy (TEM), UV/Vis spectroscopy, photoluminescence spectroscopy (PL), and X-ray diffraction (XRD). The effect of precursor concentration on the morphology and size of the nanoparticles was investigated. It was observed that an increase in the precursor concentration resulted in an increase in particle sizes with different morphologies for both Ag and Cu nanoparticles. The increase in particle sizes for Ag nanoparticles was due to Ostwald ripening, while for Cu nanoparticles it was due to agglomeration, as Cu tends to oxidize in the atmosphere, leading to a change in particle size and shape. However, the ability to control and manipulate their physical and chemical properties depends on tuning their size and shape. Therefore, varying the precursor concentration helped in selecting the optimal concentration for this study. The nanoparticles produced were used in another study as fillers or additives for the production of nanofiber composites. The development of nanofibers by electrospinning process has led to potential applications in filtration, tissue engineering scaffolds, drug delivery, wound dressing and etc. The current study is an attempt to fabricate composite nanofibers that can be used as wound dressing material for effective wound healing. The approach involves the blending of two different polymers both being biocompatible and biodegradable were one is a natural polymer and the other is a synthetic polymer. In this study, different weight ratios of CS/PVA blends, Ag/Cu/CS/PVA, Ag/CS/PVA and Cu/CS/PVA composite fibers have been successfully prepared by the electrospinning process. The tip-to-collector distance was kept at 15 cm and the applied voltage was varied from 15 to 25 kV. The effects of the weight ratios applied voltage and the nanoparticles loading on the morphology and diameter of the fibers were investigated. The resultant fibers were characterized using scanning electron microscopy (SEM), XRD, Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric analysis (TGA) and UV-Vis spectroscopy. The SEM results showed that an increase the amount of chitosan in the CS/PVA blend resulted in a decrease in the fiber diameters while an increase in the voltage from 15 to 25 kV led to a decrease in the fiber diameters. Furthermore, an increase in fiber diameters was observed with irregular morphologies upon addition of Ag/Cu nanoparticles into the blend. The latter changes are perceived to be as a result of an increased conductivity and a higher charge density. The XRD results showed peaks which correspond to Ag in the face centred cubic. Ag peaks are more dominant than Cu peaks in the XRD of the mixed nanoparticles. The FTIR spectra of the Ag/Cu/CS/PVA composite fibers gave almost identical features as the blend. This proves that there was an interaction between CS and PVA polymer due to intermolecular hydrogen bonding. The TGA curves showed no significant effect on the thermal stability of the composite fibers upon addition of different nanoparticles loadings. The absorption spectra of the composite fibers showed an improved optical properties compared to the blend. For Ag and Cu nanoparticles composite fibers it was observed that addition of Ag nanoparticles in the blend resulted in an increase in fiber diameters with uniform morphology whereas for Cu resulted in a decrease in fiber diameters. Both Ag and Cu composite fibers showed an improved optical properties. The effect of CS/PVA, Ag/Cu, Ag, and Cu nanofibers on the selected microorganism (K.pneumoniae, S. aureus, P. aeruginosa, and E.coli) was evaluated using the disk diffusion method. It was observed that Ag/Cu/CS/PVA composite fibers showed greater activity against all microorganisms compared to Ag and Cu composite fibers. The alamar blue and Pierce Lactase dehydrogenase (LDH) assay were used to assess the effect of the blend and the composite fibers on cell viability and cytotoxicity, respectively. The results show that the prepared blend and the composite fibers did not have any toxic effect on human adipose derived stem cells (hADSC). The results also showed that as the concentration of Ag/Cu nanoparticles was increased the viability of the cells also increased after 24 hour incubation. More proliferation was observed in day 1 compared to day 3. The 30/70 blend showed more viable cell compared to the negative control. For Ag and Cu composite fibers the 30/70 CS/PVA blend increased cell proliferation after 3 days with 17% more viable cells compared to the negative control. These results show that the prepared blend with its composite fibers are biocompatible with human (ADSC) and may be suitable for use in biomedical application such as wound dressing.

Despite enormous efforts and investments, the efficiency of InGaN-based green and yellow-green light emitters remains relatively low, and that limits progress in developing full color display, laser diodes, and bright light sources for general lighting. The low efficiency of light emitting devices in the green-to-yellow spectral range, also known as the “Green Gap”, is considered a global concern in the LED industry. The polar c-plane orientation of GaN, which is the mainstay in the LED industry, suffers from polarization-induced separation of electrons and hole wavefunctions (also known as the “quantum confined Stark effect”) and low indium incorporation efficiency that are the two main factors that contribute to the Green Gap phenomenon. One possible approach that holds promise for a new generation of green and yellow light emitting devices with higher efficiency is the deployment of nonpolar and semi-polar crystallographic orientations of GaN to eliminate or mitigate polarization fields. In theory, the use of other GaN planes for light emitters could also enhance the efficiency of indium incorporation compared to c-plane. In this thesis, I present a systematic exploration of the suitable GaN orientation for future lighting technologies. First, in order to lay the groundwork for further studies, it is important to discuss the analysis of processes limiting LED efficiency and some novel designs of active regions to overcome these limitations. Afterwards, the choice of nonpolar orientations as an alternative is discussed. For nonpolar orientation, the (1-100)-oriented (m-plane) structures on patterned Si (112) and freestanding m-GaN are studied. The semi-polar orientations having substantially reduced polarization field are found to be more promising for light-emitting diodes (LEDs) owing to high indium incorporation efficiency predicted by theoretical studies. Thus, the semi-polar orientations are given close attention as alternatives for future LED technology. One of the obstacles impeding the development of this technology is the lack of suitable substrates for high quality materials having semi-polar and nonpolar orientations. Even though the growth of free-standing GaN substrates (homoepitaxy) could produce material of reasonable quality, the native nonpolar and semi-polar substrates are very expensive and small in size. On the other hand, GaN growth of semi-polar and nonpolar orientations on inexpensive, large-size foreign substrates (heteroepitaxy), including silicon (Si) and sapphire (Al2O3), usually leads to high density of extended defects (dislocations and stacking faults). Therefore, it is imperative to explore approaches that allow the reduction of defect density in the semi-polar GaN layers grown on foreign substrates. In the presented work, I develop a cost-effective preparation technique of high performance light emitting structures (GaN-on-Si, and GaN-on-Sapphire technologies). Based on theoretical calculations predicting the maximum indium incorporation efficiency at θ ~ 62º (θ being the tilt angle of the orientation with respect to c-plane), I investigate (11-22) and (1-101) semi-polar orientations featured by θ = 58º and θ = 62º, respectively, as promising candidates for green emitters. The (11-22)-oriented GaN layers are grown on planar m-plane sapphire, while the semi-polar (1-101) GaN are grown on patterned Si (001). The in-situ epitaxial lateral overgrowth techniques using SiNx nanoporous interlayers are utilized to improve the crystal quality of the layers. The data indicates the improvement of photoluminescence intensity by a factor of 5, as well as the improvement carrier lifetime by up to 85% by employing the in-situ ELO technique. The electronic and optoelectronic properties of these nonpolar and semi-polar planes include excitonic recombination dynamics, optical anisotropy, exciton localization, indium incorporation efficiency, defect-related optical activities, and some challenges associated with these new technologies are discussed. A polarized emission from GaN quantum wells (with a degree of polarization close to 58%) with low non-radiative components is demonstrated for semi-polar (1-101) structure grown on patterned Si (001). We also demonstrated that indium incorporation efficiency is around 20% higher for the semi-polar (11-22) InGaN quantum wells compared to its c-plane counterpart. The spatially resolved cathodoluminescence spectroscopy demonstrates the uniform distribution of indium in the growth plane. The uniformity of indium is also supported by the relatively low exciton localization energy of Eloc = 7meV at 15 K for these semi-polar (11-22) InGaN quantum wells compared to several other literature reports on c-plane. The excitons are observed to undergo radiative recombination in the quantum wells in basal-plane stacking faults at room temperature. The wurtzite/zincblende electronic band-alignment of BSFs is proven to be of type II using the time-resolved differential transmission (TRDT) method. The knowledge of band alignment and degree of carrier localization in BSFs are extremely important for evaluating their effects on device properties. Future research for better understanding and potential developments of the semi-polar LEDs is pointed out at the end.

Les objectifs de ce travail sont d'une part d'étudier la structure électronique de carbures de titane bidimensionnels appartenant à la famille des MXènes, et d'autre part de synthétiser des films minces pour caractériser certaines de leurs propriétés. L'étude de la structure électronique a été réalisée sur le système Ti3C2T2 avec une attention particulière portée aux groupements de surface T (T=OH, F ou O) en comparant les résultats obtenus par spectroscopie de perte d'énergie des électrons à ceux des calculs ab initio. Cette étude, portée à la fois sur les excitations du gaz d'électrons de valence et des électrons de coeur, a permis de mettre en évidence la localisation des groupements de surface, ainsi que leur influence sur la structure électronique du MXene. La comparaison des simulations et des spectres expérimentaux a également permis de caractériser la nature chimique des groupements de surface. Enfin, la limite d'une telle étude est discutée en considérant les phénomènes d'irradiation responsables de la perte d'atomes d'hydrogène. La synthèse d'échantillons modèles nécessite la synthèse préalable d'un film mince de phase MAX précurseur pour le MXene : nous avons choisi la phase Ti2AlC, précurseur de Ti2C. La synthèse de Ti2AlC a été réalisée par recuit ex-situ de systèmes multicouches déposés à température ambiante. Les films ont été caractérisés par diffraction des rayons X et microscopie électronique en transmission. Au-delà de l'obtention d'un film mince de Ti2AlC texturé, cette étude a permis de montrer que la phase recherchée était obtenue via des mécanismes d'interdiffusions induisant la formation d'une solution solide métastable vers 400°C qui se transforme en phase MAX vers 600°C. Enfin, l'application de ce procédé à la phase V2AlC a permis de montrer l'importance de l'orientation de la phase initiale pour l'obtention d'un film mince texturé. / The aim of this work is at first to study the electronic structure of bidimensional titanium carbide systems, belonging to the MXene family and also to synthesize thin films of such new materials to characterize their properties. The study of the electronic structure has been performed for the Ti3C2T2 MXene with a special attention to the T surface groups by using a combination of electron energy loss spectroscopy and ab initio calculations. This study, focused on both valence and core electrons excitations, enabled the identification of the surface group localization, their influence on the MXene electronic structure as well as their chemical nature. The limits of our TEM-based study is also discussed in view of irradiation phenomena which induce the loss of hydrogen atoms. The synthesis of a MXene thin film requires, beforehand, that of a MAX phase thin film: we opted for Ti2AlC, the precursor for the Ti2C MXene. The MAX phase thin film synthesis was carried out by ex-situ annealing of a multilayer layers. X-ray diffraction experiments and cross-sectional transmission electron microscopy observations show that a highly textured Ti2AlC thin film is obtained above 600°C after the formation, at 400°C, of a metastable solid solution. Finally, by using the same process for V2AlC, we demonstrate that the initial phase orientation plays a key role for the texture of the thin film so obtained.

The thermal atomic layer deposition (ALD) of copper oxide films from the non-fluorinated yet liquid precursor bis(tri-<it>n</it>-butylphosphane)copper(I)acetylacetonate, [(^<it>n</it>Bu₃P)₂Cu(acac)], and wet O₂ on Ta, TaN, Ru and SiO₂ substrates at temperatures of < 160&deg;C is reported. Typical temperature-independent growth was observed at least up to 125&deg;C with a growth-per-cycle of ~ 0.1 &Aring; for the metallic substrates and an ALD window extending down to 100&deg;C for Ru. On SiO₂ and TaN the ALD window was observed between 110 and 125&deg;C, with saturated growth shown on TaN still at 135&deg;C. Precursor self-decomposition in a chemical vapor deposition mode led to bi-modal growth on Ta, resulting in the parallel formation of continuous films and isolated clusters. This effect was not observed on TaN up to about 130&deg;C and neither on Ru or SiO₂ for any processing temperature. The degree of nitridation of the tantalum nitride underlayers considerably influenced the film growth. With excellent adhesion of the ALD films on all substrates studied, the results are a promising basis for Cu seed layer ALD applicable to electrochemical Cu metallization in interconnects of ultralarge-scale integrated circuits.<br> &copy; 2009 The Electrochemical Society. All rights reserved. <br> / Es wird die thermische Atomlagenabscheidung (ALD) von Kupferoxidschichten, ausgehend von der unfluorierten, fl&uuml;ssigen Vorstufenverbindung Bis(tri-<it>n</it>-butylphosphan)kupfer(I)acetylacetonat, [(^<it>n</it>Bu₃P)₂Cu(acac)], sowie feuchtem Sauerstoff, auf Ta-, TaN-, Ru- und SiO₂-Substraten bei Temperaturen < 160&deg;C berichtet. Typisches temperaturunabh&auml;ngiges Wachstum wurde zumindest bis 125&deg;C beobachtet. Damit verbunden wurde f&uuml;r die metallischen Substrate ein Zyklenwachstum von ca. 0.1 &Aring; erzielt sowie ein ALD-Fenster, das f&uuml;r Ru bis zu einer Temperatur von 100&deg;C reicht. Auf SiO₂ und TaN wurde das ALD-Fenster zwischen 110 und 125&deg;C beobachtet, wobei auch bei 135&deg;C noch ges&auml;ttigtes Wachstum auf TaN gezeigt werden konnte. Die selbst&auml;ndige Zersetzung des Precursors &auml;hnlich der chemischen Gasphasenabscheidung f&uuml;hrte zu einem bimodalen Schichtwachstum auf Ta, wodurch gleichzeitig geschlossene Schichten und voneinander isolierte Cluster gebildet wurden. Dieser Effekt wurde auf TaN bis zu einer Temperatur von 130&deg;C nicht beobachtet. Ebensowenig trat er im untersuchten Temperaturbereich auf Ru oder SiO₂ auf. Der Nitrierungsgrad der TaN-Schichten beeinflusste hierbei das Schichtwachstum stark. Mit einer sehr guten Haftung der ALD-Schichten auf allen untersuchten Substratmaterialien erscheinen die Ergebnisse vielversprechend f&uuml;r die ALD von Kupferstartschichten, die f&uuml;r die elektrochemische Kupfermetallisierung in Leitbahnsystemen ultrahochintegrierter Schaltkreise anwendbar sind.

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