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We present a self-consistent calculation of the mono vacancy formation energy for seven simple metals Li, Na, K, Rb, Cs (all bcc), Al (fcc) and Mg (hcp) using both model and ab initio pseudopotential used in earlier unified studies. The local model pseudopotential calculations show small variations with respect to different exchange-correlation functions and the results are in fair agreement with other similar calculations and the available experimental data. The comparisons show that reliable model (pseudo) potential for simple metals can indeed be obtained for explaining a host of properties. Also, considering the importance of third order term in ab initio calculations, the results of our second order calculation appear fairly reasonable and are comparable with other first principle calculations. The perturbation series being an oscillating one, we hope to improve the calculational results using suitable series convergence acceleration method in the next part of our study.

La0.6Ca0.4Mn0.8Ni0.2O3-, La0.6Ca0.4Mn0.8Fe0.2O3- und La0.75Ca0.25Mn0.5Fe0.5O3-Volumenmaterialien wurden im potentiometrischen Messaufbau bereits erfolgreich auf ihre NO-Sensitivität getestet. Keramischen Nanomaterialien werden generell eine Reihe neuer oder verbesserter Eigenschaften (verbessertes Sinterverhalten, erhöhte NOx-Sensitivität, höhere Leitfähigkeit) zugesprochen. La0.6Ca0.4Mn0.8Ni0.2O3, La0.6Ca0.4Mn0.8Fe0.2O3 und La0.75Ca0.25Mn0.5Fe0.5O3 wurden mittels PVA/Sucrose-Methode, Aktivkohlemethode und Fällungssynthese als Nanomaterialien sowie mit Festkörperreaktion als Volumenmaterialien dargestellt und mit typischen Charakterisierungsmethoden untersucht. Die Materialien wurden in verschiedenen Schichtdicken auf YSZ-Substrate aufgetragen und potentiometrisch sowie impedanzspektroskopisch auf ihre NO-Sensitivität und die Querempfindlichkeit gegenüber NO2 und Propylen geprüft. Potentiometrische Messungen im NO-Gasstrom ergeben eine Abhängigkeit der NO-Sensitivität von der Partikelgröße, der Schichtdicke und der Beschichtungsmethode. Impedanzspektroskopische Messungen an beidseitig beschichteten YSZ-Substraten zeigen ebenfalls eine Abhängigkeit des Zellwiderstands von der NO-Konzentration und der Partikelgröße. Die Nanomaterialien zeigen bei unterschiedlichen Sauerstoffpartialdrücken im untersuchten Temperaturbereich (300°C bis 850°C) höhere Leitfähigkeiten als die Volumenmaterialien gleicher Zusammensetzung. Dieses Verhalten wird mit dem höheren Sauerstoffaustausch der Nanomaterialien in Verbindung gebracht, der zur Erzeugung zusätzlicher Defekte in der Kristallstruktur führt. Die Nanostruktur und somit eine entsprechend hohe Leitfähigkeit bleiben bei hohen Sintertemperaturen (T > 1000°C), die der Herstellung gasdichter Presslinge dienen, erhalten. XANES- und Photoelektronenspektroskopie wurden verwendet, um die Punktdefekte zu definieren.

Galliumnitrid (GaN) ist ein Schlüsselmaterial zur Produktion von elektronischen Hochfrequenz- und Hochleistungsbauelementen sowie Leuchtdioden. Zum Erreichen der optimalen Bauelementleistung ist ein tiefgreifendes Verständnis sowie die Kontrolle von Punktdefekten unabdingbar um die elektrischen und optischen Substrateigenschaften präzise einzustellen. Im Rahmen dieser Arbeit wurden Punktdefekte in GaN mittels Photolumineszenz (PL)-spektroskopie untersucht. Häufige Übergangsmetallverunreinigungen (Fe, Mn und Cr) wurden anhand ihrer internen Übergänge, die sich durch scharfe Lumineszenz- und Absorptionslinien im nahen Infrarot auszeichnen, identifiziert. Mn und Cr wurden als Ursprung für ungewollte Substratfärbungen bestimmt. Teilweise Entfärbung konnte durch Mn-Si-Kodotierung erreicht werden. Der Zusammenhang zwischen Absorption und Emission des Cr-Zentrums wurde durch polarisationsabhängige PL-Anregungsspektroskopie analysiert. Weiterhin wurde der Einfluss von Kohlenstoffdotierung auf die Eigenschaften von GaN-Substraten durch PL- und PL-Anregungsspektroskopie untersucht. Eine neue Emissionsbande um 1,62 eV, die am effizientesten bei 2,7 eV angeregt wird, wurde für hochdotiertes GaN:C beobachtet und einem internen Übergang C_N-C_Ga-C_N-Komplexen zugeschrieben. / Gallium nitride (GaN) is a key material for the production of high frequency and high power electronics as well as light emitting diodes. Optimum device performance requires a profound understanding and control of the point defect formation in order to determine the electrical and optical substrate properties. Within this thesis, photoluminescence (PL) spectroscopy was applied to analyze point defects in GaN. Common transition metal impurities (Fe, Mn and Cr) were identified by their internal transitions characterized by sharp luminescence and absorption lines in the near infrared region. Among them, Mn and Cr were shown to be the origin of undesirable substrate coloration. Partial decoloration was achieved by an Mn-Si codoping approach. The relationship of absorption and emission processes of the Cr impurity center was further analyzed by polarization dependent PL excitation spectroscopy. Furthermore, the impact of C-doping on GaN substrate properties was investigated by PL and PL excitation spectroscopy. A new emission band around 1.6 eV, most efficiently excited at 2.7 eV, was reported for highly C-doped GaN and proposed to originate from an internal transition of C_N-C_Ga-C_N complexes.

Le fer et les alliages à base de fer présentent un intérêt considérable pour la communauté de la modélisation des matériaux en raison de l’immense importance technologique de l’acier. Les alliages ferritiques à base de fer sont largement utilisés dans les industries aéronautique et nucléaire en raison de leur résistance mécanique élevée, de leur faible dilatation à haute température et de leur résistance à la corrosion. Ces propriétés sont cependant affectées par des défauts ponctuels intrinsèques et extrinsèques. Dans cette thèse, nous décrivons en détail la cinétique des défauts ponctuels dans le fer α en utilisant la technique d’activation-relaxation cinétique (ARTc), une méthode de Monte Carlo cinétique hors réseau avec construction de catalogue à la volée. Plus précisément, nous nous intéressons aux mécanismes de diffusion du carbone (C) et des amas de lacunes dans le fer α. Dans un premier temps, nous étudions l’effet de la pression sur la diffusion du carbone dans le joint de grains de fer α. Nous constatons que l’effet de la pression peut fortement modifier la stabilité et la diffusivité du carbon dans le joint de grains d’une manière qui dépend étroitement de l’environnement local et de la nature de la déformation. Ceci peut avoir un impact majeur sur l’évolution des matériaux hétérogènes, avec des variations de pression locale qui altéreraient fortement la diffusion à travers le matériau. Nous étudions également l’évolution structurale des amas de lacunes contenant de deux à huit lacunes dans le fer α. Nous décrivons en détail le paysage énergétique, la cinétique globale et les mécanismes de diffusion associés à ces défauts. Nos résultats montrent des mécanismes de diffusion complexes même pour des défauts aussi simples que de petits amas de lacunes. Enfin, dans le dernier chapitre, nous discutons une approche de gestion de petites barrières par bassin local dans ARTc. Les simulations de Monte Carlo cinétiques deviennent inefficaces dans les systèmes où le paysage énergétique est constitué de bassins avec de nombreux états reliés par des barrières énergétiques très faibles par rapport à celles nécessaires pour quitter ces bassins. Au fur et à mesure que le système évolue état par état, il est beaucoup plus susceptible d’effectuer des événements répétés (appelés oscillateurs) à l’intérieur du bassin d’énergie de piégeage que de s’échapper du bassin. De tels osccilateurs ne font pas progresser la simulation et ne fournissent que peu d’informations au-delà d’uen première évaluation de ces états. Notre algorithme de bassin local détecte, à la volée, des groupes d’états oscillants et les consolide en bassins locaux, que nous traitons avec la méthode de taux moyen d’auto-construction de bassin (bac-MRM), une approche de type équation maîtresse selon la méthode du taux moyen. / Iron and iron-based alloys are of considerable interest to the materials modelling community because of the immense technological importance of steel. Iron-based ferritic alloys are widely used in aeronautic and nuclear industries due to their high mechanical strength, low expansion at high temperatures, and corrosion resistance. These properties are affected by intrinsic and extrinsic point defects, however. In this thesis, we describe in detail the kinetics of point defects in α−iron using the kinetic activation-relaxation technique (kART), an off-lattice kinetic Monte Carlo method with on-the-fly catalog building. More specifically, we focus on the diffusion mechanisms of carbon and vacancy clusters in α−iron. First, we study the pressure effect on carbon diffusion in the grain boundary (GB) of α−iron. We find that the effect of pressure can strongly modify the C stability and diffusivity in the GB in ways that depend closely on the local environment and the nature of the deformation. This can have a major impact on the evolution of heterogeneous materials, with variations of local pressure that would strongly alter diffusion across the material. We also study the structural evolution of vacancy clusters containing two to eight vacancies in α−iron. We describe in detail the energy landscape, overall kinetics, and diffusion mechanisms associated with these defects. Our results show complex scattering mechanisms even for defects as simple as small vacancy clusters. Finally, in the last chapter, we discuss a local basin approach to managing low barrier events in the kART. Kinetic Monte Carlo simulations become inefficient in systems where the energy landscape consists of basins with numerous states connected by very low energy barriers compared to those needed to leave these basins. As the system evolves state by state, it is much more likely to perform repeated events (so-called flickers) inside the trapping energy basin than to escape the basin. Such flickers do not progress the simulation and provide little insight beyond the first identification of those states. Our local basin algorithm detects, on the fly, groups of flickering states and consolidates them into local basins, which we treat with the basin-auto-constructing Mean Rate Method (bac-MRM), a master equation-like approach based on the mean-rate method.

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Materials intended for disposal of spent nuclear fuel require a particular combination of physical and chemical properties. The driving forces and mechanisms underlying the material’s behavior must be scientifically understood in order to enable modeling at the relevant time- and length-scales. The processes that determine the mechanical behavior of copper canisters and iron inserts, as well as the evolution of their mechanical properties, are strongly dependent on the properties of various defects in the bulk copper and iron alloys. The first part of the present thesis deals with precipitation in the cast iron insert. A nodular cast iron insert will be used as the inner container of the spent nuclear fuel. Precipitation is investigated by computing effective interaction energies for point defect pairs (solute–solute and vacancy–solute) in bcc iron using first-principles calculations. The main considered impurities in the iron matrix include 3sp (Si, P, S) and 3d (Cr, Mn, Ni, Cu) solute elements. By computing interaction energies possibility of formation of different second phase particles such as late blooming phases (LBPs) in the cast iron insert is evaluated. The second part is devoted to the fundamentals of dislocations and their role in plastic deformation of metals. Deformation of single-crystal copper under high strain rates is simulated by employing dislocation dynamics (DD) method to examine the effect of strain rate on mechanical properties as well as dislocation microstructure development. Creep deformation of copper canister at low temperatures is studied. The copper canister will be used in the long-term storage of spent nuclear fuel as the outer shell of the waste package to provide corrosion protection. A glide rate is derived based on the assumption that at low temperatures it is controlled by the climb rate of jogs on the dislocations. Using DD simulation creep deformation of copper at low temperatures is modeled by taking glide but not climb into account. Moreover, effective stresses acting on dislocations are computed using the data extracted from DD simulations. / <p>QC 20170428</p>

At present, focus of the SiC crystal growth development is on improving the crystalline quality without polytype inclusions, micropipes and the occurrence of extended defects. The purity of the grown material, as well as intentional doping must be well controlled and the processes understood. High-quality substrates will significantly improve device performance and yield. One of the aims of the thesis is further understanding of polytype inclusion formation as well as impurity control in SiC bulk crystals grown using PVT method also termed seeded sublimation method. Carbonization of the source was identified as a major reason behind the polytype inclusion occurrence during the growth. The aim of this work was further understanding of sublimation growth process of 4H-SiC bulk crystals in vacuum, in absence of an inert gas. For comparison growth in argon atmosphere (at 5 mbar) was performed. The effect of the ambient on the impurity incorporation was studied for different growth temperatures. For better control of the process in vacuum, tantalum as a carbon getter was utilized. The focus of the SiC part of the thesis was put on further understanding of the PVT epitaxy with an emphasis on the high growth rate and purity of grown layers. High resistivity 4H-SiC samples grown by sublimation with high growth rate were studied. The measurements show resistivity values up to high 104 cm. By correlation between the growth conditions and SIMS results, a model was applied in which it is proposed that an isolated carbon vacancy donor-like level is a possible candidate responsible for compensation of the shallow acceptors in p-type 4H-SiC. A relation between cathodoluminescence (CL) and DLTS data is taken into account to support the model. To meet the requirements for high voltage blocking devices such as high voltage Schottky diodes and MOSFETs, 4H-SiC epitaxial layers have to exhibit low doping concentration in order to block reverse voltages up to few keV and at the same time have a low on-state resistance (Ron). High Ron leads to enhanced power consumption in the operation mode of the devices. In growth of thick layers for high voltage blocking devices, the conditions to achieve good on-state characteristics become more challenging due to the low doping and pronounced thicknesses needed, preferably in short growth periods. In case of high-speed epitaxy such as the sublimation, the need to apply higher growth temperature to yield the high growth rate, results in an increased concentration of background impurities in the layers as well as an influence on the intrinsic defects. On-state resistance Ron estimated from current density-voltage characteristics of Schottky diodes on thick sublimation layers exhibits variations from tens of mΩ.cm2 to tens of Ω.cm2 for different doping levels. In order to understand the occurrence of high on-state resistance, Schottky barrier heights were first estimated for both forward and reverse bias with the application of thermionic emission theory and were in agreement with literature reported values. Decrease in mobility with increasing temperature was observed and its dependencies of T–1.3 and T–2.0 for moderately doped and low doped samples, respectively, were estimated. From deep level measurements by Minority Carrier Transient Spectroscopy (MCTS), an influence of shallow boron related levels and D-center on the on-state resistance was observed, being more pronounced in low doped samples. Similar tendency was observed in depth profiling of Ron. This suggests a major role of boron in a compensation mechanism. In the second part of the thesis growth and characterization of GaN is presented. Excellent electron transport properties with high electron saturate drift velocity make GaN an excellent candidate for electronic devices. Especially, AlGaN/GaN based high electron mobility transistors (HEMT) have received an increased attention in last years due to their attractive properties. The presence of strong spontaneous and piezoelectric polarization due to the lattice mismatch between AlGaN and GaN is responsible for high free electrons concentrations present in the vicinity of the interface. Due to the spatial separation of electrons and ionized donors or surface states, 2DEG electron gas formed near the interface of the heterostructure exhibits high sheet carrier density and high mobility of electrons. Al0.23Ga0.77N/GaN based HEMT structures with an AlN exclusion layer on 100 mm semiinsulating 4H-SiC substrates have been grown by hot-wall MOCVD. The electrical properties of the two-dimensional electron gas (2DEG) such as electron mobility, sheet carrier density and sheet resistance were obtained from Hall measurements, capacitance-voltage and contact-less eddy-current techniques. The effect of different scattering mechanisms on the mobility have been taken into account and compared to the experimental data. Hall measurements were performed in the range of 80 to 600 K. Hall electron mobility is equal to 17140 cm2(Vs)-1 at 80 K, 2310 cm2(Vs)-1 at room temperature, and as high as 800 cm2(Vs)-1 at 450 K, while the sheet carrier density is 1.04x1013 cm-2 at room temperature and does not vary very much with temperature. Estimation of different electron scattering mechanisms reveals that at temperatures higher than room temperature, experimental mobility data is mainly limited by optical phonon scattering. At relevant high power device temperature (450 K) there is still an increase of mobility due to the AlN exclusion layer. We have studied the behaviour of Ga-face GaN epilayers after in-situ thermal treatment in different gas mixtures in a hot-wall MOCVD reactor. Influence of N2, N2+NH3 and N2+NH3+H2 ambient on the morphology was investigated in this work. The most stable thermal treatment conditions were obtained in the case of N2+NH3 gas ambients. We have also studied the effect of the increased molar ratio of hydrogen in order to establish proper etching conditions for hot-wall MOCVD growth.

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