Philosophiae Doctor - PhD / The domesticated apple (Malus x domestica Borkh.) has been distributed into diverse climatic conditions worldwide for commercial production of fruit. Apple trees need exposure to cold temperatures, referred to as chill unit (CU) accumulation during winter, in order for budbreak to occur promptly and uniformly after winter. In warmer production areas the application of dormancy breaking chemicals has enabled successful production of high chilling requiring apple cultivars in suboptimal environmental conditions. In the Western Cape region of South Africa it is common orchard practice to apply dormancy breaking chemicals after winter in order to stimulate vegetative growth. If this is not done prolonged dormancy symptoms (PDS) are experienced which include extended rest, less synchronised breaking of buds and reduced branching. An increasing awareness of both global warming and the negative effects associated with the use of chemical sprays (for both pest and disease resistance and growth regulation) has resulted in the need to breed cultivars better adapted to current and future environmental conditions. The breeding of new cultivars using conventional breeding methods is a time consuming process, especially in perennial tree species with a long juvenile phase such as apple. The implementation of marker-assistedbreeding (MAB) and selection (MAS) will enable the selection of favourable genotypes at a very early seedling stage. Although markers linked to genes involved in disease resistance for a variety of known apple pathogens have been identified and are already in use in breeding programs, the genetic determinants of dormancy related characteristics residing within the bud itself iii (endodormancy) are poorly understood. This hampers the genetic improvement of such characters. Although this study focused on time of initial vegetative budbreak IVB, there are various other characteristics that can be associated with dormancy, such as position and number of budbreak and budbreak duration.

Dans cette thèse, nous avons étudié la conception, le prototypage et la caractérisation de microsystèmes photovoltaïques à concentration à base de cellules solaires Cu(In,Ga)Se2. L'objectif est de réduire l'utilisation de matériaux rares en utilisant la concentration de la lumière, et bénéficier des effets de la miniaturisation, comme la dissipation de la chaleur et des pertes résistives inférieurs. Tout d'abord, la conception optique des systèmes à concentration sur la base des microlentilles sphériques est présentée. À l'aide d'un logiciel de tracés de rayon Zemax OpticStudio, nous avons évalué la meilleure combinaison d'éléments, l'épaisseur et les rayons de courbure des lentilles, ainsi que les tolérances de fabrication et de positionnement du système. Un système optique de 1 mm d'épaisseur avec un rapport géométrique de 100 et une tolérance angulaire de +/- 3,5 ° a été conçu. D'autre part, des procédés de fabrication ont été créés et optimisés pour fabriquer un prototype de 5x5 cm² avec 2500 microcellules. Le meilleur mini-module a montré un facteur de concentration de 72x avec une augmentation en valeur absolue de l'efficacité de + 1,6%. Ensuite, des études numériques et expérimentales ont été réalisées sur des systèmes basés sur des concentrateurs luminescents (LSC) et des concentrateurs paraboliques (CPC). Les LSC ont montré un facteur de concentration faible et souffraient de problèmes de répétabilité tandis que les CPC sont une solution très efficace, mais très difficile à fabriquer à l¿échelle du micron. Enfin, nous avons développé un code MATLAB pour estimer l'énergie produite des systèmes conçus, pour évaluer la pertinence des choix technologiques futurs. / In this thesis, we studied the design, prototyping and characterization of micro-concentrated photovoltaic systems based on Cu(In,Ga)Se2 solar cells. The objective is to reduce the use of rare materials using the concentration of light, and benefit from the effect of miniaturization such as heat dissipation and lower resistive losses. First, the optical design of 1D and 2D concentrating systems based on spherical microlenses is presented. Using a ray-tracing software Zemax OpticStudio, we evaluated the best combination of elements, thickness and radii of curvature of the lenses, as well as the tolerances of fabrication and positioning of the system. An optical system of 1 mm thickness with a geometrical ratio of 100 and an angular tolerance of +/- 3.5° has been designed. Second, fabrication processes have been created and optimized to fabricate a 5x5 cm² prototypes with 2500 microcells. The best mini-module showed a concentration factor of 72x with an absolute increase of the efficiency of +1.6%. Third, numerical and experimental studies have been performed on concentrating systems based on Luminescent Solar Concentrators (LSC) and Compound Parabolic Concentrators (CPC). The LSC showed a low concentration factor and suffered from repeatability issues while the CPC is a very efficient solution but its specific geometry makes it difficult to fabricate at the micron scale. Finally, we developed a MATLAB code to estimate the producible energy of the designed systems, in order to evaluate the relevance of future technological choices that will be made.

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No description available.

Aluminum was deposited onto both Teflon AF and Parylene AF surfaces by chemical vapor deposition of trimethylaluminum. This work shows that similar thin film (100 Angstroms) aluminum oxide adlayers form on both polymers at the low temperature dosing conditions used in the studies. Upon anneal to room temperature and above, defluorination of the polymer surfaces increased and resulted in fluorinated aluminum oxide adlayers; the adlayers were thermally stable to the highest temperatures tested (600 K). Angle-resolved spectra showed higher levels of fluorination toward the polymer/adlayer interface region. Copper films were also deposited at low temperature onto Teflon AF using a copper hexafluoroacetylacetonate-cyclooctadiene precursor. Annealing up to 600 K resulted in the loss of precursor ligands and a shift to metallic copper. As with aluminum adlayers, some polymer defluorination and resulting metal (copper) fluoride was detected. Parylene AF and polystyrene films surfaces were modified by directly dosing with water vapor passed across a hot tungsten filament. Oxygen incorporation into polystyrene occurred exclusively at aromatic carbon sites, whereas oxygen incorporation into parylene occurred in both aromatic and aliphatic sites. Oxygen x-ray photoelectron spectra of the modified polymers were comparable, indicating that similar reactions occurred. The surface oxygenation of parylene allowed enhanced reactivity toward aluminum chemical vapor deposition. Silicon-carbon (Si-Cx) films were formed by electron beam bombardment of trimethylvinylsilane films which were adsorbed onto metal substrates at low temperatures in ultra-high vacuum. Oxygen was also added to the films by coadsorbing water before electron beam bombardment; the films were stable to more than 700 K, with increasing silicon-oxygen bond formation at elevated temperatures. Copper metal was sputter deposited in small increments onto non-oxygenated films. X-ray photoelectric spectra show three-dimensional copper growth (rather than layer-by-layer growth), indicating only weak interaction between the copper and underlying films. Annealing at elevated temperatures caused coalescence or growth of the copper islands, with spectra indicating metallic copper rather than copper oxide.

<p>Cu-zeolites have received renewed attention as catalytic materials that facilitate partial methane oxidation (PMO) to methanol, with a variety of mononuclear, binuclear, and multinuclear Cu active site motifs that have been proposed in prior literature. Our approach to more precisely identify and probe the Cu structures that activate O₂ and reduce in CH₄relies on the synthesis of model supports with varying composition and well-defined Cu speciation, which also facilitates connections between experimental data and theoretical models. Chabazite (CHA) zeolites are high-symmetry frameworks that contain a single lattice tetrahedral site (T-site), in which Cu²⁺ ions exchange at paired Al sites in a six-membered ring (6-MR) while CuOH⁺ species exchange at isolated 6-MR Al sites, the latter of which can react to form binuclear O/O₂-bridged Cu structures. In this work, Cu-CHA zeolites were synthesized to contain predominantly Cu²⁺ (Z₂Cu) or CuOH⁺ (ZCuOH) species of varying density, or a mixture of Z₂Cu and ZCuOH sites. Z₂Cu and ZCuOH sites were quantified by titration of residual Brønsted acid sites with NH₃, which respectively exchange with 2:1 or 1:1 H⁺:Cu²⁺ stoichiometry. Stoichiometric PMO reaction cycles on Cu-zeolites involved high-temperature (723 K) activation in O₂, and then moderate-temperature (473 K) reduction in CH₄ and treatment in H₂O (473 K) to extract CH₃OH. <i>I</i><i>n-situ</i> UV-Visible spectroscopy under oxidizing (O₂, 723 K) and reducing (CO, 523 K; CH₄, 473 K; He, 723 K) conditions detected the presence of mononuclear and binuclear Cu site types, while <i>in-situ</i> Cu K-edge X-ray absorption spectroscopy after such treatments was used to quantify Cu(I) and Cu(II) contents and <i>in situ</i> Raman spectroscopy was used to identify the Cu structures formed. ZCuOH, but not Z₂Cu sites, are precursors to binuclear O/O₂-bridged Cu sites that form upon O₂ activation and subsequently produce methanol after stoichiometric PMO cycles, at yields (per total Cu) that increased systematically with ZCuOH site density. The fraction of Cu(II) sites that undergo auto-reduction in inert at high temperatures (He, 723 K) is identical, within experimental error, to the fraction that reduces in CH₄ at temperatures relevant for PMO (473 K), providing a quantitative link between the binuclear Cu site motifs involved in both reaction pathways and motivating refinement of currently postulated PMO reaction mechanisms. These Cu-CHA zeolites were also studied for other redox chemistries including the selective catalytic reduction (SCR) of NO_x with NH₃. <i>In situ </i>UV-Visible and X-ray absorption spectroscopies were used to monitor and quantify the transient partial reduction of Cu(II) to Cu(I) during exposure to NH₃ (473 K), in concert with titration methods that use NO and NH₃ co-reductants to fully reduce all Cu(II) ions that remain after treatment in NH₃ alone to the Cu(I) state, providing quantitative evidence that both Z₂Cu and ZCuOH sites are able to reduce in NH₃ alone to similar extents as a function of time. These findings provide new insight into the reaction pathways and mechanisms in which NH₃ behaves as a reductant of mononuclear Cu(II) sites in zeolites, which are undesired side-reactions that occur during steady-state NO_x SCR and that often unintendedly result in Cu(II) reduction prior to spectroscopic or titrimetric characterization. Overall, the strategy in this dissertation employs synthetic methods to control framework Al density and arrangement in zeolite supports to emphasize extra-framework Cu site motifs of different structure and at different spatial densities, and to interrogate these model materials using a combination of <i>in situ</i> spectroscopic techniques together with theory, in order to elucidate active site structure and proximity requirements in redox catalysis. This work demonstrates how quantitative reactivity and site titration data, brought together with an arsenal of tools available in contemporary catalysis research, can provide detailed mechanistic insights into transition metal-catalyzed redox cycles on heterogeneous catalysts.</p>

A new materials system of a single layered Co(W) barrier/liner coupled with a Cu(Mn) alloy seed was investigated. Atom probe tomography visualized the sub-nanoscale structure of Cu(Mn)/Co(W) system, and thereby revealed Cu diffusion behavior of Co(W). Grain boundaries of Co were found to be the diffusion path, and successfully stuffed by W. Mn in Cu(Mn) also segregated to stuff the grain boundaries of Co. Combination of these two additives enabled high barrier property against Cu diffusion of Cu(Mn)/Co(W). Foreseeing tiny and high-aspect-ratio Cu interconnect features, Cu(Mn)/Co(W) was fabricated by ALD/CVD processes. To maximize the performance, minor impurities of the film incorporated from the ligand of the precursors were controlled by precursor selection. Thin, conformal, and smooth films were finally demonstrated onto a trench substrate.

Aufgrund von guten Eigenschaften als Kupferdiffusionsbarriere und guter elektrischer Leitfähigkeit könnte sich Ruthenium und Ruthenium basierte Legierungen als Kupferdiffusionsbarriere eignen. Auf eine theoretische Aufarbeitung von Elektromigrationsmechanismen und in der Praxis eingesetzte Elektromigrationsteststrukturen folgen beschleunigte elektrische Elektromigrationstestergebnisse. Es konnte gezeigt werden, dass das System Kupfer, Ruthenium, Tantalnitrid Elektromigrationsstabiler als das konventionelle System Kupfer, Tantal, Tantalnitrid ist.:1 Einleitung 1 2 Stand der Forschung 2 2.1 Migrationsarten 2 2.2 Praktische Formulierung des Mechanismus der Elektromigration 2 2.3 Transportpfade der Elektromigration 3 2.4 Einflüsse auf die Elektromigration 4 2.4.1 Übersicht 4 2.4.2 Quereinfluss des mechanischen Stresses (Blech-Effekt) 5 2.4.3 Quereinfluss durch thermisch induziertem Stress 6 2.4.4 Materialwanderung aufgrund eines Temperaturgradienten 8 2.4.5 Einfluss des Leiterbahnmaterials (Legierung) 8 2.4.6 Einflüsse der Mikrostruktur 8 2.4.7 Einflüsse der Passivierung der Leiterbahnen 9 3 Theoretische Untersuchungen 9 3.1 Untersuchte Elektromigrationsteststrukturen 9 3.1.1 NIST-Struktur 9 3.1.2 Untersuchungen mithilfe der NIST-Struktur 10 3.1.3 Schlitz-Struktur 11 3.1.4 Bestimmung des Flächenwiderstandes RF = r=A der Schlitz-Struktur 12 3.1.5 Schlitzlängenänderungsgeschwindigkeit der Schlitz-Struktur 13 3.1.6 Prinzipielles Vorgehen zur Bestimmung der Schlitzlängenänderungsgeschwindigkeit als Kriterium für Elektromigrationsbeständigkeit 14 3.1.7 Blech-Struktur 15 3.1.8 Untersuchungen mithilfe der Blechstruktur 16 3.2 Vergleich der untersuchten Elektromigrationsteststrukturen 16 4 Experimentelle Untersuchungen 17 4.1 Beschreibung des Versuchsaufbaus 17 4.2 Evaluation der Messvorraussetzungen 18 4.2.1 Temperaturbeständigkeit der Messanordnungen 18 4.2.2 Oxidationsbeständigkeit der Schlitz- & Blechstruktur 19 4.2.3 Vernachlässigung Kupfer- und Leitungswiderstände 21 II 4.2.4 Untersuchungen bei verschiedenen Stromdichten (Schlitzstruktur) 22 4.2.5 Evaluation der günstigsten Schlitzlänge für Klassifikationstests 24 4.3 Untersuchungen an der NIST-Struktur 26 4.3.1 Ergebnisse 26 4.3.2 Probleme beim Versuchsaufbau und mögliche Lösungen 27 4.4 Untersuchungen an der Schlitz-Struktur 28 4.4.1 Bestimmung des Flächenwiderstands RF 28 4.4.2 Bestimmung der Schlitzlängenänderungsgeschwindigkeit 28 4.4.3 Optische Probenauswertung mittels TEM und FIB-Schnitt 30 4.4.4 Vergleich von Ta mit Ru und Ru0;95Mn0;05 31 4.4.5 Probleme beim Messaufbau und mögliche Lösungen 31 4.5 Untersuchungen an der Blechstruktur 33 4.5.1 Untersuchungen bei verschiedenen Stromdichten 33 4.5.2 Untersuchung bei verschiedenen Temperaturen 35 4.5.3 Probleme bei den Messungen und mögliche Lösungen 36 5 Zusammenfassung 37 6 Literaturverzeichnis 38

This diploma thesis deals with the use of modern powder fertilizers with growth stimulators, which were used for afforestation of hollow Norway spruce (Picea abies / L./Karst.) after bulldozer soil preparation in the Ore Mountains at LS Klášterec nad Ohří. On these scarified areas of the 7th forest vegetation stage two research areas of Bojiště and Kiosek were established. The battlefield area Bojiště was divided into 6 plots, one of which served only as a check. On these parcels were distinguished Norway spruce (Picea abies / L./Karst.) specimens from growing trees (A) and seedlings (B). Norway spruce seedlings were fertilized with fertilizers series Silvamix® (Sivamix® SR50 + S2, Silvamix® SR30 + S2 and Agluform 90S + S2) and organomineral fertilizers Vermaktiv Stimul and Fungil. Samples of the last year of needles were taken once per year, as well as samples of the soil environment. Support of nutrients were extended and growth spruce cultivation especially by using fertiliziers series Silvamix®. Individual fertilizers were contributed to the promotion of the different nutrients, of course in relation to the composition of fertilizers. Further these fertilizers contributed to improving the vitality of individuals Norway spruce (Picea abies / L./Karst.). The area of the Kiosek was treated with the new fertilizer UNICON. On this area carried two years of research for the sampling of soil samples and the last year needles of Norway spruce (Picea abies / L./Karst.). Against a control variant UNICON has demonstrated the benefits of optimizing the soil enviroment of sprececulture. The overall effect of this fertilizer contributed growth of individuals on the surface and the overall balancing takings nutrients.

One main reason for the use of Fe-Cu-C system in PM industry is the presence of liquid phase (copper) at the start of sintering (1120oC). The diffusion of liquid copper into iron causes swelling in the structure. This in turn can cause high dimensional change and, if not controlled properly, may cause distortion. So it is of paramount importance to control the copper diffusion. Carbon, added as graphite, reduces the swelling of copper by changing the dihedral angle. The affect of graphite on copper diffusion depends on the graphite type, particle size of graphite and heating rate. The aim of this work was to find the influence of graphite type and particle size of graphite on copper diffusion. Water Atomized iron (ASC100.29) produced in Höganäs AB was taken as the base powder.  Two types of graphite were used each with two different particle sizes. Two different graphite quantities (0.2% &amp; 0.8%) for each type was taken. Natural fine graphite (UF4), Natural coarse graphite (PG44), Synthetic fine graphite (F10) and  Synthetic coarse graphite (KS44) were the graphites used in this work. Powders were compacted at 600 Mpa and the sintering was done at 1120oC for 30 minutes in 90/10 N2/H2. Dilatometry and metallographic investigation of the samples sintered in the production furnace were used to understand the graphite influence.   The investigation showed that at low graphite levels (0.2%), the affect of graphite type or graphite size was not significant on copper diffusion. At high graphite levels (0.8%),  synthetic graphites were more effective in reducing the swelling of copper. Influence of  particle size of synthetic graphites on Cu diffusion was not significant compared to the influence of particle size of natural graphite. There was also a considerable affect of heating rate on graphite dissolution and copper swelling.