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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Ruthenium(II) arene complexes for asymmetric catalysis

Zhu, Zhenyu 09 August 2019 (has links)
Within the last few years, a significant contribution to the discovery of sp2C−H activation processes and useful applications for cross-coupling C−C bond formation has been achieved by the use of ruthenium(II) arene catalysts. The aim of this thesis is to describe a modular approach for the synthesis of several ruthenium(II) arene complexes with the potential for C−H activation. Another cutting-edge field, catalytic enantioselective functionalization of C−H bonds by transitional metal catalysts, has also been realized within the last few years. It represents a highly atom- and step-economic approach toward the generation of structural complexity. However, the majority of current methodologies rely on the usage of late third- row transition metals such as pallidum, iridium and rhodium. There is a need that motivates the search for cheaper, relative earth abundant metals that could have similar catalytic ability. Herein is also represented a preliminary study of a ruthenium(II)-catalyzed enantioselective access to chromane moiety enabled by chiral transient directing group.
2

Amélioration et compréhension du mécanisme d'activation de l'alliage FeTi dopé avec de l'hafnium, pour le stockage de l'hydrogène / Enhancement and study of activation process of FeTi alloy doped with hafnium, for hydrogen storage

Razafindramanana, Volatiana 20 December 2017 (has links)
La problématique de la première absorption (i.e. étape d’activation) de l’intermétallique FeTi, pour le stockage de l’hydrogène est souvent un frein pour son industrialisation. Le challenge réside dans la conception d’un « nouveau matériau » dont la première étape d’hydrogénation, s’effectue dans les mêmes conditions de température et de pression modérées, que lors de l’hydrogénation réversible. Une solution est de faire appel aux performances d’un élément dopant et/ou à la technique du broyage mécanique. Dans ce manuscrit, nous proposons l’utilisation de l’hafnium comme dopant. Ce projet complète les études qui ont été effectuées sur le zirconium (e.g. le zirconium commercial contient toujours une certaine quantité d’hafnium). L’ajout d’une faible quantité d’hafnium induit la formation d’une phase secondaire, « riche » en hafnium et en fer. Grâce à la présence de cette phase, la cinétique de première absorption est considérablement améliorée, et ce, sans traitement thermique préalable. L’étape d’activation comprend un seul mécanisme lorsque la taille des particules est faible. A contrario, un second mécanisme est mis en évidence, pour des particules de taille supérieure à 0,5 mm. La mécanosynthèse a permis non seulement d’obtenir la phase principale FeTi, mais aussi de favoriser la première absorption d’hydrogène. Des paramètres d’élaboration méticuleusement optimisés ont rendu possible la conception d’un matériau « modèle », par pulvérisation cathodique magnétron, sous forme de couche mince. Ce matériau modèle pourrait servir à étudier et à comprendre la diffusion de l’hydrogène à l’interface de la matrice FeTi et du dopant Zr ou Hf. / The issue of the first hydrogenation (i.e. activation process) of the intermetallic FeTi for the storage of hydrogen is often a brake for its use in industry. The challenge lies in the design of a "new material" whose first hydrogenation is carried out under the same conditions of moderate temperature and pressure, as during reversible absorption. Efficient solutions are to use a doping element and/or mechanical alloying process. In this work, we propose to use hafnium as a dopant. This project completes the studies that have been carried out on zirconium (e.g. commercial zirconium always contains a certain amount of hafnium). The addition of a small amount of hafnium induces the formation of a secondary phase, "rich" in hafnium and iron. Thanks to the presence of this phase, the kinetics of activation process is improved, without prior heat treatment. The activation process consists of a single step, when the particle size is small. However, a second step appears, for particles bigger than 0.5 mm. The mechanical alloying allowed the formation of the main phase FeTi, and also enhanced the activation process. An accurate control of deposition conditions allow us to design a ″model″ material by magnetron sputtering as thin layers. This ″model″ material can be used to study and understand the hydrogen diffusion, at the interface of the matrix (FeTi) and the dopant (Zr or Hf).
3

Thin film CDTE solar cells deposited by pulsed DC magnetron sputtering

Yilmaz, Sibel January 2017 (has links)
Thin film cadmium telluride (CdTe) technology is the most important competitor for silicon (Si) based solar cells. Pulsed direct current (DC) magnetron sputtering is a new technique has been developed for thin film CdTe deposition. This technique is industrially scalable and provides uniform coating. It is also possible to deposit thin films at low substrate temperatures. A series of experiments are presented for the optimisation of the cadmium chloride (CdCl2) activation process. Thin film CdTe solar cells require CdCl2 activation process to improve conversion efficiencies. The role of this activation process is to increase the grain size by recrystallisation and to remove stacking faults. Compaan and Bohn [1] used the radio-frequency (RF) sputtering technique for CdTe solar cell deposition and they observed small blisters on CdTe layer surface. They reported that blistering occurred after the CdCl2 treatment during the annealing process. Moreover, void formation was observed in the CdTe layer after the CdCl2 activation process. Voids at the cadmium sulphide (CdS)/CdTe junction caused delamination hence quality of the junction is poor. This issue has been known for more than two decades but the mechanisms of the blister formation have not been understood. One reason may be the stress formation during CdTe solar cells deposition or during the CdCl2 treatment. Therefore, the stress analysis was performed to remove the defects observed after the CdCl2 treatment. This was followed by the rapid thermal annealing to isolate the CdCl2 effect by simply annealing. Small bubbles observed in the CdTe layer which is the first step of the blister formation. Using high resolution transmission electron microscopy (HR-TEM), it has been discovered that argon (Ar) working gas trapped during the deposition process diffuses in the lattice which merge and form the bubbles during the annealing process and grow agglomeration mainly at interfaces and grain boundaries (GBs). Blister and void formation were observed in the CdTe devices after the CdCl2 treatment. Therefore, krypton (Kr), neon (Ne) gases were used as the magnetron working gas during the deposition of CdTe layer. The results presented in this thesis indicated that blister and void formation were still existing with the use of Kr an Ne. Xe, which has a higher atomic mass than Kr, Ne, Ar, Cd and Te, was used as the magnetron working gas and it resulted in surface blister and void free devices.

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