Grafting of 'push-pull' systems on germanium: towards the electric passivation

Despite its excellent electronic properties, germanium is limited by the low passivation of its oxide. Therefore, new dielectrics must be developed. Furthermore, germanium sensitivity requires the creation of a passivation layer on the surface. Even if numerous studies were carried out on new inorganic dielectrics, this research project concerns the design, the realization and the development of thin passivating organic dielectric films on germanium for nanoelectronics applications. This work principally involves the synthesis of new push-pull molecules (π-conjugated systems bearing a donor and an acceptor part) and germanium functionalization. New donor-acceptor systems and π-conjugated linear systems containing an anchoring group were synthesized through new ways. In particular, a series of azobenzene derivatives with different acceptors (fluorinated groups, pyridinium, nitro) and donors (amines, alkoxyl) and various anchoring groups (thiol, carboxylic acid, diazonium salt, triazene) was obtained. Meanwhile, preparation and functionalization of germanium surfaces was studied. A new process to etch the native oxide and obtain halogenated surfaces with low roughness was developed. Germanium substrates were then functionalized with thiol but also with diazonium salts. This new spontaneous grafting process considerably decreased the reaction time (15 minutes spontaneous grafting of diazonium salts against 3 days for self-assembled monolayers of thiol formation) in mild conditions. Thin films obtained present stability similar to the one of thiol monolayers. Π-conjugated linear systems were grafted both as thiol and diazonium salt to probe the influence of the aromatic core on the film formation and properties. Finally, push-pull systems were also grafted. Electronic studies on gold with π-conjugated systems were realized. These studies were extended to germanium and allow expecting significant results with push-pull molecules.