Conditionnement et fonctionnalisation de la surface du nitrure de silicium

Abstract : Covalent grafting of organic molecules on glass can modify its surface physico-chemical properties or improve the adhesion of a coating. Such a functionalization usually relies on a silanisation reaction, bonding molecules to the surface through Si-O-Si bonds. Unfortunately, the resulting molecular layers do not exhibit long-term stability due to the hydrolysis of siloxane groups. One solution would consist in depositing a silicon nitride layer on glass, allowing the glass surface to be functionalized through more stable bonds N-C or Si-C. Silicon nitride layers are frequently used in glass industry. They are well-known for their durability properties and are often used as a protective layer against glass corrosion.The aim of this project is to characterize and control the non-oxidized silicon nitride surface, then to optimize and understand the surface modification by covalent grafting of organic molecules.When silicon nitride is exposed to atmosphere, an oxynitride layer is formed on its surface. Several efficient ways to remove this native oxynitride are first studied and optimized. The quantitative characterization and control of the surface chemical composition provide a reliable starting point for the functionalization step. The surface chemical composition is quantitatively investigated by combining Attenuated Total Reflection InfraRed spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and chemical dosing. The etching in HF-based solutions efficiently removes the oxynitride layer and leads to a surface mainly covered with Si-F bonds and smaller amounts of Si-OH and N-H bonds. The surface composition can be modified by a H2 plasma treatment performed after the wet etching or by changing the silicon nitride layer composition (silicon enrichment), leading in either case to the formation of Si-H bonds on surface. An etching mechanism is suggested from these experimental observations.The second part of this work is focused on the grafting of the alkyl chains on the silicon nitride surface. The surface is reacted with a 1-alkene, using photochemical or thermal activation. The grafting efficiency depends on the surface composition and the activation conditions. The presence of surface Si-H bonds and the effect of Si enrichment are considered in details. In a final part, in an applicative view, functional hydrophobic molecules are grafted on the silicon nitride surface.
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Marine Brunet. Conditionnement et fonctionnalisation de la surface du nitrure de silicium. Matériaux. Université Paris-Saclay, 2016. Français. ⟨NNT : 2016SACLX100⟩. ⟨tel-01508952⟩

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