Organometallic chemistry on silicon surfaces: formation of functional monolayers bound through Si–C bonds

Wet chemical routes to the assembly of organic monolayers on silicon surfaces via the formation of Si–C bonds: surface preparation, passivation and functionalization

“…51,52,168 For further details on the early body of work on the photochemical hydrosilylation, the reader should consult the comprehensive reviews of Buriak. 27,28 Here we will mainly focus our discussion on more recent advances, while trying to bring to the attention of the reader the need for conclusive data to resolve the details of the surface hydrosilylation reaction mechanism, both under illumination and thermal conditions. Interestingly, as discovered by Stewart and Buriak 170 for porous silicon and more recently reported by Sudho¨lter and co-workers for crystalline Si(100) and Si (111) substrates (Fig.…”

Carboxyl functionalization of ultrasmall luminescent silicon nanoparticles through thermal hydrosilylation

“…However, unlike the II-VI systems, silicon has a low inherent toxicity 20 and can form strong and stable covalent bonds with organic materials, providing for a much broader range of possible surface chemistries and functionalities. 21,22 Along with their excellent compatibility with Si-based electronics, this makes possible a wide range of applications for Si-np from biological labeling 8 to inorganic-organic hybrid microelectronics. 5,6 In addition,…”

“…In this process, the terminal double bond of the organic linker is directly inserted into a Si-H bond to form the Si-C linkage without breaking Si-Si bonds. 21,22 In this work, we report on hydrosilylation between ultrasmall (y1 nm) Si-np-H and an v-functional, 1-alkene to prepare ester and carboxyl functionalized nanoparticles (Si-np-COOX, X = Me or H). Nuclear magnetic resonance (NMR), infrared absorption spectroscopy (FTIR), size exclusion chromatography (SEC), and PL spectroscopy are used to characterize the Si-np dispersions.…”

“…38 Similarly, alkylation with Grignard or alkyl lithium reagents occurs through nucleophilic attack by a carbanion on an electron deficient Si atom, cleaving a Si-Si bond to form Si-C and silyl anion (Si 2 ) species. 21,22 To generate a highly robust system, it is preferable to minimize reactions such as these that can degrade the Si core and irreversibly quench their PL. As was demonstrated on flat, [39][40][41][42][43] porous, 21,22,[44][45][46] and nanocrystalline 8,[31][32][33] hydride-terminated Si, this can be accomplished through hydrosilylation with 1-alkenes.…”

Vapor-phase silanization of oxidized porous silicon for stabilizing composition and photoluminescence

“…23 As a result, modification of the porous silicon surface appears highly attractive since it might provide a more stable surface which could be used as a tool, either for device applications or for the test of fundamental models aiming at explaining the mechanisms involved in the luminescence of porous silicon. 24 One strategy for achieving stability of PSi is to tether passivative ligands to the surface by reacting it with the silicon hydride covering freshly formed porous silicon, [25][26][27] but the stabilizing effect of the bulk silicon that leads to slow reaction kinetics hinders their use as surface modification agents. 28 As to silicon-based substrates, the most commonly used method for surface derivative is silanization, which generally occurs at the surface of SiO 2 .…”