Wet chemical surface functionalization of oxide-free silicon

Silicon is by far the most important semiconductor material in the microelectronic industry mostly due to the high quality of the Si/SiO2 interface. Consequently, applications requiring chemical functionalization of Si substrates have focused on molecular grafting of SiO2 surfaces. Unfortunately, there are practical problems affecting homogeneity and stability of many organic layers grafted on silicon oxide (SiO2), such as silanes and phosphonates, related to polymerization and hydrolysis of Si-O-Si and Si-O-P bonds. These issues have stimulated efforts in grafting functional molecules on oxide-free Si surfaces, mostly with wet chemical processes. This review focuses therefore directly on wet-chemical surface functionalization of oxide-free Si surfaces, starting from H-terminated Si surfaces. The main preparation methods of oxide-free H-terminated Si and their stability are first summarized. Functionalization is then classified into indirect substitution of H-termination by functional organic molecules, such as hydrosilylation, and direct substitution by other atoms (e.g. halogens) or small functional groups (e.g. OH, NH2) that can be used for further reaction. An emphasis is placed on a recently discovered method to produce a nanopattern of functional groups on otherwise oxide-free, H-terminated and atomically flat Si(111) surfaces. Such model surfaces are particularly interesting because they make it possible to derive fundamental knowledge of surface chemical reactions.