Bashouti, M.Y.; Garzuzi, C.A.; de la Mata, M.; Arbiol, J.; Ristein, J.; Haick, H.; Christiansen, S.: Role of Silicon Nanowire Diameter for Alkyl (Chain Lengths C1-C18) Passivation Efficiency through Si-C Bonds. Langmuir 31 (2015), p. 2430-2437
10.1021/la5047244
Abstract:
The effect of silicon nanowire (Si NW) diameter on the functionalization efficiency as given by covalent Si−C bond formation is studied for two distinct examples of 25 ± 5 and 50 ± 5 nm diameters (Si NW25 and Si NW50, respectively). A two-step chlorination/alkylation process is used to connect alkyl chains of various lengths (C1−C18) to thinner and thicker Si NWs. The shorter the alkyl chain lengths, the larger the surface coverage of the two studied Si NWs. Increasing the alkyl chain length (C2−C9) changes the coverage on the NWs: while for Si NW25 90 ± 10% of all surface sites are covered with Si−C bonds, only 50 ± 10% of all surface sites are covered with Si−C bonds for the Si NW50 wires. Increasing the chain length further to C14−C18 decreases the alkyl coverage to 36 ± 6% in thin Si NW25 and to 20 ± 5% in thick Si NW50. These findings can be interpreted as being a result of increased steric hindrance of Si−C bond formation for longer chain lengths and higher surface energy for the thinner Si NWs. As a direct consequence of these findings, Si NW surfaces have different stabilities against oxidation: they are more stable at higher Si−C bond coverage, and the surface stability was found to be dependent on the Si−C binding energy itself. The Si−C binding energy differs according to (C1−9)−Si NW > (C14−18)−Si NW, i.e., the shorter the alkyl chain, the greater the Si−C binding energy. However, the oxidation resistance of the (C2−18)−Si NW25 is lower than for equivalent Si NW50 surfaces as explained and experimentally substantiated based on electronic (XPS and KP) and structure (TEM and HAADF) measurements.