White-light induced grafting of 3-MPA on the Si(111)–H surface for catalyzing Au nanoparticles’ in situ growth

A novel, mild and effective method was designed for grafting of high-quality organic monolayers on a silicon surface to catalyze nanoparticles' growth. By using a white-light source, 3-mercaptopropionic acid (3-MPA) molecules were attached to hydrogen-terminated Si(111) surfaces at room temperature. The attached monolayers were characterized using X-ray photoelectron spectroscopy to provide detailed information. The in situ growth of Au nanoparticles (AuNPs) with dimensions below 20 nm was catalyzed on a silicon surface with highly uniform and compact structure morphology. The AuNPs can grow selectively in a certain region on a patterned Si-Si3N4 chip. p-Nitrothiophenol (p-NTP) was used as the probe to evaluate the SERS enhancement of the highly uniform and compact AuNP-Si substrate. In order to better understand the white light initiation of the addition reaction of 3-MPA on the Si(111)-H surface, the mechanism was elucidated by density functional theoretical (DFT) calculations, which indicated that the formation of the Si-O bond occurred at the PEC of the first singlet excited state (S1) with a very low activation barrier about 30% of the ground state (S0) value.