Olefin additions on H-Si(111): evidence for a surface chain reaction initiated at isolated dangling bonds

We report the surface chain reaction of styrene with hydrogen-terminated Si(111), H-Si(111) initiated at isolated surface dangling bonds. Electrons from a scanning tunneling microscope in ultrahigh vacuum are used to create surface isolated dangling bonds on H-Si(111) prepared by aqueous ammonium fluoride etch. Exposure of dangling bonds on an otherwise hydrogen terminated surface to as little as 5 langmuirs of styrene leads to the formation of compact islands containing multiple styrene adsorbates bonded to the surface through individual C-Si bonds. From this observation we conclude that these adsorbate islands are the result of a surface chain reaction of styrene with H-Si(111). This result suggests that the key radical-chain propagation step of hydrogen atom abstraction from the silicon surface for the proposed mechanism of reaction of liquid phase terminally unsaturated organic molecules with hydrogen-terminated silicon under free-radical conditions readily occurs.NRC publication: Ye