In situRaman spectra ofSiHx,Si–F, and Si–Si vibrations from Si surfaces in HF aqueous solutions are obtained using a highly sensitive confocal microprobe Raman system. Electrochemical roughening pretreatment and laser-assisted roughening procedure enable good quality surface Raman spectra to be obtained. The surface Raman and photoluminescence spectra from the Si surface in the etching environment and the correlation of the two types of spectra are discussed. The Raman spectroscopy is shown to have high potential in serving as an important tool forin situinvestigating of Si surface bonding during the etching process. ©1998 American Institute of Physics.