A structure of surface reaction layer of poly-Si substrate during fluorocarbon plasma etching was studied by using a plasma beam irradiation apparatus and a quasi-in situ x-ray photoelectron spectroscopy. A fluorinated silicon (SiF) layer was formed under a fluorocarbon (CF) layer. It was found that the thickness of the SiF layer linearly increased with the etch yield of poly-Si regardless of the change of the CF layer thickness. The average ratio of the number of Si to that of F in the SiF layer did not strongly depend on the etch yield. The carbon-rich region of the CF layer was formed just above the SiF layer due to the consumption of fluorine for the formation of SiF layer. (c) 2006 American Vacuum Society.