The etching of Si, SiO2, Si3N4, and SiCH in fluorocarbon plasmas is accompanied by the formation of a thin steady-state fluorocarbon film at the substrate surface. The thickness of this film and the substrate etch rate have often been related. In the present work, this film has been characterized for a wide range of processing conditions in a high-density plasma reactor. It was found that the thickness of this fluorocarbon film is not necessarily the main parameter controlling the substrate etch rate. When varying the self-bias voltage, for example, we found a weak correlation between the etch rate of the substrate and the fluorocarbon film thickness. Instead, for a wide range of processing conditions, it was found that ion-induced defluorination of the fluorocarbon film plays a major role in the etching process. We therefore suggest that the fluorocarbon film can be an important source of fluorine and is not necessarily an etch-inhibiting film. © 2004 American Vacuum Society.