We have studied CF4/O2 based plasma and reactive ion etching of dc magnetron-sputtered tungsten, chemical vapor deposited tungsten silicide and single-crystal silicon. Etch rates and optical emission intensities of atomic fluorine and oxygen in the gas phase were determined as a function of gas composition. Etched surfaces were characterized using in situ x-ray photoelectron spectroscopy (XPS) and low-energy ion scattering spectrometry. All three materials exhibit an etch rate maximum as a function of oxygen addition. For silicon (7% 02) and WSi2 (10% 02) it occurs for a smaller percentage of added oxygen than the optical emission maximum of atomic fluorine (15% 02), whereas for W films (35% 02) it occurs at a greater percentage of added oxygen. In postplasma XPS analysis it is shown that for all materials the etch rate decrease coincides with the onset of significant oxidation. From the analysis of the degree of fluorination of the top surface, the oxygen/fluorine ratio of the reaction layer, and the oxygen percentage of the etch rate maximum relative to the fluorine emission maximum, we conclude that the etching of Si and WSi2 is limited by a reduction of fluorine adsorption because of competitive oxygen adsorption. For tungsten, which shows a very low degree of fluorination of the top surface, both the drop in etch rate and the formation of tungsten oxide can be explained by a reduced arrival rate of fluorine atoms to the tungsten surface when etching in oxygen-rich gas mixtures. © 1989, American Vacuum Society. All rights reserved.