Surface modifications and etching mechanisms of several nanoporous low-k dielectrics (spin-on and PECVD) using fluorocarbon plasmas have been investigated by ToF-SIMS and AFM and compared with those of SiO2. The results show a fluoropolymer film growing on the materials using highly polymerizing discharges (C4F8). The fluoropolymers are converted into fluoroether-like compounds upon etching low-porosity dielectrics in ion-rich C4F8/90% Ar plasmas. These layers mitigate the influx of plasma species and inhibit the etching rate. No surface roughness develops for these conditions, keeping the plasma/material interaction regime stationary. On the other hand, the surface coverage by fluoroethers is reduced when the porosity exceeds a given threshold. Consequently, direct plasma/dielectric interactions including ion bombardment take place, causing an increase of the etching rate, surface roughening and severe modifications of the pristine dielectric. (c) 2006 Elsevier B.V. All rights reserved.