Investigation of the drastic change in the sputter rate of polymers at low ion fluence

The polymer sputter rate dependence on ion fluence and ion chemistry (Ar, N2, O2) at 1 keV energy was investigated using a quartz crystal microbalance (QCM) which allowed to do real time etch rate measurements and to study kinetics of sputtering. The obtained sputter rates differed drastically from polymer to polymer showing, that the chemical structure of polymer is an important factor in the polymer etch yield. A decrease in the sputter rate was observed up to ion fluence of 5 x 1014-5 x 1015 cm-2 (depending on the polymer type and ion chemistry) followed by the saturation in the rate at prolonged ion bombardment. Polymer removal was accompanied by the formation of degradation products, cross-linking or branching, modification of the surface chemical structure, which was studied in situ using XPS. The dependence of the surface glass transition temperature, T gs on the ion fluence was studied using the method based on the embedding of metallic nanoparticles. The correlation between chemical yield data and ablation rate is discussed