On the relationship between SiF4 plasma species and sample properties in ultra low-k etching processes

The temporal behavior of the molecular etching product SiF4 in fluorocarbon-based plasmas used for the dry etching of ultra low-k (ULK) materials has been brought into connection with the polymer deposition on the surface during plasma treatment within the scope of this work. For this purpose, time-resolved measurements of the density of SiF4 have been performed by quantum cascade laser absorption spectroscopy. A quantification of the non-linear time dependence was achieved by its characterization via a time constant of the decreasing SiF4 density over the process time. The time constant predicts how fast the stationary SiF4 density is reached. The higher the time constant is, the thicker the polymer film on top of the treated ultra low-k surface. A correlation between the time constant and the ULK damage was also found. ULK damage and polymer deposition were proven by Variable Angle Spectroscopic Ellipsometry and X-ray Photoelectron Spectroscopy. In summary, the observed decay of the etching product concentration over process time is caused by the suppressed desorption of the SiF4 molecules due to a more dominant adsorption of polymers.