Mechanistic study of plasma damage of low k dielectric surfaces

Plasma damage to low k dielectric materials was investigated from a mechanistic point of view. Low k dielectric films were treated by Ar, O 2 , N 2 , N 2 ∕ H 2 , and H 2 plasmas in a standard reactive ion etching chamber and the damage was characterized by angle resolved x-ray photoelectron spectroscopy, x-ray reflectivity, Fourier transform infrared spectroscopy, and contact angle measurements. Both carbon depletion and surface densification were observed on the top surface of damaged low k materials while the bulk remained largely unaffected. Plasma damage was found to be a complicated phenomenon involving both chemical and physical effects, depending on chemical reactivity and the energy and mass of the plasma species. A downstream hybrid plasma source with separate ions and atomic radicals was employed to study their respective roles in the plasma damage process. Ions were found to play a more important role in the plasma damage process. The dielectric constant of low k materials can increase up to 20% due to plasma damage and we attributed this to the removal of the methyl group making the low k surface hydrophilic. Annealing was generally effective in mitigating moisture uptake to restore the k value but the recovery was less complete for higher energy plasmas. Quantum chemistry calculation confirmed that physisorbed water in low k materials induces the largest increase of dipole moments in comparison with changes of surface bonding configurations, and is primarily responsible for the dielectric constant increase.