Reaction mechanisms of thermal atomic oxygen interaction with organosilicate low k dielectric materials from ab initio molecular dynamics simulations

The interactions of the oxidizing plasma with the low k dielectric materials and the associated damage mechanisms are of great technological interest for processing current and next generation low k materials. Density functional theory based ab initio molecular dynamics simulations have been performed to evaluate the reaction mechanisms of thermal atomic oxygen [in triplet (³P) or singlet (¹D) state] with the organosilicate low k materials represented by model systems. The threshold kinetic energies of attacking atomic oxygen and the reaction pathway were found to be highly incident angle dependent. Carbon abstraction through methyl radical formation can happen at energy barriers as low as 0.1 eV when O radical attack occurs along the axes inclined to the Si–C bond. The simulation results agree well with recent experiments and support diffusion-controlled etching rate dependence, and dielectric constant increases due to oxygen plasma etching.