Surface reactions and structural evolution of organosilicate glass under Ar plasma bombardment

Abstract

Ab initio molecular dynamics (AIMD) simulations with a variable time step setup were used to investigate collision reactions, collision cascades and subsequent structural changes of organosilicate glass (OSG) low-k dielectric surfaces under Ar plasma bombardment with kinetic energies up to 100eV. Reactions that result in carbon loss and glass network structure changes during plasma treatment were carefully examined, since carbon loss increases the dielectric constant of the low-k dielectrics and the susceptibility to water attack, thus adversely affecting the performance of these dielectric materials in microelectronic devices. Results from AIMD based collision cascade simulations have provided mechanistic understanding of collision reactions during plasma bombardment. It was found that Si–CH3 bond scission and CH3 abstraction reactions are the primary methods of carbon loss. Two distinct mechanisms were identified for CH3 removal from 100eV plasma bombardment, one due to direct momentum transfer from the high-energy incident Ar atom to a Si–O bond on the OSG surface, and the other due to generation of highly reactive atomic oxygen radicals during collision cascades. Atomic oxygen radicals generated during cascades were found to occur at a rate of 1–3 per 100eV Ar impact with radical kinetic energies ranging from 2.2 to 42.6eV, well above the minimum energy of 0.1eV for Si–CH3 bond breakage. Both reaction mechanisms were examined through atomic charge analysis and the results indicated that the Ar atom ionizes when it impacts the OSG surface, causing temporary charge transfer from the Ar atom to the Si–O bond and playing a role in CH3 removal. The cascading atomic oxygen radicals and the ionization of the Ar atom during the Si–CH3 bond scission and CH3 removal demonstrate the secondary effects of Ar bombardment which must be considered during plasma etching of low-k dielectrics.