Effect of Plasma Treatment and TMCTS Vapor Annealing on the Reinforcement of Porous low-k Films

A novel process of TMCTS vapor annealing combined with a plasma treatment has been developed for improving the mechanical strength of porous silica films having ultralow dielectric constant. When porous silica films annealed under 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS) vapor were treated with argon plasma and then re-treated with TMCTS vapor, the mechanical strength (i.e., elastic modulus, hardness) of the films increased significantly. Results of Fourier transform infrared spectroscopy (FT-IR) suggested an accelerative effect resulted from the plasma treatment on the conversion of Si-CH3 and Si-H groups to Si-OH groups. The latter group appears to react faster with TMCTS from the second annealing to form cross-linked polymer network on the porous silica wall surfaces. The resulting cross-linked network is thought to keep the low permittivity and enhance the mechanical strength of the low-k films.