Effect of surfactants on the porogen size in the low-k methylsilsesquioxane/polystyrene hybrid films

An anionic surfactant, sodium dodecylbenzenesulfonate (NaDBS) and a cationic surfactant, domiphen bromide (DB) were used to modify the surface potential of polystyrene (PS) porogen in a post-integration porogen removal scheme. The effect of surfactant modification on the porogen and pore size in the low-k methylsilsesquioxane (MSQ)/PS hybrid films at 10 wt% PS loading, under a slow curing rate, was studied by grazing incidence small-angle X-ray scattering, viscosity measurement, and Fourier-transform infrared analysis. For PS porogen without modification, the porogen aggregated and its size increased from 10.0 to 16.5 nm at different rates, up to 200 degrees C, depending on the porogen diffusivity and steric hindrance by the successively cross-linked MSQ matrix at T >= T-g. In contrast, the NaDBS- and DB-modified porogens with higher surface potential impede their aggregation within the cross-linking MSQ matrix, resulting in a smaller porogen size, by electrostatic repulsion and increased viscosity due to electroviscous effect. Also, the columbic attraction between Si-OH groups of MSQ matrix and the positively charged, DB-modified PS, restrains the PS porogen, thus reduces its aggregation during cure step, leading to a small porogen size and tight distribution (8.7 +/- 2 nm) at 200 degrees C and later a similar pore size after porogen removal at 400 degrees C. (C) 2012 Elsevier Inc. All rights reserved.