Effect of mold treatment by solvent on PDMS molding into nanoholes

Polydimethylsiloxane (PDMS) is the most popular and versatile material for soft lithography due to its flexibility and easy fabrication by molding process. However, for nanoscale patterns, it is challenging to fill uncured PDMS into the holes or trenches on the master mold that is coated with a silane anti-adhesion layer needed for clean demolding. PDMS filling was previously found to be facilitated by diluting it with toluene or hexane, which was attributed to the great reduction of viscosity for diluted PDMS. Here, we suggest that the reason behind the improved filling for diluted PDMS is that the diluent solvent increases in situ the surface energy of the silane-treated mold and thus the wetting of PDMS to the mold surface. We treated the master mold surface (that was already coated with a silane anti-adhesion monolayer) with toluene or hexane, and found that the filling by undiluted PMDS into the nanoscale holes on the master mold was improved despite the high viscosity of the undiluted PDMS. A simple estimation based on capillary filing into a channel also gives a filling time on the millisecond scale, which implies that the viscosity of PMDS should not be the limiting factor. We achieved a hole filling down to sub-200-nm diameter that is smaller than those of the previous studies using regular Sylgard PDMS (not hard PDMS, Dow Corning Corporation, Midland, MI, USA). However, we are not able to explain using a simple argument based on wetting property why smaller, e.g., sub-100-nm holes, cannot be filled, for which we suggested a few possible factors for its explanation.