Hydrophobic recovery of cross-linked polydimethylsiloxane films and its consequence in soft nano patterning

Cross-linked polydimethylsiloxane (PDMS) films and surfaces obtained by thermal cross-linking of commercially available Sylgard 184 are widely utilized in many areas of science, due to superior thermal stability, low dielectric constant, transparency and biocompatibility. Cross-linked PDMS surfaces are weakly hydrophobic and several experiments, particularly the ones that utilize capillary-driven microscale flow require the modulation of the surface wettability. A well-known strategy to achieve the same is by exposing the Sylgard 184 surface to UV/ozone (UVO) treatment at room temperature. Depending on the duration of exposure, the wettability drops from hydrophobic to a near-complete wetting (water contact angle ~10°), due to the formation of a surface oxide layer. However, under normal atmospheric conditions, these surfaces recover their hydrophobicity over a period of time due to diffusive migration of the uncrosslinked oligomers to the surface, and formation of a hydrophobic dimethyl silicone layer. We explore the hydrophobic recovery process as a function of cross-linker concentration and UVO exposure time and show how a partially or fully recovered PDMS stamp may influence subsequent nanopatterning, including the possible creation of features with different morphology using a single stamp.