Polymer dewetting in solvent-non-solvent environment- new insights on dynamics and lithography-free patterning

We show that one may employ polymer dewetting in solvent-non-solvent environment to obtain lithography-free fabrication of well-defined nano- to micro- scale polymer droplets arrays from pre-patterned polymer films. The polymer droplet pattern may be converted to a series of hybrid organic-inorganic and inorganic well-defined nano-patterns by using sequential infiltration synthesis (SIS). In particular, we scrutinize the physical parameters which govern the dewetting of flat and striped polymer thin films, which is the key to obtaining our objective of lithography-free ordered nano-patterns.

We immerse polystyrene (PS) and polymethyl methacrylate (PMMA) thin films in water in the presence of chloroform vapors. We study the ensuing polymer dewetting dynamics and the pattern formation of nanospheres by employing in-situ light microscopy and scanning electron microscopy. We then investigate pattern formation by dewetting of polymer stripes, fabricated by directed solvent evaporation, and SIS of AlO_x from vapor phase precursors, trimethyl aluminum (TMA) and H₂O, within the nanosphere patterns.

We find that solvent- non-solvent environments render film dewetting rates, which are an order of magnitude faster than solvent vapor dewetting, and supports the formation of small solid polymer droplets, down to sub-100 nm droplet size, of large contact angles with the solid substrate. Pre-patterned polymer film stripes support the formation of highly ordered structures of polymer droplets, which are easily transformed to hybrid polymer-AlO_x nanosphere patterns and templated AlO_x nanosphere via SIS.