Low-density polymer thin film formation in supercritical carbon dioxide

We report a method for producing stable low-density polymer films by using supercritical carbon dioxide (scCO2). Two different molecular weight polystyrene films with various thicknesses were exposed to scCO2 along the density fluctuation ridge in P–T phase diagram. The swollen structures could be then frozen by flash evaporation of CO2 without forming additional voids. X-ray reflectivity data clearly showed that exposure to scCO2 could be used to produce uniform low-density films of about 2Rg thick or less, where Rg is radius of polymer gyration.