Polystyrene thin films in CO(2).

Abstract

In air, or vacuum environments, liquid polystyrene (PS) thin films (thickness, h<100 nm ) supported by SiOx /Si substrates are structurally metastable or unstable, depending on film thickness. They rupture and eventually form droplets on the SiOx /Si substrates (dewet) due to the influence of destabilizing long-ranged van der Waals dispersion forces. We used scanning force microscopy to examine the structural stability of liquid PS films in the thickness range 5 nm<h<100 nm in liquid and in supercritical carbon dioxide ( CO2 ) environments. All films in this thickness range were metastable; holes developed throughout the films and over time these holes grew, impinged, and eventually formed droplets. The rate of destabilization is controlled by three factors: film thickness, temperature, and CO2 pressure (which dictates CO2 volume fraction in the films). Calculations of the effective interface potentials suggest that the energy barrier for nucleation and growth of holes in CO2 is larger than that in air, and in the limit of vanishingly low PS volume fraction the films should be stable.