Solvent quality influences surface structure of glassy polymer thin films after evaporation

Molecular dynamic simulations are used to investigate the structural effects of treating a glassy polymer thin film with solvents of varying quality and subsequently evaporating the solvent. Both a monodisperse film and a polydisperse film are studied for poor to good solvent conditions, including the limit in which the polymer film is fully dissolved. In agreement with previous studies, the dissolved polymer-solvent mixtures form a polymer-rich skin on top of the forming film during evaporation. In the case of the polydisperse films, a segregation of the lower molecular weight polymer to the film interface is observed. We provide a detailed, systematic analysis of the interface structure and properties during and after evaporation. We find that for non-dissolved films, the surface width of the film after solvent evaporation is enhanced compared to the case without solvent. Our results show that due to the kinetic arrest of the surface structure, the increased surface width is preserved after solvent evaporation for both mono- and polydisperse films. We conclude that it is important to take poor solvent effects into account for the surface morphology of already formed thin glassy films, an effect which is often neglected.