Film Thickness Dependent Stability and Glass Transition Temperature of Polymer Films Produced by Physical Vapor Deposition

We report measurements of the onset temperature of rejuvenation, T_{onset}, and the fictive temperature, T_{f}, for ultrathin stable polystyrene with thicknesses from 10 to 50 nm prepared by physical vapor deposition. We also measure the T_{g} of these glasses on the first cooling after rejuvenation as well as the density anomaly of the as-deposited material. Both the T_{g} in rejuvenated films and the T_{onset} in stable films decrease with decreasing film thickness. The T_{f} value increases for decreasing film thickness. The density increase typical of stable glasses also decreases with decreasing film thickness. Collectively, the results are consistent with a decrease in apparent T_{g} due to the existence of a mobile surface layer, as well as a decrease in the film stability as the thickness is decreased. The results provide the first self-consistent set of measurements of stability in ultrathin films of stable glass.