Contraction and reexpansion of polymer thin films.

We report x-ray reflectivity measurements on polystyrene thin films supported on silicon wafer. In annealing experiments, we found fast and slow contraction processes in the thin films above the glass transition temperature. The former is the normal relaxation (annealing) process observed in bulk, and the latter is unexpected and enhanced in thin films below approximately 20 nm. In addition, we found unexpected extremely slow reexpansion processes in the glassy state. These unexpected very slow processes are discussed in terms of lateral contraction and expansion processes driven by entropic changes at the interfaces and the difference of the expansivities between polystyrene and silicon wafer.