Character of the glass transition in thin supported polymer films

We have used ellipsometry to study the thermal expansivity of thin polystyrene films on silicon substrates with thicknesses of 10–200 nm. We find well-defined glass transitions, and detailed analysis of the expansivities shows that for thinner films the transition width is broadened, while the strength of the transition, defined by the difference between the expansivities in the liquid and glassy state, is reduced; the expansivity in the glassy state is higher than in the bulk. These phenomena are consistent with the idea that a layer of roughly constant thickness, of order 10 nm, near the surface of the film has liquidlike thermal properties at all experimental temperatures.