The role of the molecular weight of the adsorbed layer on a substrate in the suppressed dynamics of supported thin polystyrene films.

The adsorbed layer on a solid surface plays a crucial role in the dynamics of nanoconfinement polymer materials. However, the influence of the adsorbed layer is complex, and clarifying this influence on the dynamics of confined polymers remains a major challenge. In this paper, SiO2-Si substrates with various thicknesses and adsorbed layers of PS with various molecular weights were used to reveal the effect of the adsorbed layer on the corresponding segmental dynamics of the supported thin PS films. Strongly suppressed segmental dynamics of thin PS films were observed for the films supported on thicker adsorbed layers or prepared using higher molecular weight. Neutron reflectivity revealed that the overlap region thickness between the adsorbed layer and the top overlayer increased with increasing thickness and molecular weight of the adsorbed layer, both of which correlate well with the distance over which the polystyrene dynamics were depressed by the adsorbed layer. The results show that the influencing distance of the adsorbed layer is related to the overlap zone formed between the adsorption layer and the upper thin film. The effect of the adsorbed layer molecular weight can be ascribed to the fact that large loops and long tails in the adsorbed layer result in stronger interpenetrations and entanglements between polymer chains in the adsorbed layer and in the overlayer, causing a stronger substrate effect and suppression of the segment dynamics of the supported thin PS films.