Thickness-Dependent Segmental Dynamics in Supported Thin Films: Insights from a Dynamically Correlated Network Model

A large body of experimental studies shows that the local dynamics in supercooled liquids are significantly altered by spatial nanoconfinement. In a previous study, we proposed a concept of a dynamically correlated network (DCN) model, which assumes that segments in a supercooled liquid undergo cooperative rearrangements within a network-like cluster. We further demonstrated that a model modified for freestanding thin films can predict for the glass transition dynamics in atactic polystyrene (PS) films consistent with experimental results. In this study, we adapted the model to apply it to supported thin films by introducing a layer of virtual vacant segments at the free surface and virtual anchoring segments at the liquid/substrate interface. The latter segments, carrying a finite number of virtual segments, reduce mobility at the interface. We evaluated the cooperative cluster size and distribution with respect to temperature and film thickness, along with the average relaxation time and glass transition temperature <i>T</i>_g for supported thin films of PS. The model predicted that the thickness dependence of <i>T</i>_g for PS becomes stronger with increasing time scale, and this result agreed well with experimental data across different timescales from pseudothermodynamic and dynamic measurements. The results provide insights into the origin of the dynamical decoupling between pseudothermodynamic and dynamic glass transition behaviors.