Thickness Dependence of the Glass Transition Temperature in Thin Polymer Films

In this study the glass transition temperature in thin polymer films has been studied. Ellipsometry has been used to measure $T_{g}$ of thin film as a function of film thickness. Empirical equation has been proposed to fit the measured $T_{g}$ pattern with thickness. Also, a continuous multilayer model was proposed and derived to describe the effect of surface on the observed $T_{g}$ reduction in thin films, and the depth-dependent $T_{g}$ profile was obtained. These results showed that $T_{g}$ at the top surface was much lower than the bulk $T_{g}$ and gradually approached the bulk $T_{g}$ with increasing distance from the edge of the film. The model and equation were modified to apply for the polymer coated on the strongly favorable substrate and the freely standing film.