Changes in the temperature-dependent specific volume of supported polystyrene films with film thickness

Recent studies have measured or predicted thickness-dependent shifts in density or specific volume of polymer films as a possible means of understanding changes in the glass transition temperature Tg(h) with decreasing film thickness with some experimental works claiming unrealistically large (25%-30%) increases in film density with decreasing thickness. Here we use ellipsometry to measure the temperature-dependent index of refraction of polystyrene (PS) films supported on silicon and investigate the validity of the commonly used Lorentz-Lorenz equation for inferring changes in density or specific volume from very thin films. We find that the density (specific volume) of these supported PS films does not vary by more than ±0.4% of the bulk value for film thicknesses above 30 nm, and that the small variations we do observe are uncorrelated with any free volume explanation for the Tg(h) decrease exhibited by these films. We conclude that the derivation of the Lorentz-Lorenz equation becomes invalid for very thin films as the film thickness approaches ∼20 nm, and that reports of large density changes greater than ±1% of bulk for films thinner than this likely suffer from breakdown in the validity of this equation or in the difficulties associated with accurately measuring the index of refraction of such thin films. For larger film thicknesses, we do observed small variations in the effective specific volume of the films of 0.4 ± 0.2%, outside of our experimental error. These shifts occur simultaneously in both the liquid and glassy regimes uniformly together starting at film thicknesses less than ∼120 nm but appear to be uncorrelated with Tg(h) decreases; possible causes for these variations are discussed.