Experimental investigation of the glass transition of polystyrene thin films in a broad frequency range.

In this study, we investigate the α process of a polystyrene thin film using inelastic neutron scattering (INS), dielectric relaxation spectroscopy (DRS), and thermal expansion spectroscopy (TES). The DRS and TES measurements exhibited a decrease in glass transition temperature (T_{g}) with film thickness. On the other hand, an increase in T_{g} was observed in INS studies. In order to interpret this contradiction, we investigated the temperature dependence of the peak frequency (f_{m}) of the α process probed by DRS and TES. The experiments revealed an increase in the peak frequency (f_{m}) with decreasing film thickness in the frequency region. This observation is consistent with the observed decrease in T_{g} with thickness. Interestingly, the increase in T_{g} with film thickness was confirmed by fitting the temperature dependence measurements of the peak frequency with the Vogel-Fulcher-Tammann equation, within the frequency region probed by INS. The discrepancy between INS and DRS or TES descriptions of the α process is likely to be attributed to a decrease in the apparent activation energy with film thickness and reduced mobility, due to the impenetrable wall effect.