Insights into glass surface dynamics from fast scanning calorimetry studies of softening and vaporization of ultrathin molecular films.

Chemical and physical processes on the surfaces of amorphous solids have been the focus of many studies over the past decades. These studies have established that dynamics in a thin layer near a glass surface are often dramatically faster than those in the glass bulk. Nevertheless, recent advances also emphasize the need for new experimental techniques capable of characterizing the structure and dynamics of the near-surface regions in glassy materials at the molecular length scale. Using a quasi-adiabatic fast scanning calorimetry (FSC) technique, we have investigated softening and vaporization of pure amorphous methylbenzene films of moderately heightened kinetic stability with thicknesses ranging from 1 to 20 nm. The analysis of the FSC thermograms reveals the existence of a high fictive temperature (liquid-like) layer on the surface of the solid glass with a thickness of 3.5 ± 0.5 nm or seven molecular diameters. Furthermore, the width of the boundary between liquid-like and solid layers in the films is less than 1 nm. These preliminary findings compliment and substantiate past determinations of the mobile surface layer thicknesses obtained by introduction of nanoparticles or spectroscopic molecular probes to near-surface regions of amorphous samples. The developed FSC methodology will advance the theoretical and computational research by providing calorimetric data on the enhanced interfacial dynamics phenomenon in a variety of low-molecular-weight amorphous materials.