Surface-Bulk Interplay in Vapor-Deposited Glasses: Crossover Length and the Origin of Front Transformation.

Thin film stable glasses transform into a liquid by a moving front that propagates from surfaces or interfaces with higher mobility. We use calorimetric data of vapor-deposited glasses of different thicknesses and stabilities to identify the role of glassy and liquid dynamics on the transformation process. By invoking the existence of an ultrathin intermediate layer whose transformation strongly depends on the properties of both the liquid and the glass, we show that the recovery to equilibrium is driven by the mismatch in the dynamics between glass and liquid. The lifetime of this intermediate layer associated with the moving front is the geometric mean between the bulk transformation time and the alpha relaxation time. Within this view, we explain the observed dependencies of the growth front velocity and the crossover length with both stability and temperature. Extrapolation of these results points towards ordinary thin film glasses transforming via a frontlike transformation mechanism if heated sufficiently fast, establishing a close connection between vapor-deposited and liquid-cooled glasses.

Kinetic arrest of front transformation to gain access to the bulk glass transition in ultrathin films of vapour-deposited glasses.

Physical vapour deposition has emerged as the technique to obtain glasses of unbeatable stability. However, vapour deposited glasses exhibit a different transformation mechanism to ordinary glasses produced from liquid. Vapour deposited glasses of different thermodynamic stability, from ultrastable to those similar to ordinary glasses, transform into the liquid state via front propagation starting at the most mobile surfaces/interfaces, at least for the first stages of the transformation, eventually dynamiting the high thermal stability achieved for some of these glasses. A previous study showed that it was possible to avoid this transformation front by capping the films with a higher Tg material. We show here fast calorimetry measurements on TPD and IMC vapour deposited glasses capped respectively with TCTA and TPD. This capped configuration is very effective in suppressing the heterogeneous transformation of the stable glasses into the supercooled liquid and shifts the devitrification temperature to much higher values, where the bulk homogeneous mechanism becomes active. This approach may be useful to further study the bulk glass transition in thin films.