Influence of Substrate Temperature on the Transformation Front Velocities That Determine Thermal Stability of Vapor-Deposited Glasses

Stable organic glasses prepared by physical vapor deposition transform into the supercooled liquid via propagating fronts of molecular mobility, a mechanism different from that exhibited by glasses prepared by cooling the liquid. Here we show that spectroscopic ellipsometry can directly observe this front-based mechanism in real time and explore how the velocity of the front depends upon the substrate temperature during deposition. For the model glass former indomethacin, we detect surface-initiated mobility fronts in glasses formed at substrate temperatures between 0.68Tg and 0.94Tg. At each of two annealing temperatures, the substrate temperature during deposition can change the transformation front velocity by a factor of 6, and these changes are imperfectly correlated with the density of the glass. We also observe substrate-initiated fronts at some substrate temperatures. By connecting with theoretical work, we are able to infer the relative mobilities of stable glasses prepared at different substrate temperatures. An understanding of the transformation behavior of vapor-deposited glasses may be relevant for extending the lifetime of organic semiconducting devices.