Dynamical heterogeneity in a vapor-deposited polymer glass

Recently, there has been great interest in "ultrastable" glasses formed via vapor deposition, both because of emerging engineering applications of these materials (e.g., active layers in light-emitting diodes and photovoltaics) and, theoretically, as materials for probing the equilibrium properties of glassy materials below their glass transition, based on the conjecture that these materials are equivalent to glassy materials aged over astronomical time scales. We use molecular dynamics simulations to examine the properties of ultrastable vapor-deposited and ordinary polymer glasses. Based on the difference in the energy of the deposited and ordinary films, we estimate the effective cooling rate for the vapor deposited films to be 1 to 3 orders of magnitude larger than that of the ordinary film, depending on the deposition temperature. Similarly, we find an increase in the average segmental relaxation time of the vapor-deposited film compared to the ordinary glass. On the other hand, the normal mode spectrum is essentially identical for the vapor-deposited and the ordinary glass film, suggesting that the high-frequency dynamics should be similar. In short, the segmental relaxation dynamics of the polymer vapor-deposited glass are consistent with those of an ordinary polymer glass with a somewhat slower effective cooling rate. Of course, one would expect a larger effect on dynamics approaching the experimental glass transition, where the cooling rates are much slower than accessible in simulation. To more precisely probe the relationship between the dynamics of these glasses, we examine dynamical heterogeneity within the film. Due to the substantial mobility gradient in the glassy films, we find that it is crucial to distinguish the dynamics of the middle part of the film from those of the entire film. Considering the film as a whole, the average dynamical heterogeneity is dominated by the mobility gradient, and as a consequence the heterogeneity is nearly indistinguishable between the ordinary and vapor deposited glass films. In contrast, in the middle part of the film, where there is almost no mobility gradient, we find the dynamical heterogeneity within the deposited film is somewhat larger than that of the ordinary film at the same temperature. We further show that the scale of the interfacial region grows on cooling in the equilibrium film, but this trend reverses in the glass state. We attribute this reversal in part to a shrinking ratio of the relaxation time in the middle of the film to that of the interfacial layer in the non-equilibrium state. The dynamics in this mobile interfacial layer for the ordinary and deposited film are nearly the same, suggesting that the interfacial region is always in a near-equilibrium state. These results emphasize the importance of distinguishing between interfacial and internal relaxation processes in this emerging class of materials.