Exploring the broadening and the existence of two glass transitions due to competing interfacial effects in thin, supported polymer films.

In this report, we use ellipsometry to characterize the glass transition in ultra-thin films of poly(2-vinyl pyridine) (P2VP) supported on a silicon substrate. P2VP is known to have attractive substrate interactions, which can increase the Tg of ultra-thin films compared to the bulk value. Here, we use an extended temperature range to show that the glass transition can be extremely broad, indicating that a large gradient of the dynamics exists through the film with slow dynamics near the substrate and enhanced dynamics at the free surface. To observe the effect of these two interfaces on the average thin film dynamics, cooling rate-dependent Tg (CR-Tg) measurements were used to indirectly probe the average relaxation times of the films. We demonstrate that ultra-thin films have lower fragility compared to bulk films, and, when cooled at slow cooling rates (<1 K/min), exhibit extreme broadening of the dynamics (<70 nm) and eventually complete decoupling between the free surface and substrate regions to produce films with two distinct Tg's (<16 nm). Tg,high increases with decreasing thickness in a similar manner to what has been observed in previous studies on P2VP, and Tg,low decreases with decreasing film thickness in a similar manner to what has been observed in polymer films with enhanced free surfaces and neutral substrate interactions. These observations indicate that the dynamics in thin films of P2VP can be strongly coupled over a length scale of ∼10-20 nm, resulting in two co-existing layers with two distinct glass transitions when the range of the dynamical gradients become too large to sustain (breadth of the transition > 50 K).