Ethan Glor

Long-range correlated dynamics in ultra-thin molecular glass films

It has been previously shown that the free surface of molecular glasses has enhanced surface diffusion compared to the bulk. However, the degree by which the glass dynamics are affected by the free surface remains unexplored. Here, we measure enhanced dynamics in ultra-thin molecular glass films as a function of film thickness. We demonstrate that these films exhibit a sharp transition from glassy solid to liquid-like behavior when the thickness is reduced below 30 nm. This liquid-like behavior persists even at temperatures well below the glass transition temperature, Tg. The enhanced dynamics in these films can produce large scale morphological features during physical vapor deposition and lead to a dewetting instability in films held at temperatures as low as Tg − 35 K. The effective viscosity of these films are measured by monitoring the dewetting kinetics. These measurements combined with cooling-rate dependent Tg measurements show that the apparent activation barrier for rearrangement decreases sharp...

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 Tgs (<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).

Cooling Rate Dependent Ellipsometry Measurements to Determine the Dynamics of Thin Glassy Films.

This report aims to fully describe the experimental technique of using ellipsometry for cooling rate dependent Tg (CR-Tg) experiments. These measurements are simple high-throughput characterization experiments, which can determine the glass transition temperature (Tg), average dynamics, fragility and the expansion coefficient of the super-cooled liquid and glassy states for a variety of glassy materials. This technique allows for these parameters to be measured in a single experiment, while other methods must combine a variety of different techniques to investigate all of these properties. Measurements of dynamics close to Tg are particularly challenging. The advantage of cooling rate dependent Tg measurements over other methods which directly probe bulk and surface relaxation dynamics is that they are relatively quick and simple experiments, which do not utilize fluorophores or other complicated experimental techniques. Furthermore, this technique probes the average dynamics of technologically relevant thin films in temperature and relaxation time (τα) regimes relevant to the glass transition (τα > 100 sec). The limitation to using ellipsometry for cooling rate dependent Tg experiments is that it cannot probe relaxation times relevant to measurements of viscosity (τα << 1 sec). Other cooling rate dependent Tg measurement techniques, however, can extend the CR-Tg method to faster relaxation times. Furthermore, this technique can be used for any glassy system so long as the integrity of the film remains throughout the experiment.