Lithography, lubrication and active components in organic electronic devices are diverse applications of polymer thin films. Confinement and interfacial interactions have a profound effect on the properties of thin films and are responsible for behavior that is often counterintuitive and difficult to predict. Phenomena ranging from interfacial instabilities to thickness-dependent properties such as the glass transition (T_g) and viscosity are challenges associated with the design, processing, fabrication and performance of polymer thin films. In this dissertation, we examined three basic problems: the first concerns the morphology of interfacial instabilities, the second is the film thickness dependence of the viscosity, and the third is the thickness dependence of the T_g of thin film polymer-polymer mixtures.

Thin liquid films in the nanometer thickness range often succumb to interfacial instabilities leading to break-up and droplet formation. While the destabilization process is well understood, the mechanisms by which the instability proceeds are not. One mechanism by which the dewetting process begins is with the formation and subsequent growth of circular holes. We show that fingering instabilities can develop at the periphery of these holes and that the morphology of the instability depends on chain length and the nature of the substrate-polymer interactions. The details of this secondary instability are examined and compared to fingering instabilities observed in macroscopic liquid fronts.

A related issue in these systems is that the dynamics can be film thickness dependent. Since the viscosity and capillary forces determine the dynamics of interfacial instabilities, the time dependence of the hole size provides a method to measure the viscosity of the film. We used this approach to examine the influence of carbon nanotubes on the dewetting dynamics and determine the thickness dependence of the viscosity, which was found to depend on the thickness dependent T_g of the system.

For the third problem, we examined the thickness dependence of the T_g of miscible thin film polymer-polymer mixtures. Using incoherent neutron scattering, and ellipsometry, we showed that effects associated with chain connectivity and dynamics of the individual blend components, together with interfacial interactions, determine the effective T_g of miscible polymer-polymer thin film mixtures.