Pattern formation and evolution in thin polymer films

Abstract

Thin polymer films are important for many technologies. They are used as coatings, adhesives, lubricants and for device technologies, such as polymer based light-emitting diodes. Several concerns arise when processing and using thin polymer films. Properties of thin polymer films (e.g., viscosity, diffusion, glass transition temperature) are different from bulk properties due to finite size effects (e.g., confinement of the chains) and to interfacial interactions (e.g., presence of the free surface and the substrate). Moreover, the stability of the film on the substrate is of concern. Thin polymer films, of thickness h < 100 nm, fabricated on a substrate may rupture under destabilizing forces, such as van der Waals forces. Rupturing exposes the underlying substrate and the exposed regions will grow, provided that the spreading coefficient is negative. This process is known as dewetting. Thus far, two dewetting morphologies have been vii identified but little is understood about their formation and evolution. The first morphology consists of circular holes throughout the film and the second morphology is reminiscent of patterns associated with spinodal decomposition processes. In this research, we investigated four problems. First, we examined fundamental questions related to the formation and evolution of patterns on the substrate. We documented the existence of different dynamic stages of evolution associated with different driving forces for both “conventional” morphologies (circular holes and “spinodal-like”). Second, we discovered a new morphology that occurs in a thin random copolymer film on a silicon substrate. This morphology results from heterogeneous interactions of the chain segments with the substrate. Third, we examined flow processes in thin polymer films (chain dynamics near surfaces). We show that a fingering instability develop spontaneously at the moving liquid front when the film is below a critical thickness that depends on the length of the chains. This behavior is an intrinsic property of entangled polymer liquids and is nonexistent in simple liquids under the same flow conditions. Fourth and finally, based on our understanding of structural instabilities in thin films, we developed an alternate method to measure viscosity as a function of film thickness in these systems.