Achieving Stable Patterns in Multicomponent Polymer Thin Films Using Marangoni and van der Waals Forces

Topographically patterned polymer films are promising for applications such as fabrication of integrated circuit elements in microelectronics, optical gratings, photonic crystals, and sensors and actuators. Liquid-air interfaces can be deformed by surface-tension gradients to create topography, a phenomenon useful for polymer film patterning. A recently developed method creates these gradients by photochemically patterning a solid polymer film. Heating the film to the liquid state leads to flow driven by the patterned surface-tension gradients, but capillary leveling and diffusion of surface-active species facilitate eventual dissipation of the topography. However, experiments demonstrate that using blends of high- and low-molar-mass polymers can considerably delay the decay in topography. To gain insight into this observation, we develop a model based on lubrication theory that yields coupled nonlinear partial differential equations describing how the film height and species concentrations evolve with time and space. Incorporation of a non-monotonic disjoining pressure is found to significantly increase the lifetime of topographical features, making the model predictions qualitatively consistent with experiments. A parametric study reveals the key variables controlling the kinetics of film deformation and provides guidelines for photochemically induced Marangoni patterning of polymer films.