Viscoelastic leveling of annealed thin polystyrene films

Theoretical and experimental work on nanoscale viscoelastic flows of polystyrene melts is presented. The reflow above the glass transition temperature (Tg) of a continuous patterned film is characterized. Attention is paid to the topographical consequences of the flow rather than to the temporal description of the leveling of the film. In the framework of capillary wave theory, it is shown that only the shortest spatial wavelengths of the topography exhibit an elastic behavior, while long waves follow a viscous decay. The threshold wavelength depends on the surface tension, on the elastic plateau modulus, and, for ultrathin films, on the film thickness. Besides, for polystyrene, this threshold is a nanoscale parameter and weakly depends on the temperature of annealing. Experiments are conducted on polystyrene 130 kg/mol submicrometer films. The samples are embossed using thermal nanoimprint technology and then annealed at different temperatures between Tg + 10 °C and Tg + 50 °C. The smoothed topographies of the films are measured by atomic force microscopy and compared to a single-mode Maxwell leveling model and a more elaborated model based on reptation theory. © 2014 American Chemical Society