Film thickness dependent ordering dynamics of lamellar forming diblock copolymer thin films

Ellipsometry is used in a novel way to study the ordering dynamics of symmetric poly(styrene-methyl methacrylate) diblock copolymer thin films. Ordered thin films form lamellae parallel to the substrate which can form islands or holes at the free surface to ensure commensurability of the layers. The sensitivity of ellipsometry provides the unique ability to probe morphological changes during the ordering process before the ultimate formation of islands or holes at the free surface. We observe three distinct stages in the ordering process: i) an ordering into an intermediate state, ii) an incubation time where the film structure remains constant and iii) the nucleation of islands or holes to achieve equilibrium lamellar morphology. The time-resolved measurement of an incubation period and initial ordering stage provides a means for studying the effect of thickness on the ordering kinetics. The dependence of incubation time on the commensurability of the initial film height is explained using strong segregation theory.Graphical abstract