Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends

The slow kinetics of block copolymer self assembly may hinder, or even prevent, the realization of expected equilibrium ordered morphologies. Here we investigate the self assembly kinetics of cylinder-forming polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) and its corresponding ternary blends with low molecular weight PS and PMMA in thin films ranging from <1 to several cylinder layers in thickness. In situ grazing-incidence X-ray scattering coupled with ex situ electron microscopy reveals pathway-dependent ordering substantially altered by homopolymer blending. In particular, the neat (unblended) block copolymer (BCP) is kinetically frustrated in films more than similar to 1 cylinder layer thick and is unable to reach a state of ordered hexagonally packed cylinders during the annealing interval. On the other hand, while blends exhibit similar pattern coarsening behavior to neat BCPs for hexagonally ordered cylinders, reorientation transitions between vertical or horizontal cylinders are dramatically accelerated in blend thin films. We infer that more rapid early stage ordering observed in blends can be attributed in part to faster reorientation transitions.