Spatiotemporal Mapping of Hole Nucleation and Growth during Block Copolymer Terracing with High-Speed Atomic Force Microscopy

As a platform for investigating two-dimensional phase separation, we track the structural evolution of block copolymer thin films during thermal annealing with environmentally controlled atomic force microscopy (AFM). Upon thermal annealing, block copolymer films with incommensurate thickness separate into a terraced morphology decorated with holes. With in situ imaging at 200 °C, we follow the continuous progression of terrace formation in a single region of a cylinder-forming poly­(styrene-block-methyl methacrylate) thin film, beginning with the disordered morphology on an unpatterned silicon substrate and continuing through nucleation and coarsening stages. Topographic AFM imaging with nanoscale resolution simultaneously captures ensemble hole growth statistics while locally tracking polymer diffusion through measurements of the film thickness. At early times, we observe homogeneous hole nucleation and isotropic growth, with kinetics following the predictions of classical nucleation theory. At later times, however, we find anomalous hole growth which arises due to the combination of Ostwald ripening and coalescence mechanisms. In each case, our real-space observations highlight the importance of hole interactions for determining coarsening kinetics, mediated either through the interconnected phase for Ostwald ripening or through binary collision events for coalescence.