Thickness-dependence of block copolymer coarsening kinetics


Black, C.T.; Forrey, C.; Yager, K.G. "Thickness-dependence of block copolymer coarsening kinetics" Soft Matter 2017, 13 3275–3283.
doi: 10.1039/C7SM00212B


We demonstrate that partial films of block-copolymer material order more rapidly than complete layers, since film edges act as 'sinks' for defects.


Despite active research, many fundamental aspects of block copolymer ordering remain unresolved. We studied the thickness-dependence of block copolymer grain coarsening kinetics, and find that thinner films order more rapidly than thicker films. Bilayer films, or monolayers with partial layers of islands, order more slowly than monolayers because of the greater amount of material that must rearrange in a coordinated fashion. Sub-monolayer films order much more rapidly than monolayers, exhibiting considerably smaller activation energies, as well as larger exponents for the time-growth power-law. Using molecular dynamics simulations, we directly study the motion of defects in these film regimes. We attribute the enhanced grain growth in sub-monolayers to the film boundaries, where defects can be spontaneously eliminated. The boundaries thus act as efficient sinks for morphological defects, pointing towards methods for engineering rapid ordering of self-assembling thin films.