Photomodulated phase-separation kinetics in block copolymer melts: a DPD simulation study

Abstract

We study phase-separation kinetics of symmetric diblock copolymer (BCP) melt in (Formula presented.) subjected to sequential light on/off cycles. The incompatible blocks of each BCP chain are connected by a photosensitive bond, which undergoes breakage during photo-illumination (on-cycle) and recombination during the off-cycle. We set a shorter fixed time limit for each on-cycles and focus on analysing how the much longer duration of the light off-cycles affects the segregation kinetics. We explore two scenarios for each off-cycle time variation: one with equal and another with increasing durations. For both cases, we determine the rate constants for bond formation and degradation reactions and assess their influence on the dynamical scaling functions and the growth scale of evolving morphologies. The average domain size typically exhibits diffusive growth ((Formula presented.)) for a couple of cycles in the beginning. However, the domain growth nearly freezes during the rest of the cycles, resulting in bicontinuous and nearly frozen isotropic morphologies. © 2024 Informa UK Limited, trading as Taylor & Francis Group.