Phase Behavior of Rod-Coil Block Copolymers in the Melt and At Fluid Interfaces

Conjugated rod-coil block copolymers have attracted increasing interest in applications that include photovoltaics and organic electronics due to their novel supramolecular structures. These structures are a result of the coupling of microphase separation and liquid-crystalline ordering. However, due to the complex nature of the interactions between the polymer chains, the theoretical tools used to describe rod-coil block copolymers are not nearly as mature as those used to study flexible block copolymers. In this work, we have employed a multiscale modeling approach that includes atomistic and coarse-grained molecular dynamics as well as highly efficient Monte Carlo simulations to study the phase behavior of rod-coil block copolymers in the bulk phase and the solvent environments. Our Monte Carlo simulations capture the main characteristics of rod-coil block copolymers in the melt while fully incorporating the fluctuations in three dimensions. Our atomistic and coarse-grained modeling are used to determine the self-assembly behavior both in solution and at fluid interfaces, where we find significant differences compared to flexible, coil-coil block copolymers.