Directing the Self-Assembly of Block Copolymers into A Metastable Complex Network Phase via A Deep and Rapid Quench

The free-energy landscape of self-assembling block copolymer systems is characterized by a multitude of metastable minima. Using particle-based simulations of a soft, coarse-grained model, we explore opportunities to reproducibly direct the spontaneous ordering of these self-assembling systems into a metastable complex network morphology-specifically, Schoen's I-WP periodic minimal surface-starting from a highly unstable state that is generated by a rapid expansion. This process-directed self-assembly provides an alternative to fine-tuning molecular architecture or blending for fabricating complex network structures. Comparing our particle-based simulation results to recently developed free-energy techniques, we critically assess their ability to predict spontaneous formation and highlight the importance of non-equilibrium molecular conformations in the starting state and the local conservation of density.