Processive Pathways to Metastability in Block Copolymer Thin Films

Block copolymers (BCPs) self-assemble into intricate nanostructures that enhance a multitude of advanced applications in semiconductor processing, membrane science, nanopatterned coatings, nanocomposites, and battery research. Kinetics and thermodynamics of self-assembly are crucial considerations in controlling the nanostructure of BCP thin films. The equilibrium structure is governed by a molecular architecture and the chemistry of its repeat units. An enormous library of materials has been synthesized and they naturally produce a rich equilibrium phase diagram. Non-equilibrium phases could potentially broaden the structural diversity of BCPs and relax the synthetic burden of creating new molecules. Furthermore, the reliance on synthesis could be complicated by the scalability and the materials compatibility. Non-equilibrium phases in BCPs, however, are less explored, likely due to the challenges in stabilizing the metastable structures. Over the past few decades, a variety of processing techniques were introduced that influence the phase transformation of BCPs to achieve a wide range of morphologies. Nonetheless, there is a knowledge gap on how different processive pathways can induce and control the non-equilibrium phases in BCP thin films. In this review, we focus on different solvent-induced and thermally induced processive pathways, and their potential to control the non-equilibrium phases with regards to their unique aspects and advantages. Furthermore, we elucidate the limitations of these pathways and discuss the potential avenues for future investigations.