Emergence of layered nanoscale mesh networks through intrinsic molecular confinement self-assembly

Block copolymer self-assembly is a powerful tool for two-dimensional nanofabrication; however, the extension of this self-assembly concept to complex three-dimensional network structures is limited. Here we report a simple method to experimentally generate three-dimensional layered mesh morphologies through intrinsic molecular confinement self-assembly. We designed triblock bottlebrush polymers with two Janus domains: one perpendicular and one parallel to the polymer backbone. The former enforces a lamellar superstructure that intrinsically confines the intralayer self-assembly of the latter, giving rise to a mesh-like monoclinic (54°) M¹⁵ network substructure with excellent long-range order, as well as a tetragonal (90°) T¹³¹ mesh. Numerical simulations show that the spatial constraints exerted on the polymer backbone drive the assembly of M¹⁵ and yield T¹³¹ in the strong segregation regime. This work demonstrates that intrinsic molecular confinement is a viable path to bottom-up assembly of new geometrical phases of soft matter, extending the capabilities of block copolymer nanofabrication.