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


Block copolymer self-assembly is a powerful tool for 2D nanofabrication; however, its extension to complex 3D network structures, which would be useful for a range of applications, is limited. Here, we report a simple method to generate unprecedented 3D 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 intra-layer self-assembly of the latter, giving rise to a mesh-like monoclinic M15 network substructure with excellent long-range order. Dissipative particle dynamics simulations show that the spatial constraints exerted on the polymer backbone drive the emergence of M15, as well as a tetragonal T131 in the strong segregation regime. This work demonstrates intrinsic molecular confinement as a path to bottom-up assembly of new geometrical phases of soft matter, extending the capabilities of block copolymer nanofabrication.


Supplementary material

Supplementary Information
PDF file containing Supplementary Figures, tables, and text.
Supplementary Video 1
STEM tomography raw data (tilt series) and the depth slice stack of the reconstructed tomogram.
Supplementary Video 2
Volume rendering of the 3D tomography reconstruction for the M15 substructure and its comparison with the mathematical model.
Supplementary Data 1
The 3D structures for the ball-and-stick model as well as the math model within a unit cell. (The models in the VRML file format (.wrl) are provided, which can be visualized by built-in apps in Windows such as Print 3D and 3D builder, etc. For Mac OS users, a PowerPoint file is provided with the same contents.)