Polymer Science

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

Authors

Abstract

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.

Content

Thumbnail image of manuscript.pdf

Supplementary material

Thumbnail image of SupplementaryInformation.pdf
Supplementary Information
PDF file containing Supplementary Figures, tables, and text.
Thumbnail image of 001.mp4
Supplementary Video 1
STEM tomography raw data (tilt series) and the depth slice stack of the reconstructed tomogram.
Thumbnail image of 002.mp4
Supplementary Video 2
Volume rendering of the 3D tomography reconstruction for the M15 substructure and its comparison with the mathematical model.
Thumbnail image of SupplementaryData1.zip
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.)