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

Zehao Sun; Runze Liu; Tingyu Su; Hejin Huang; Ken Kawamoto; Ruiqi Liang; Bin Liu; Mingjiang Zhong; Alfredo Alexander-Katz; Caroline A Ross; Jeremiah A Johnson

doi:10.1038/s41565-022-01293-z

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

Nat Nanotechnol. 2023 Mar;18(3):273-280. doi: 10.1038/s41565-022-01293-z. Epub 2023 Jan 9.

Authors

Zehao Sun^#¹, Runze Liu^#¹, Tingyu Su², Hejin Huang¹, Ken Kawamoto³, Ruiqi Liang⁴, Bin Liu³, Mingjiang Zhong⁴, Alfredo Alexander-Katz¹, Caroline A Ross⁵, Jeremiah A Johnson^{6

7}

Affiliations

¹ Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA.
² Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA.
³ Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA.
⁴ Department of Chemical and Environmental Engineering, Yale University, New Haven, CT, USA.
⁵ Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA. caross@mit.edu.
⁶ Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA. jaj2109@mit.edu.
⁷ Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA. jaj2109@mit.edu.

^# Contributed equally.

PMID: 36624206
DOI: 10.1038/s41565-022-01293-z

Abstract

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.

Abstract

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