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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

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BEING VIEWED BY OTHERS PRIMING SELF-ASSEMBLY PATHWAYS BY STACKING BLOCK COPOLYMERS Article Open access 14 November 2022 CONVOLUTED MICELLAR MORPHOLOGICAL TRANSITIONS DRIVEN BY TAILORABLE

MESOGENIC ORDERING EFFECT FROM DISCOTIC MESOGEN-CONTAINING BLOCK COPOLYMER Article Open access 06 April 2024 HIERARCHICALLY ENGINEERED NANOSTRUCTURES FROM COMPOSITIONALLY ANISOTROPIC

MOLECULAR BUILDING BLOCKS Article 10 November 2022 DATA AVAILABILITY The raw data for STEM tomography and 3D reconstruction is provided in Supplementary Video 1. The LAMMPS input and output

datasets are too large to be shared publicly but are available from the corresponding authors upon request. All other data needed to evaluate the conclusions of this study are available

within the Article and its Supplementary Information. CODE AVAILABILITY The code generated during this study is available via GitHub at https://github.com/Z-H-Sun/IMCmesh. REFERENCES *

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particle dynamics. _Europhys. Lett._ 19, 155–160 (1992). Google Scholar  Download references ACKNOWLEDGEMENTS J.A.J. acknowledges support from Eni S.p.A. through the MIT Energy Initiative.

C.A.R. and A.A.-K. acknowledge support from NSF DMREF award 2118678. M.Z. acknowledges support from the NSF DMR award 2003875. This work was carried out in part through the use of MIT.nano’s

facilities and APS, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory (contract no. DE-AC02-06CH11357).

The shared facilities of CMSE, NSL and MRSEC under award DMR1419807 were used. We acknowledge the MIT Satori, the MIT SuperCloud, MIT Research Computing Project and Lincoln Laboratory

Supercomputing Center for providing the high-performance computing resources that have contributed to the research results reported here. We thank E. Cho and A. Penn for help with STEM

imaging and Y. Ouyang for helpful discussion. AUTHOR INFORMATION Author notes * These authors contributed equally: Zehao Sun, Runze Liu. AUTHORS AND AFFILIATIONS * Department of Materials

Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA Zehao Sun, Runze Liu, Hejin Huang, Alfredo Alexander-Katz, Caroline A. Ross & Jeremiah A. Johnson *

Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA Tingyu Su * Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

Ken Kawamoto, Bin Liu & Jeremiah A. Johnson * Department of Chemical and Environmental Engineering, Yale University, New Haven, CT, USA Ruiqi Liang & Mingjiang Zhong Authors * Zehao

Sun View author publications You can also search for this author inPubMed Google Scholar * Runze Liu View author publications You can also search for this author inPubMed Google Scholar *

Tingyu Su View author publications You can also search for this author inPubMed Google Scholar * Hejin Huang View author publications You can also search for this author inPubMed Google

Scholar * Ken Kawamoto View author publications You can also search for this author inPubMed Google Scholar * Ruiqi Liang View author publications You can also search for this author

inPubMed Google Scholar * Bin Liu View author publications You can also search for this author inPubMed Google Scholar * Mingjiang Zhong View author publications You can also search for this

author inPubMed Google Scholar * Alfredo Alexander-Katz View author publications You can also search for this author inPubMed Google Scholar * Caroline A. Ross View author publications You

can also search for this author inPubMed Google Scholar * Jeremiah A. Johnson View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS Z.S., K.K.

and B.L. synthesized the JBBCPs. Z.S., R. Liu and T.S. prepared the samples. Z.S., R. Liu, T.S. and R. Liang conducted the structure and property characterization. Z.S., R. Liu, H.H. and

A.A.-K. conducted the simulations. Z.S., R. Liu, M.Z., C.A.R. and J.A.J. conceived the idea. Z.S., C.A.R. and J.A.J. wrote the manuscript. CORRESPONDING AUTHORS Correspondence to Caroline A.

Ross or Jeremiah A. Johnson. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. PEER REVIEW PEER REVIEW INFORMATION _Nature Nanotechnology_ thanks Maria

Sammalkorpi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. ADDITIONAL INFORMATION PUBLISHER’S NOTE Springer Nature remains neutral with regard

to jurisdictional claims in published maps and institutional affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary Figs. 1–56, Tables 1 and 2, text and materials

and methods. SUPPLEMENTARY VIDEO 1 STEM tomography raw data (tilt series) and 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 and math model within a unit cell.

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permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Sun, Z., Liu, R., Su, T. _et al._ Emergence of layered nanoscale mesh networks through intrinsic molecular confinement self-assembly. _Nat.

Nanotechnol._ 18, 273–280 (2023). https://doi.org/10.1038/s41565-022-01293-z Download citation * Received: 24 June 2022 * Accepted: 10 November 2022 * Published: 09 January 2023 * Issue

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