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

Nature Nanotechnology volume 18, pages 273–280 (2023)Cite this article

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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 nanofabrication.

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Fig. 1: Fabrication of multilayer nanomeshes based on intrinsic molecular confinement self-assembly of triblock JBBCPs.
Fig. 2: SEM imaging of the multilayer nanomesh structures.
Fig. 3: STEM imaging and tomography evidence for the M15 substructure.
Fig. 4: Comparison of the networks and phase diagrams between di- and triblock JBBCPs.

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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.

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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.

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Author notes

  1. These authors contributed equally: Zehao Sun, Runze Liu.

Authors and Affiliations

  1. 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

  2. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Tingyu Su

  3. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Ken Kawamoto, Bin Liu & Jeremiah A. Johnson

  4. Department of Chemical and Environmental Engineering, Yale University, New Haven, CT, USA

    Ruiqi Liang & Mingjiang Zhong

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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.

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Nature Nanotechnology thanks Maria Sammalkorpi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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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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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

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