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Multiscale hierarchical structures from a nanocluster mesophase


Spontaneous hierarchical self-organization of nanometre-scale subunits into higher-level complex structures is ubiquitous in nature. The creation of synthetic nanomaterials that mimic the self-organization of complex superstructures commonly seen in biomolecules has proved challenging due to the lack of biomolecule-like building blocks that feature versatile, programmable interactions to render structural complexity. In this study, highly aligned structures are obtained from an organic–inorganic mesophase composed of monodisperse Cd37S18 magic-size cluster building blocks. Impressively, structural alignment spans over six orders of magnitude in length scale: nanoscale magic-size clusters arrange into a hexagonal geometry organized inside micrometre-sized filaments; self-assembly of these filaments leads to fibres that then organize into uniform arrays of centimetre-scale bands with well-defined surface periodicity. Enhanced patterning can be achieved by controlling processing conditions, resulting in bullseye and ‘zigzag’ stacking patterns with periodicity in two directions. Overall, we demonstrate that colloidal nanomaterials can exhibit a high level of self-organization behaviour at macroscopic-length scales.

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Fig. 1: Hierarchical self-assembly of 1.5 nm MSCs into centimetre-scale aligned bands.
Fig. 2: Method and mechanism for patterning of aligned films using different geometric confinements.
Fig. 3: Characterization of hierarchically patterned thin films.
Fig. 4: Tuning of thin film morphology through solvent evaporation rate and concentration.
Fig. 5: Optical properties of thin films.

Data availability

The data supporting the findings of this study are available within the paper, and other findings of this study are available from the corresponding authors upon reasonable request.


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This work was supported in part by the National Science Foundation (NSF) under award numbers CHE-1507753, CHE-2003586, CMMI-1941135, CHE-1665305 and DMR-1809429. Electron microscopy was supported by the NSF under award number DMR-1654596. This work was partially supported by the Cornell Center for Materials Research and made use of the Cornell Center for Materials Research shared facilities, with funding from the the NSF MRSEC programme (number DMR-1719875). R.S.S. acknowledges financial support from the NSF Graduate Research Fellowship Programme under grant no. DGE-1650441. From the Department of Chemical and Biomolecular Engineering at Cornell University, we thank Y. Cheng for AFM analysis and K. Niccum and M. Johnson for their pioneering work.

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Authors and Affiliations



H.H. and S.K. synthesized high-quality MSCs and thin films used in the main studies. H.H., S.K., C.B.W. and D.R.N. performed OM and POM. H.H. performed atomic force microscopy, scanning electron microscopy and UV-vis absorption spectroscopy. S.K. conducted laser diffraction experiments, simulations, and optical analysis. H.H. and Y.Y. measured circular and LD spectroscopy and carried out TEM imaging. B.H.S. and L.F.K. carried out high-resolution STEM. R.S.S. and J.D. contributed to the modelling and understanding of how the strain energy of twisting leads to monodisperse cable thickness. M.X. synthesized and prepared thin films from CdOl nanoclusters and CdS nanoparticles. O.V. calculated dipoles and dipole–dipole interactions between MSCs. S.J.W. contributed the theoretical model for the self-assembly mechanism. R.D.R. and T.H. conceived this project, supervised and guided the design, analysis and interpretation and wrote the manuscript. All authors contributed to the interpretation of results and preparation of the manuscript.

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Correspondence to Tobias Hanrath or Richard D. Robinson.

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Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–40 and Table 1.

Supplementary Video 1

Alteration in surface texture of thin film following change of focal plane.

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Han, H., Kallakuri, S., Yao, Y. et al. Multiscale hierarchical structures from a nanocluster mesophase. Nat. Mater. 21, 518–525 (2022).

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