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Competition of shape and interaction patchiness for self-assembling nanoplates

Abstract

Progress in nanocrystal synthesis and self-assembly enables the formation of highly ordered superlattices. Recent studies focused on spherical particles with tunable attraction and polyhedral particles with anisotropic shape, and excluded volume repulsion, but the effects of shape on particle interaction are only starting to be exploited. Here we present a joint experimental–computational multiscale investigation of a class of highly faceted planar lanthanide fluoride nanocrystals (nanoplates, nanoplatelets). The nanoplates self-assemble into long-range ordered tilings at the liquid–air interface formed by a hexane wetting layer. Using Monte Carlo simulation, we demonstrate that their assembly can be understood from maximization of packing density only in a first approximation. Explaining the full phase behaviour requires an understanding of nanoplate-edge interactions, which originate from the atomic structure, as confirmed by density functional theory calculations. Despite the apparent simplicity in particle geometry, the combination of shape-induced entropic and edge-specific energetic effects directs the formation and stabilization of unconventional long-range ordered assemblies not attainable otherwise.

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Figure 1: Synthesis and structural characterization of monodisperse lanthanide fluoride nanocrystals.
Figure 2: 2D superlattices self-assembled from lanthanide fluoride nanoplates.
Figure 3: Monte Carlo simulations of hard polygonal plates.
Figure 4: Atomic structure of DyF3 surfaces.
Figure 5: Modelling and simulation of interacting lanthanide fluoride nanoplates.

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Acknowledgements

X.Y. and C.B.M. acknowledge support from the Office of Naval Research Multidisciplinary University Research Initiative on Optical Metamaterials through award N00014-10-1-0942. J.C. acknowledges support from the Materials Research Science and Engineering Center program of the National Science Foundation (NSF) under award DMR-1120901. C.B.M. is also grateful to the Richard Perry University Professorship for support of his supervisor role. M.E., J.A.M. and S.C.G. acknowledge support by the Assistant Secretary of Defense for Research and Engineering, US Department of Defense (N00244-09-1-0062). Any opinions, findings, and conclusions or recommendations expressed in this publication are those of the authors and do not necessarily reflect the views of the DOD/ASD (R&E). W.L., L.Q. and J.L. acknowledge support from the NSF (DMR-1120901). G.X. and C.R.K. acknowledge support from the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering (Award DE-SC0002158). Correspondence and requests for materials should be addressed to S.C.G. and C.B.M.

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Contributions

X.Y. and J.E.C. carried out nanocrystal syntheses. X.Y. and J.C. performed nanocrystal self-assembly and structural characterization. M.E. conceived the Monte Carlo simulations. J.A.M. performed and analysed the Monte Carlo simulations. W.L. and L.Q. performed DFT calculations. G.X. conducted atomic force microscopy (AFM) characterization. S.C.G. and C.B.M. designed the study and supervised the project. All authors discussed the results and co-wrote the manuscript.

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Correspondence to Sharon C. Glotzer or Christopher B. Murray.

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Ye, X., Chen, J., Engel, M. et al. Competition of shape and interaction patchiness for self-assembling nanoplates. Nature Chem 5, 466–473 (2013). https://doi.org/10.1038/nchem.1651

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