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Crystallization of binary nanocrystal superlattices and the relevance of short-range attraction

Nature Synthesis volume 3, pages 111–122 (2024)Cite this article

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An Author Correction to this article was published on 24 November 2023

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Abstract

The synthesis of binary nanocrystal superlattices (BNSLs) enables the targeted integration of orthogonal physical properties, such as photoluminescence and magnetism, into a single superstructure, unlocking a vast design space for multifunctional materials. However, the formation mechanism of BNSLs remains poorly understood, restricting the prediction of the structure and properties of superlattices. Here we use a combination of in situ scattering and molecular simulation to elucidate the self-assembly of two common BNSLs (AlB2 and NaZn13) through emulsion templating. Our self-assembly experiments reveal that no intermediate structures precede the formation of the final binary phases, indicating that their formation proceeds through classical nucleation. Using simulations, we find that, despite the formation of AlB2 and NaZn13 typically being attributed to entropy, their self-assembly is most consistent with the nanocrystals possessing short-range interparticle attraction, which we find can accelerate nucleation kinetics in BNSLs. We also find homogeneous, classical nucleation in simulations, corroborating our experiments. These results establish a robust correspondence between experiment and theory, paving the way towards prediction of BNSLs.

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Fig. 1: Formation of colloidal AlB2 BNSLs.
Fig. 2: Formation of colloidal NaZn13 BNSLs.
Fig. 3: The influence of attractive forces in binary mixtures.
Fig. 4: The self-assembly of AlB2 and NaZn13 in spherical droplets.

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Data availability

The authors declare that the data supporting the findings of this study are available within the Article and its Supplementary Information files. Source data for the figures in the main text are available in the Supplementary Information.

Code availability

The source code for HOOMD-blue is available at https://github.com/glotzerlab/hoomd-blue. The source code for freud is available at https://github.com/glotzerlab/freud. The source code for signac is available at https://github.com/glotzerlab/signac. Source data for the figures in the main text are available in the Supplementary Information. Sample codes are available in the Supplementary Information.

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Acknowledgements

The authors acknowledge primary support from the National Science Foundation under grant DMR-2019444. E.M., S.Y., and C.B.M. (sample preparation and characterization) and R.A.L. and S.C.G. (theory, modeling & simulation) acknowledge support from the Office of Naval Research Multidisciplinary University Research Initiative Award ONR N00014-18-1-2497 for sample preparation and characterization. E.M. is grateful to the National Recovery and Resilience Plan (NRRP) PNR 2021-2022 (CUP B79J21038330001) for funding his position at Unipa. E.M. acknowledges the Fondo Finalizzato Alla Ricerca Di Ateneo (FFR) 2022-2023 of Unipa for funding. A.W.K. and C.R.K. acknowledge support from the Semiconductor Research Corporation (SRC) under the Nanomanufacturing Materials and Processes (NMP) trust via Task 2797.001. D.J.R. acknowledges support from the VIEST fellowship. T.C.M. supported by a grant from the Simons Foundation (256297, SCG). G.G. acknowledges Solvay for financial support. C.B.M. acknowledges the Richard Perry University Professorship at the University of Pennsylvania. Support for the Dual Source and Environmental X-ray Scattering Facility at the University of Pennsylvania was provided by the Laboratory for Research on the Structure of Matter which is funded in part by NSF MRSEC 1720530. This research used resources of the Center for Functional Nanomaterials and the National Synchrotron Light Source II, which are US DOE Office of Science Facilities, at Brookhaven National Laboratory under contract number DESC0012704. Computational work used resources from the Extreme Science and Engineering Discovery Environment (XSEDE)123, which is supported by National Science Foundation grant number ACI-1548562; XSEDE award DMR 140129. Additional computational resources and services were supported by Advanced Research Computing at the University of Michigan, Ann Arbor.

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Author notes

  1. These authors contributed equally: Emanuele Marino, R. Allen LaCour.

Authors and Affiliations

  1. Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA

    Emanuele Marino, Sjoerd W. van Dongen, Di An, Shengsong Yang, Guillaume Gouget, Cherie R. Kagan & Christopher B. Murray

  2. Dipartimento di Fisica e Chimica, Università degli Studi di Palermo, Palermo, Italy

    Emanuele Marino

  3. Department of Chemical Engineering, University of Michigan, Ann Arbor, MI, USA

    R. Allen LaCour, Timothy C. Moore & Sharon C. Glotzer

  4. Physical Chemistry and Soft Matter, Wageningen University and Research, Wageningen, Netherlands

    Sjoerd W. van Dongen & Thomas E. Kodger

  5. Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA, USA

    Austin W. Keller, Daniel J. Rosen, Cherie R. Kagan & Christopher B. Murray

  6. Brookhaven National Laboratory, Center for Functional Nanomaterials, Upton, NY, USA

    Esther H. R. Tsai

  7. Department of Electrical and Systems Engineering, University of Pennsylvania, Philadelphia, PA, USA

    Cherie R. Kagan

  8. Biointerfaces Institute, University of Michigan, Ann Arbor, MI, USA

    Sharon C. Glotzer

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  1. Emanuele Marino
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Contributions

E.M. designed the experiment. E.M., S.W.v.D., A.W.K. and D.A. synthesized and characterized the NC building blocks. E.M., S.W.v.D., S.Y., D.J.R. and E.H.R.T. measured the in situ scattering. E.M. measured the ex situ scattering. E.M. analysed in situ and ex situ scattering results. E.H.R.T. provided local support at the beamline. E.M., G.G. and S.W.v.D. performed the electron microscopy studies. D.J.R. performed the magnetic measurements. R.A.L. and T.C.M. performed the simulations and analysed the results. T.E.K., S.C.G., C.R.K. and C.B.M. supervised the project. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Corresponding authors

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

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Nature Synthesis thanks Y. Charles Cao, Tobias Kraus and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–25, text and references.

Supplementary Video 1

Time-dependent scattering pattern for the binary dispersion including larger Fe3O4 and smaller PbS nanocrystals at a stoichiometry of 1:2.

Supplementary Video 2

Time-dependent scattering pattern for the binary dispersion including larger FICO and smaller PbS nanocrystals at a stoichiometry of 1:2.

Supplementary Video 3

Time-dependent scattering pattern for the binary dispersion including larger FICO and smaller PbS nanocrystals at a stoichiometry of 1:13.

Supplementary code 1

Sample codes for molecular dynamics simulations.

Source data

Source Data Fig. 1

Source data for Fig. 1 of the main text.

Source Data Fig. 2

Source data for Fig. 2 of the main text.

Source Data Fig. 3

Source data for Fig. 3 of the main text.

Source Data Fig. 4

Source data for Fig. 4 of the main text.

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Marino, E., LaCour, R.A., Moore, T.C. et al. Crystallization of binary nanocrystal superlattices and the relevance of short-range attraction. Nat. Synth 3, 111–122 (2024). https://doi.org/10.1038/s44160-023-00407-2

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