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Enhancing nanoscale charged colloid crystallization near a metastable liquid binodal

Nature Physics volume 21, pages 1594–1602 (2025)Cite this article

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Abstract

Achieving predictive control over crystallization using non-classical nucleation while avoiding kinetic traps would be a step towards designing materials with new functionalities. We address these challenges by inducing the bottom-up assembly of nanocrystals into ordered arrays, or superlattices. Using electrostatics—rather than density—to tune the interactions between particles, we watch self-assembly proceed through a metastable liquid phase. We systematically investigate the phase behaviour as a function of quench conditions in situ and in real time using small-angle X-ray scattering. By fitting to colloid, liquid and superlattice models, we extract the time evolution of each phase and the system phase diagram, which we find to be consistent with short-range attractive interactions. Using the predictive power of the phase diagram, we establish control of the self-assembly rate over three orders of magnitude, and we identify one- and two-step self-assembly regimes, with only the latter implicating the metastable liquid as an intermediate. The presence of the metastable liquid increases the superlattice formation rate relative to the equivalent one-step pathway, and the superlattice order increases with the rate, revealing a generalizable kinetic strategy for promoting and enhancing ordered assembly.

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Fig. 1: Impact of interparticle potentials on thermodynamics and kinetics of self-assembly.
Fig. 2: Quantitative analysis of quench- and volume-fraction-dependent SAXS patterns.
Fig. 3: Kinetic analysis of quench- and volume-fraction-dependent SAXS.
Fig. 4: Deduced design principles for optimal SL self-assembly.

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Data availability

The data contained in the plots within this paper and other findings of this study are available from the corresponding author on reasonable request.

Code availability

The code used to analyse the data is available from the corresponding author upon reasonable request.

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Acknowledgements

We thank M. Delor for help designing the set-up for dynamic light scattering. This work was supported by the Office of Basic Energy Sciences, US Department of Energy (DOE) (Award No. DE-SC0019375). The work on NC synthesis was partially supported by the US DOE, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division (Grant No. DE-SC0025256) and made use of the shared facilities at the University of Chicago Materials Research Science and Engineering Center, which is supported by the National Science Foundation (Award No. DMR-2011854). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the DOE, Office of Science, Office of Basic Energy Sciences (Contract No. DE-AC02-76SF00515). Use of beamline 7.3.3 at the Advanced Light Source, Lawrence Berkeley National Laboratory, is supported by the DOE, Office of Science, Office of Basic Energy Sciences (Contract No. DE-AC02-05CH11231). C.P.N.T., V.R.K.W. and R.B.W. were supported by an NSF Graduate Research Fellowship. L.M.H. and J.A.T. acknowledge a National Defense Science and Engineering Graduate Fellowship. J.K.U. was supported by an Arnold O. Beckman Postdoctoral Fellowship in Chemical Sciences from the Arnold and Mabel Beckman Foundation. A.D. and L.M.H. were supported by Philomathia Graduate Student Fellowships from the Kavli Energy NanoScience Institute at UC Berkeley. A.J. was partially supported by a graduate fellowship from Kwanjeong Educational Foundation. D.T.L. was supported by an Alfred P. Sloan Research Fellowship. N.S.G. and D.V.T. were supported by David and Lucile Packard Foundation Fellowships for Science and Engineering and Camille and Henry Dreyfus Teacher-Scholar Awards.

Author information

Author notes

  1. Avishek Das

    Present address: AMOLF, Amsterdam, The Netherlands

  2. James K. Utterback

    Present address: Institut des NanoSciences de Paris, Sorbonne Université, CNRS, Paris, France

  3. These authors contributed equally: Christian P. N. Tanner, Vivian R. K. Wall.

Authors and Affiliations

  1. Department of Chemistry, University of California, Berkeley, CA, USA

    Christian P. N. Tanner, Vivian R. K. Wall, Avishek Das, James K. Utterback, Leo M. Hamerlynck, Jonathan G. Raybin, Rebecca B. Wai, Jenna A. Tan, Mumtaz Gababa, David T. Limmer & Naomi S. Ginsberg

  2. Department of Chemistry, James Franck Institute, University of Chicago, Chicago, IL, USA

    Joshua Portner, Ahhyun Jeong & Dmitri V. Talapin

  3. Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, USA

    Joshua Portner, Ahhyun Jeong & Dmitri V. Talapin

  4. Department of Physics, Arizona State University, Tempe, AZ, USA

    Matthew J. Hurley, Nicholas Leonard & Samuel W. Teitelbaum

  5. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Chenhui Zhu & Eric Schaible

  6. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Christopher J. Tassone

  7. Chemical Sciences and Materials Sciences Divisions, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    David T. Limmer & Naomi S. Ginsberg

  8. Kavli Energy NanoSciences Institute, University of California, Berkeley, CA, USA

    David T. Limmer & Naomi S. Ginsberg

  9. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, IL, USA

    Dmitri V. Talapin

  10. Department of Physics, University of California, Berkeley, CA, USA

    Naomi S. Ginsberg

  11. Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Naomi S. Ginsberg

  12. STROBE, NSF Science & Technology Center, Berkeley, CA, USA

    Naomi S. Ginsberg

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  1. Christian P. N. Tanner
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Contributions

N.S.G., D.V.T. and D.T.L. conceived and supervised the research. C.P.N.T., J.K.U., C.J.T., J.P., R.B.W., J.A.T., D.V.T., S.W.T. and N.S.G. designed and performed the early experiments. C.P.N.T., V.R.K.W., J.P., A.J., M.J.H., N.L., L.M.H., J.G.R., E.S. and C.Z. performed further experiments. C.P.N.T., A.D., V.R.K.W., D.T.L. and N.S.G. formulated the analytical and numerical models and performed the simulations. M.G. and C.P.N.T. performed supporting measurements. C.P.N.T. and V.R.K.W. analysed the data. All authors helped to prepare or review the paper.

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Correspondence to Naomi S. Ginsberg.

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Tanner, C.P.N., Wall, V.R.K., Portner, J. et al. Enhancing nanoscale charged colloid crystallization near a metastable liquid binodal. Nat. Phys. 21, 1594–1602 (2025). https://doi.org/10.1038/s41567-025-02996-5

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