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Nonlinear optical colloidal metacrystals

Nature Photonics volume 19, pages 20–27 (2025)Cite this article

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Abstract

Atomic and molecular structure inversion symmetry breaking in naturally occurring crystals dictate their physical properties including nonlinear optical (NLO) effects, piezo- or ferroelectricity, and non-reciprocal charge transport behaviour. With metamaterials composed of nanoscale building blocks (that is, meta-atoms), the spatial inversion symmetry violation on planar surfaces leads to spin-controlled photonics as well as NLO metasurfaces. Synthetically, low-symmetry 3D metacrystals can be synthesized, but NLO behaviour has not been identified so far (for example, harmonic generations). Herein we show how DNA-mediated assembly of octahedron-shaped plasmonic gold nanocrystals can be used to design and deliberately synthesize non-centrosymmetric and centrosymmetric colloidal crystals. Importantly, while the centrosymmetric structures do not exhibit substantial second-harmonic generation, the non-centrosymmetric crystals do—a consequence of the asymmetric distribution of localized electric fields in plasmonic hotspots. Moreover, this non-centrosymmetric NLO metacrystal represents a 3D NLO metamaterial being developed via a bottom-up approach, exhibiting a maximum second-harmonic generation conversion efficiency of 10−9 to surpass the efficiencies observed in the majority of plasmonic 2D metasurfaces. Finally, the DNA-loading density on the particle building blocks can be used to toggle between the centrosymmetric and non-centrosymmetric phases.

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Fig. 1: Design of DNA-programmed colloidal crystal growth with controllable symmetries and characterization of these structures by SEM.
Fig. 2: Second-harmonic generation experiments on the non-centrosymmetric colloidal crystal.
Fig. 3: Simulated electric field maps of the non-centrosymmetric superlattice.
Fig. 4: Comparison of the SHG responses of three superlattices with different symmetries.
Fig. 5: Overview of the SHG conversion efficiencies and the effective χ(2) of the NLO metacrystal.

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All the data supporting the findings of this study are available within this Article and its Supplementary Information. Any additional information can be obtained from the corresponding authors on reasonable request. Source Data are provided with this paper.

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Acknowledgements

We thank J. Orbeck for providing editorial input, and R. Chan, K. Landy, Z. Li and K. Gibson for technical help and fruitful discussions. We also thank M. Hersam for supporting the access to the laser equipment. This material is based on work supported by the Air Force Office of Scientific Research award FA9550-22-1-0300 (nanocrystal synthesis and assembly, optical simulation); the Center for Bio-Inspired Energy Science, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences award DE-SC0000989 (DNA functionalization); an Army Research Office grant W911NF-23-1-0141 (SEM characterizations); and the Sherman Fairchild Foundation (SHG measurements). This work made use of the EPIC facility (NUANCE Center-Northwestern University), which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); and the State of Illinois, through the IIN.

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Authors and Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Ye Zhang, David D. Xu, Wenjie Zhou & Chad A. Mirkin

  2. International Institute for Nanotechnology, Northwestern University, Evanston, IL, USA

    Ye Zhang, David D. Xu, Ibrahim Tanriover, Wenjie Zhou, Yuanwei Li, Koray Aydin & Chad A. Mirkin

  3. Department of Electrical and Computer Engineering, Northwestern University, Evanston, IL, USA

    Ibrahim Tanriover & Koray Aydin

  4. Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL, USA

    Yuanwei Li & Chad A. Mirkin

  5. Department of Material Science and Engineering, Northwestern University, Evanston, IL, USA

    Rafael López-Arteaga & Chad A. Mirkin

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  1. Ye Zhang
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Contributions

Y.Z. and C.A.M. conceived the idea. Y.Z. performed the synthesis and characterization of colloidal crystals with the help from W.Z. and Y.L. D.D.X. and Y.Z. designed and performed the SHG experiments. I.T. performed the optical simulation. R.L.A. conducted pulse width measurement experiments. C.A.M. and K.A. supervised the project. Y.Z. analysed the data and wrote the initial draft. All authors contributed to interpreting the data and writing or commenting on the manuscript.

Corresponding authors

Correspondence to Koray Aydin or Chad A. Mirkin.

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Nature Photonics thanks Huigao Duan, Hui Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Sections 1–4, Tables 1–10 and Figs. 1–26.

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Zhang, Y., Xu, D.D., Tanriover, I. et al. Nonlinear optical colloidal metacrystals. Nat. Photon. 19, 20–27 (2025). https://doi.org/10.1038/s41566-024-01558-0

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