Nonlinear optical colloidal metacrystals

Ye Zhang; David D. Xu; Ibrahim Tanriover; Wenjie Zhou; Yuanwei Li; Rafael López-Arteaga; Koray Aydin; Chad A. Mirkin

doi:10.1038/s41566-024-01558-0

Nonlinear optical colloidal metacrystals

Ye Zhang, David D. Xu, Ibrahim Tanriover, Wenjie Zhou, Yuanwei Li, Rafael López-Arteaga, Koray Aydin^*, Chad A. Mirkin^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

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.

Original language	English (US)
Article number	6223
Pages (from-to)	20-27
Number of pages	8
Journal	Nature Photonics
Volume	19
Issue number	1
DOIs	https://doi.org/10.1038/s41566-024-01558-0
State	Published - Jan 2025

Funding

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.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Atomic and Molecular Physics, and Optics

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10.1038/s41566-024-01558-0

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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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Nonlinear optical colloidal metacrystals

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