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. 2022 Jul 6;15(10):9461–9469. doi: 10.1007/s12274-022-4562-5

Toroidal dipole-modulated dipole-dipole double-resonance in colloidal gold rod-cup nanocrystals for improved SERS and second-harmonic generation

Hao-Sen Kang 1,#, Wen-Qin Zhao 1,#, Tao Zhou 2,#, Liang Ma 1,✉, Da-Jie Yang 3,✉, Xiang-Bai Chen 1, Si-Jing Ding 2, Qu-Quan Wang 4,✉
PMCID: PMC9258465  PMID: 35818567

Abstract

Colloidal metal nanocrystals (NCs) show great potential in plasmon-enhanced spectroscopy owing to their attractive and structure-depended plasmonic properties. Herein, unique Au rod-cup NCs, where Au nanocups are embedded on the one or two ends of Au nanorods (NRs), are successfully prepared for the first time via a controllable wet-chemistry strategy. The Au rod-cup NCs possess multiple plasmon modes including transverse and longitudinal electric dipole (TED and LED), magnetic dipole (MD), and toroidal dipole (TD) modulated LED resonances, producing large extinction cross-section and huge near-field enhancements for plasmon-enhanced spectroscopy. Particularly, Au rod-cup NCs with two embedded cups show excellent surface-enhanced Raman spectroscopy (SERS) performance than Au NRs (75.6-fold enhancement excited at 633 nm) on detecting crystal violet owing to the strong electromagnetic hotspots synergistically induced by MD, LED, and TED-based plasmon coupling between Au cup and rod. Moreover, the strong TD-modulated dipole-dipole double-resonance and MD modes in Au rod-cup NCs bring a 37.3-fold enhancement of second-harmonic generation intensity compared with bare Au NRs, because they can efficiently harvest photoenergy at fundamental frequency and generate large near-field enhancements at second-harmonic wavelength. These findings provide a strategy for designing optical nanoantennas for plasmon-enhanced applications based on multiple plasmon modes.

graphic file with name 12274_2022_4562_Fig1_HTML.jpg

Electronic Supplementary Material

Supplementary material (SEM image of Au rod-one-cup NCs; TEM image of Au/PbS hybrids; SEM image of Au rod-two-cup NCs; low-amplification SEM image of Au rod-two-cup NCs; experimental extinction and calculated electric field distributions of Au NR excited at different wavelengths; calculated absorption and scattering spectra of Au rod-one-cup NCs; schematic illustration of the cut plane and the corresponding magnetic field distribution under L3 excitation; Raman spectra of CV (10−6 M) adsorbed on Au rod-cup NCs with different cup sizes; calculated magnetic field distribution of Au rodcup NCs excited at 532 and 633 nm; calculated electric field distributions of Au rod-one-cup NC excited at 600 nm along TE and LE; the models of Au rod-cup NCs used in the simulations) is available in the online version of this article at 10.1007/s12274-022-4562-5.

Keywords: plasmon, toroidal dipole, near-field enhancement, surface-enhanced Raman spectroscopy (SERS), second-harmonic generation

Electronic Supplementary Material

12274_2022_4562_MOESM1_ESM.pdf (6.1MB, pdf)

Toroidal dipole-modulated dipole-dipole double-resonance in colloidal gold rod-cup nanocrystals for improved SERS and second-harmonic generation

Acknowledgements

This research was funded by the National Natural Science Foundation of China (Nos. 11904270 and 11904332) and Hubei Key Laboratory of Optical Information and Pattern Recognition (Nos. 202004 and 202010), Wuhan Institute of Technology. H. S. K. conceived the sample preparation. W. Q. Z. and T. Z. performed the sample characterization. L. M., D. J. Y., and X. B. C. conducted theoretical analysis. L. M., S. J. D., and Q. Q. W. designed the experiment. The manuscript was written through the contributions of all authors.

Footnotes

Hao-Sen Kang, Wen-Qin Zhao, and Tao Zhou contributed equally to this work.

Contributor Information

Liang Ma, Email: maliang@wit.edu.cn.

Da-Jie Yang, Email: djyang@ncepu.edu.cn.

Qu-Quan Wang, Email: wangqq6@sustech.edu.cn.

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Supplementary Materials

12274_2022_4562_MOESM1_ESM.pdf (6.1MB, pdf)

Toroidal dipole-modulated dipole-dipole double-resonance in colloidal gold rod-cup nanocrystals for improved SERS and second-harmonic generation

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