Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Observation of inhomogeneous plasmonic field distribution in a nanocavity

Abstract

The progress of plasmon-based technologies relies on an understanding of the properties of the enhanced electromagnetic fields generated by the coupling nanostrucutres1,2,3,4,5,6. Plasmon-enhanced applications include advanced spectroscopies7,8,9,10, optomechanics11, optomagnetics12 and biosensing13,14,15,16,17. However, precise determination of plasmon field intensity distribution within a nanogap remains challenging. Here, we demonstrate a molecular ruler made from a set of viologen-based, self-assembly monolayers with which we precisely measures field distribution within a plasmon nanocavity with ~2-Å spatial resolution. We observed an unusually large plasmon field intensity inhomogeneity that we attribute to the formation of a plasmonic comb in the nanocavity. As a consequence, we posit that the generally adopted continuous media approximation for molecular monolayers should be used carefully.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Probing the plasmon field in a nanocavity.
Fig. 2: Longitudinal plasmon field distribution within the nanocavity.
Fig. 3: Measurement of longitudinal plasmon field distribution using an alternative probe and nanocavity size.

Similar content being viewed by others

Data availability

The data that support this study are available from the corresponding authors upon reasonable request.

Code availability

The codes that support this study are available from the corresponding authors upon reasonable request.

References

  1. Moskovits, M. Surface-enhanced spectroscopy. Rev. Mod. Phys. 57, 783–826 (1985).

    CAS  Google Scholar 

  2. Ciracì, C. et al. Probing the ultimate limits of plasmonic enhancement. Science 337, 1072–1074 (2012).

    Google Scholar 

  3. Maier, S. A. Plasmonics: Fundamentals and Applications (Springer, 2007).

  4. Kelly, K. L., Coronado, E., Zhao, L. L. & Schatz, G. C. The optical properties of metal nanoparticles: the influence of size, shape, and dielectric environment. J. Phys. Chem. B 107, 668–677 (2003).

    CAS  Google Scholar 

  5. Willets, K. A. & Van Duyne, R. P. Localized surface plasmon resonance spectroscopy and sensing. Annu. Rev. Phys. Chem. 58, 267–297 (2007).

    CAS  Google Scholar 

  6. Chen, W., Zhang, S., Deng, Q. & Xu, H. Probing of sub-picometer vertical differential resolutions using cavity plasmons. Nat. Commun. 9, 801 (2018).

    Google Scholar 

  7. Nie, S. & Emory, S. R. Probing single molecules and single nanoparticles by surface-enhanced Raman scattering. Science 275, 1102–1106 (1997).

    CAS  Google Scholar 

  8. Kneipp, K. et al. Single molecule detection using surface-enhanced Raman scattering (SERS). Phys. Rev. Lett. 78, 1667–1670 (1997).

    CAS  Google Scholar 

  9. van Schrojenstein Lantman, E. M., Deckert-Gaudig, T., Mank, A. J. G., Deckert, V. & Weckhuysen, B. M. Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy. Nat. Nanotechnol. 7, 583–586 (2012).

    Google Scholar 

  10. Halas, N. J., Lal, S., Chang, W. S., Link, S. & Nordlander, P. Plasmons in strongly coupled metallic nanostructures. Chem. Rev. 111, 3913–3961 (2011).

    CAS  Google Scholar 

  11. Benz, F. et al. Single-molecule optomechanics in ‘picocavities’. Science 354, 726–729 (2016).

    CAS  Google Scholar 

  12. Duan, S., Rinkevicius, Z., Tian, G. & Luo, Y. Optomagnetic effect induced by magnetized nanocavity plasmon. J. Am. Chem. Soc. 141, 13795–13798 (2019).

    CAS  Google Scholar 

  13. Cao, Y. C., Jin, R. & Mirkin, C. A. Nanoparticles with Raman spectroscopic fingerprints for DNA and RNA detection. Science 297, 1536–1540 (2002).

    CAS  Google Scholar 

  14. Sonnichsen, C., Reinhard, B. M., Liphardt, J. & Alivisatos, A. P. A molecular ruler based on plasmon coupling of single gold and silver nanoparticles. Nat. Biotechnol. 23, 741–745 (2005).

    Google Scholar 

  15. Zhou, C., Duan, X. & Liu, N. A plasmonic nanorod that walks on DNA origami. Nat. Commun. 6, 8102 (2015).

    CAS  Google Scholar 

  16. Laing, S., Jamieson, L. E., Faulds, K. & Graham, D. Surface-enhanced Raman spectroscopy for in vivo biosensing. Nat. Rev. Chem. 1, 0060 (2017).

    CAS  Google Scholar 

  17. Bodelón, G. et al. Detection and imaging of quorum sensing in Pseudomonas aeruginosa biofilm communities by surface-enhanced resonance Raman scattering. Nat. Mater. 15, 1203–1211 (2016).

    Google Scholar 

  18. Zhang, R. et al. Chemical mapping of a single molecule by plasmon-enhanced Raman scattering. Nature 498, 82–86 (2013).

    CAS  Google Scholar 

  19. Duan, S. et al. Theoretical modeling of plasmon-enhanced Raman images of a single molecule with subnanometer resolution. J. Am. Chem. Soc. 137, 9515–9518 (2015).

    CAS  Google Scholar 

  20. Duan, S., Tian, G. & Luo, Y. Visualization of vibrational modes in real space by tip-enhanced non-resonant Raman spectroscopy. Angew. Chem. Int. Ed. 55, 1041–1045 (2016).

    CAS  Google Scholar 

  21. Imada, H. et al. Real-space investigation of energy transfer in heterogeneous molecular dimers. Nature 538, 364–367 (2016).

    CAS  Google Scholar 

  22. Lee, J., Crampton, K. T., Tallarida, N. & Apkarian, V. A. Visualizing vibrational normal modes of a single molecule with atomically confined light. Nature 568, 78–82 (2019).

    CAS  Google Scholar 

  23. Tallarida, N., Lee, J. & Apkarian, V. A. Tip-enhanced Raman spectromicroscopy on the angstrom scale: bare and co-terminated Ag tips. ACS Nano 11, 11393–11401 (2017).

    CAS  Google Scholar 

  24. Ding, S.-Y. et al. Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials. Nat. Rev. Mater. 1, 16021 (2016).

  25. Zhang, C., Chen, B.-Q. & Li, Z.-Y. Optical origin of subnanometer resolution in tip-enhanced Raman mapping. J. Phys. Chem. C. 119, 11858–11871 (2015).

    CAS  Google Scholar 

  26. Li, Z. et al. Two-dimensional assembly and local redox-activity of molecular hybrid structures in an electrochemical environment. Faraday Discuss. 131, 121–143 (2006).

    CAS  Google Scholar 

  27. Liu, B., Blaszczyk, A., Mayor, M. & Wandlowski, T. Redox-switching in a viologen-type adlayer: an electrochemical shell-isolated nanoparticle enhanced Raman spectroscopy study on Au(111)-(1 × 1) single crystal electrodes. ACS Nano 5, 5662–5672 (2011).

    CAS  Google Scholar 

  28. Li, J. F. et al. Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 464, 392–395 (2010).

    CAS  Google Scholar 

  29. Chen, X. & Jensen, L. Understanding the shape effect on the plasmonic response of small ligand coated nanoparticles. J. Opt. 18, 074009 (2016).

    Google Scholar 

  30. Koh, A. L., Fernández-Domínguez, A. I., McComb, D. W., Maier, S. A. & Yang, J. K. W. High-resolution mapping of electron-beam-excited plasmon modes in lithographically defined gold nanostructures. Nano Lett. 11, 1323–1330 (2011).

    CAS  Google Scholar 

  31. Wu, Y., Li, G. & Camden, J. P. Probing nanoparticle plasmons with electron energy loss spectroscopy. Chem. Rev. 118, 2994–3031 (2018).

    CAS  Google Scholar 

  32. Ashkin, A., Dziedzic, J. M., Bjorkholm, J. E. & Chu, S. Observation of a single-beam gradient force optical trap for dielectric particles. Opt. Lett. 11, 288–290 (1986).

    CAS  Google Scholar 

  33. Novotny, L., Bian, R. X. & Xie, X. S. Theory of nanometric optical tweezers. Phys. Rev. Lett. 79, 645–648 (1997).

    CAS  Google Scholar 

  34. Juan, M. L., Righini, M. & Quidant, R. Plasmon nano-optical tweezers. Nat. Photonics 5, 349–356 (2011).

    Google Scholar 

  35. Reipa, V., Monbouquette, H. G. & Vilker, V. L. Combined spectroscopic ellipsometry and voltammetry of tetradecylmethyl viologen films on gold. Langmuir 14, 6563–6569 (1998).

    CAS  Google Scholar 

  36. Han, B., Li, Z., Wandlowski, T., Błaszczyk, A. & Mayor, M. Potential-induced redox switching in viologen self-assembled monolayers: an ATR−SEIRAS approach. J. Phys. Chem. C. 111, 13855–13863 (2007).

    CAS  Google Scholar 

  37. Frens, G. Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions. Nature 241, 20–22 (1973).

    CAS  Google Scholar 

  38. Li, C. Y. et al. In situ monitoring of electrooxidation processes at gold single crystal surfaces using shell-isolated nanoparticle-enhanced Raman spectroscopy. J. Am. Chem. Soc. 137, 7648–7651 (2015).

    CAS  Google Scholar 

  39. Hölzle, M. H., Wandlowski, T. & Kolb, D. M. Phase transition in uracil adlayers on electrochemically prepared island-free Au(100)−(1 × 1). J. Electroanal. Chem. 394, 271–275 (1995).

    Google Scholar 

  40. Li, C. Y. et al. Real-time detection of single-molecule reaction by plasmon-enhanced spectroscopy. Sci. Adv. 6, eaba6012 (2020).

    CAS  Google Scholar 

  41. Stephens, P. J., Devlin, F. J., Chabalowski, C. F. & Frisch, M. J. Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields. J. Phys. Chem. 98, 11623–11627 (1994).

    CAS  Google Scholar 

  42. Ditchfield, R., Hehre, W. J. & Pople, J. A. Self‐consistent molecular‐orbital methods. IX. An extended Gaussian‐type basis for molecular‐orbital studies of organic molecules. J. Chem. Phys. 54, 724–728 (1971).

    CAS  Google Scholar 

  43. Sagara, T., Maeda, H., Yuan, Y. & Nakashima, N. Voltammetric and electroreflectance study of thiol-functionalized viologen monolayers on polycrystalline gold: effect of anion binding to a viologen moiety. Langmuir 15, 3823–3830 (1999).

    CAS  Google Scholar 

  44. Lipparini, F. et al. A variational formulation of the polarizable continuum model. J. Chem. Phys. 133, 014106 (2010).

    Google Scholar 

  45. Bauernschmitt, R. & Ahlrichs, R. Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory. Chem. Phys. Lett. 256, 454–464 (1996).

    CAS  Google Scholar 

  46. Neugebauer, J., Reiher, M., Kind, C. & Hess, B. A. Quantum chemical calculation of vibrational spectra of large molecules—Raman and IR spectra for buckminsterfullerene. J. Comput. Chem. 23, 895–910 (2002).

    CAS  Google Scholar 

  47. Le Ru, E. & Etchegoin, P. Principles of Surface-enhanced Raman Spectroscopy and Related Plasmonic Effects (Elsevier, 2008).

  48. Purcell, E. M. in Confined Electrons and Photons: New Physics and Applications (eds Burstein, E. & Weisbuch, C.) 839 (Springer, 1995).

  49. Duan, S., Tian, G., Xie, Z. & Luo, Y. Gauge invariant theory for super high resolution Raman images. J. Chem. Phys. 146, 194106 (2017).

    Google Scholar 

  50. Le, Ru,E. C. & Etchegoin, P. G. Rigorous justification of the |E|4 enhancement factor in surface enhanced raman spectroscopy. Chem. Phys. Lett. 423, 63–66 (2006).

    Google Scholar 

  51. Tian, G. J., Duan, S., Hua, W. & Luo, Y. Dynavib v. 1.0 (Royal Institute of Technology, 2012).

  52. Duan, S., Tian, G. J. & Luo, Y. First-principles Approaches for Surface and Tip-enhanced Raman Scattering (FASTERS) v.1.0 (Royal Institute of Technology, 2016).

  53. Macak, P., Luo, Y. & Ågren, H. Simulations of vibronic profiles in two-photon absorption. Chem. Phys. Lett. 330, 447–456 (2000).

    CAS  Google Scholar 

  54. Gong, Z.-Y., Tian, G., Duan, S. & Luo, Y. Significant contributions of the Albrecht’s a term to nonresonant Raman scattering processes. J. Chem. Theory Comput. 11, 5385–5390 (2015).

    CAS  Google Scholar 

  55. Xie, Z., Duan, S., Wang, C.-K. & Luo, Y. Monitoring hydrogen/deuterium tautomerization in transient isomers of single porphine by highly localized plasmonic field. J. Phys. Chem. C. 123, 11081–11093 (2019).

    CAS  Google Scholar 

  56. Henrique, T. M., Baltar, C. M., Drozdowicz-Tomsia, K. & Goldys, E. M. in Plasmonics – Principles and Applications (ed. Kim, K. Y.) 135–156 (IntechOpen, 2012).

  57. Shaidiuk, V. & Menabde, S. G. Modal evolution in asymmetric three- and four-layer plasmonic waveguides. Opt. Express 24, 16595–16608 (2016).

    CAS  Google Scholar 

  58. Zhang, W., Huang, L., Santschi, C. & Martin, O. J. F. Trapping and sensing 10 nm metal nanoparticles using plasmonic dipole antennas. Nano Lett. 10, 1006–1011 (2010).

    Google Scholar 

Download references

Acknowledgements

We thank X. S. Zhou, Z. L. Yang, L. W. Ye, Z. Lu, Y. H. Wang and Q. Y. Dai for helpful discussions. This work was supported by the National Natural Science Foundation of China (grant nos. 21925404, 21775127, 21427813 and 21790350), the National Key Research and Development Programme of China (grant nos. 2019YFA0705400 and 2017YFA0303500), and the Anhui Initiative in Quantum Information Technologies (grant no. AHY090000). The Swedish National Infrastructure for Computing is acknowledged for computer time. S.D. is sponsored by Shanghai Pujiang Programme (grant no. 19PJ1400600).

Author information

Authors and Affiliations

Authors

Contributions

J.-F.L., Y.L., C.-Y.L. and S.D. conceived and designed the project. C.-Y.L., B.-Y.W., S.-B.L., K.M., L.-Q.X., B.-W.M. and J.-F.L. performed the experiments. S.D. and Y.L. performed the DFT and MIM calculations. S.C. performed the FEM simulations. J.-F.L., Y.L., Z.-Q.T., C.-Y.L., S.D. and J.R.A. analysed the results and wrote the manuscript. All authors contributed to the interpretation of data.

Corresponding authors

Correspondence to Yi Luo or Jian-Feng Li.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Nanotechnology thanks Javier Garcia de Abajo and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Notes I–III, Figs. 1–9 and Tables 1 and 2.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, CY., Duan, S., Wen, BY. et al. Observation of inhomogeneous plasmonic field distribution in a nanocavity. Nat. Nanotechnol. 15, 922–926 (2020). https://doi.org/10.1038/s41565-020-0753-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41565-020-0753-y

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing