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Single-molecule resonance Raman effect in a plasmonic nanocavity

Nature Nanotechnology volume 15, pages 105–110 (2020)Cite this article

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Abstract

Tip-enhanced Raman spectroscopy (TERS) is a versatile tool for chemical analysis at the nanoscale. In earlier TERS experiments, Raman modes with components parallel to the tip were studied based on the strong electric field enhancement along the tip. Perpendicular modes were usually neglected. Here, we investigate an isolated copper naphthalocyanine molecule adsorbed on a triple-layer NaCl on Ag(111) using scanning tunnelling microscope TERS imaging. For flat-lying molecules on NaCl, the Raman images present different patterns depending on the symmetry of the vibrational mode. Our results reveal that components of the electric field perpendicular to the tip should be considered aside from the parallel components. Moreover, under resonance excitation conditions, the perpendicular components can play a substantial role in the enhancement. This single-molecule study in a well-defined environment provides insights into the Raman process at the plasmonic nanocavity, which may be useful in the nanoscale metrology of various molecular systems.

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Fig. 1: Investigating the CuNc molecule via STM and STM-TERS.
Fig. 2: Preserving the intrinsic properties of the molecule using NaCl.
Fig. 3: Excitation wavelength dependence of the STM-TERS spectra.
Fig. 4: Single-molecule TERS mapping of a CuNc molecule on NaCl.

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Data availability

Data presented in this work are available upon reasonable request from Y. Kim.

References

  1. Jeanmaire, D. L. & Van Duyne, R. P. Surface Raman spectroelectrochemistry: part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode. J. Electroanal. Chem. 84, 1–20 (1977).

    CAS  Google Scholar 

  2. Fleischmann, M., Hendra, P. J. & McQuillan, A. J. Raman spectra of pyridine adsorbed at a silver electrode. Chem. Phys. Lett. 26, 163–166 (1974).

    CAS  Google Scholar 

  3. Albrecht, M. G. & Creighton, J. A. Anomalously intense Raman spectra of pyridine at a silver electrode. J. Am. Chem. Soc. 99, 5215–5217 (1977).

    CAS  Google Scholar 

  4. Stöckle, R. M., Suh, Y. D., Deckert, V. & Zenobi, R. Nanoscale chemical analysis by tip-enhanced Raman spectroscopy. Chem. Phys. Lett. 318, 131–136 (2000).

    Google Scholar 

  5. Hayazawa, N., Inouye, Y., Sekkat, Z. & Kawata, S. Metallized tip amplification of near-field Raman scattering. Opt. Commun. 183, 333–336 (2000).

    CAS  Google Scholar 

  6. Anderson, M. S. Locally enhanced Raman spectroscopy with an atomic force microscope. Appl. Phys. Lett. 76, 3130–3132 (2000).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  8. Jiang, S. et al. Distinguishing adjacent molecules on a surface using plasmon-enhanced Raman scattering. Nat. Nanotechnol. 10, 865–870 (2015).

    CAS  Google Scholar 

  9. 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 

  10. Ding, S. Y., You, E. M., Tian, Z. Q. & Moskovits, M. Electromagnetic theories of surface-enhanced Raman spectroscopy. Chem. Soc. Rev. 46, 4042–4076 (2017).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  12. Shin, H.-H. et al. Frequency-domain proof of the existence of atomic-scale SERS hot-spots. Nano Lett. 18, 262–271 (2018).

    CAS  Google Scholar 

  13. Ueba, H. Theory of charge transfer excitation in surface enhanced Raman scattering. Surf. Sci. 131, 347–366 (1983).

    CAS  Google Scholar 

  14. Persson, B. N. J. On the theory of surface-enhanced Raman scattering. Chem. Phys. Lett. 82, 561–565 (1981).

    CAS  Google Scholar 

  15. Kambhampati, P. & Campion, A. Surface enhanced Raman scattering as a probe of adsorbate–substrate charge-transfer excitations. Surf. Sci. 427, 115–125 (1999).

    Google Scholar 

  16. Albrecht, A. & Hutley, M. C. On the dependence of vibrational Raman intensity on the wavelength of incident light. J. Chem. Phys. 55, 4438–4443 (1971).

    CAS  Google Scholar 

  17. Lombardi, J. R. & Birke, R. L. A unified approach to surface-enhanced Raman spectroscopy. J. Phys. Chem. C 112, 5605–5617 (2008).

    CAS  Google Scholar 

  18. Whiteman, P. J., Schultz, J. F., Porach, Z. D., Chen, H. & Jiang, N. Dual binding configurations of subphthalocyanine on Ag(100) substrate characterized by scanning tunneling microscopy, tip-enhanced raman spectroscopy, and density functional theory. J. Phys. Chem. C 122, 5489–5495 (2018).

    CAS  Google Scholar 

  19. Jiang, N. et al. Nanoscale chemical imaging of a dynamic molecular phase boundary with ultrahigh vacuum tip-enhanced Raman spectroscopy. Nano Lett. 16, 3898–3904 (2016).

    CAS  Google Scholar 

  20. Bhattarai, A. et al. Tip-enhanced Raman scattering from nanopatterned graphene and graphene oxide. Nano Lett. 18, 4029–4033 (2018).

    CAS  Google Scholar 

  21. Repp, J., Meyer, G., Stojković, S. M., Gourdon, A. & Joachim, C. Molecules on insulating films: scanning-tunneling microscopy imaging of individual molecular orbitals. Phys. Rev. Lett. 94, 26803 (2005).

    Google Scholar 

  22. Imada, H. et al. Single-molecule investigation of energy dynamics in a coupled plasmon-exciton system. Phys. Rev. Lett. 119, 13901 (2017).

    Google Scholar 

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

    CAS  Google Scholar 

  24. 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 

  25. Swart, I., Sonnleitner, T. & Repp, J. Charge state control of molecules reveals modification of the tunneling barrier with intramolecular contrast. Nano Lett. 11, 1580–1584 (2011).

    CAS  Google Scholar 

  26. Latorre, F. et al. Spatial resolution of tip-enhanced Raman spectroscopy – DFT assessment of the chemical effect. Nanoscale 8, 10229–10239 (2016).

    CAS  Google Scholar 

  27. Neuman, T. T. et al. Coupling of molecular emitters and plasmonic cavities beyond the point-dipole approximation. Nano Lett. 18, 2358–2364 (2018).

    CAS  Google Scholar 

  28. Liu, P., Chulhai, D. V. & Jensen, L. Single-molecule imaging using atomistic near-field tip-enhanced Raman spectroscopy. ACS Nano 11, 5094–5102 (2017).

    CAS  Google Scholar 

  29. Chen, X., Liu, P., Hu, Z. & Jensen, L. High-resolution tip-enhanced Raman scattering probes sub-molecular density changes. Nat. Commun. 10, 2567 (2019).

    Google Scholar 

  30. Banik, M. et al. Surface-enhanced Raman trajectories on a nano-dumbbell: transition from field to charge transfer plasmons as the spheres fuse. ACS Nano 6, 10353–10354 (2012).

    Google Scholar 

  31. Aroyo, M. I. et al. Bilbao crystallographic server: I. Databases and crystallographic computing programs. Zeitschrift fur Krist. 221, 15–27 (2006).

    CAS  Google Scholar 

  32. Aroyo, M. I., Kirov, A., Capillas, C., Perez-Mato, J. M. & Wondratschek, H. Bilbao crystallographic server. II. Representations of crystallographic point groups and space groups. Acta Crystallogr. A 62, 115–128 (2006).

    Google Scholar 

  33. Aroyo, M. I. et al. Crystallography online: Bilbao crystallographic server. Bulg. Chem. Commun. 43, 183–197 (2011).

    CAS  Google Scholar 

  34. Doppagne, B. et al. Vibronic spectroscopy with submolecular resolution from STM-induced electroluminescence. Phys. Rev. Lett. 118, 127401 (2017).

    Google Scholar 

  35. Nečas, D. & Klapetek, P. Gwyddion: an open-source software for SPM data analysis. Cent. Eur. J. Phys. 10, 181–188 (2012).

    Google Scholar 

  36. Vincett, P. S., Voigt, E. M. & Rieckhoff, K. E. Phosphorescence and fluorescence of phthalocyanines. J. Chem. Phys. 55, 4131–4140 (1971).

    CAS  Google Scholar 

  37. Wu, S. W., Nazin, G. V. & Ho, W. Intramolecular photon emission from a single molecule in a scanning tunneling microscope. Phys. Rev. B 77, 205430 (2008).

    Google Scholar 

  38. Miwa, K., Sakaue, M., Gumhalter, B. & Kasai, H. Effects of plasmon energetics on light emission induced by scanning tunneling microscopy. J. Phys. Condens. Matter 26, 222001 (2014).

    CAS  Google Scholar 

  39. Miwa, K., Sakaue, M. & Kasai, H. Effects of interference between energy absorption processes of molecule and surface plasmons on light emission induced by scanning tunneling microscopy. J. Phys. Soc. Jpn 82, 124707 (2013).

    Google Scholar 

  40. Yang, B., Kazuma, E., Yokota, Y. & Kim, Y. Fabrication of sharp gold tips by three-electrode electrochemical etching with high controllability and reproducibility. J. Phys. Chem. C 122, 16950–16955 (2018).

    CAS  Google Scholar 

  41. Gaussian 16 Revision B.01 (Gaussian, 2016).

  42. Weigend, F. & Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy. Phys. Chem. Chem. Phys. 7, 3297–3305 (2005).

    CAS  Google Scholar 

  43. Becke, A. D. Density‐functional thermochemistry. III The role of exact exchange. J. Chem. Phys. 98, 5648 (1993).

    CAS  Google Scholar 

  44. Chai, J.-D. & Head-Gordon, M. Systematic optimization of long-range corrected hybrid density functionals. J. Chem. Phys. 128, 084106 (2008).

    Google Scholar 

  45. Runge, E. & Gross, E. K. U. Density-functional theory for time-dependent systems. Phys. Rev. Lett. 52, 997–1000 (1984).

    CAS  Google Scholar 

  46. Casida, M. E. in Recent Advances In Density Functional Methods Part I (ed. Chong, D. P.) 155–192 (World Scientific, 1995).

  47. Hirata, S. & Head-Gordon, M. Time-dependent density functional theory within the Tamm–Dancoff approximation. Chem. Phys. Lett. 314, 291–299 (1999).

    CAS  Google Scholar 

  48. Egidi, F., Bloino, J., Cappelli, C. & Barone, V. A robust and effective time-independent route to the calculation of resonance raman spectra of large molecules in condensed phases with the inclusion of Duschinsky, Herzberg–Teller, anharmonic, and environmental effects. J. Chem. Theory Comput. 10, 346–363 (2013).

    Google Scholar 

  49. Baiardi, A., Bloino, J. & Barone, V. A general time-dependent route to resonance-Raman spectroscopy including Franck-Condon, Herzberg-Teller and Duschinsky effects. J. Chem. Phys. 141, 114108 (2014).

    Google Scholar 

  50. Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).

    CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported in part by the Grant-in-Aid for Scientific Research (KAKENHI) nos 15H02025 (Y.K.), 15H03569 (N.H.), 17H04796 (H.I.), 17H05470 (H.I.), 17K18766 (H.I.), 18K14153 (R.B.J.), 16K21623 (K.M.) and 17K14428 (T.I.), and Grant-in-Aid for JSPS Fellows no. 15J03915 (K.M.) from the Ministry of Education, Culture, Sports, Science and Technology of Japan. R.B.J. acknowledges the Special Postdoctoral (SPDR) program of RIKEN. Parts of the numerical calculations were performed with the aid of the HOKUSAI supercomputer system at RIKEN. We thank H. Ueba, K. Kimura and M. Balgos for helpful discussions, D. Miyajima and T. Aida for the vacuum purification and room temperature absorbance measurements and F.C. Catalan and R. Wong for carefully reading the manuscript.

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Author notes

  1. Kuniyuki Miwa

    Present address: Department of Chemistry, Northwestern University, Evanston, IL, USA

  2. Bo Yang

    Present address: School of Science, Xijing University, Xi’an, China

Authors and Affiliations

  1. Surface and Interface Science Laboratory, RIKEN, Wako, Saitama, Japan

    Rafael B. Jaculbia, Hiroshi Imada, Kuniyuki Miwa, Bo Yang, Emiko Kazuma, Norihiko Hayazawa & Yousoo Kim

  2. PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama, Japan

    Hiroshi Imada

  3. Department of Chemistry, Faculty of Science and Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita-ku, Sapporo, Japan

    Takeshi Iwasa, Masato Takenaka & Tetsuya Taketsugu

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Contributions

R.B.J., H.I. and N.H. designed the experiments. R.B.J. performed all experiments with contributions from H.I.; R.B.J., N.H. and H.I. analysed the experimental data, and K.M. provided DFT calculations of the vibrational modes. T.I., M.T. and T.T. performed the electric field simulations. B.Y. and E.K. prepared the Au tips. Y.K. planned and supervised the project. All authors contributed to the interpretation of the results and writing the manuscript.

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Correspondence to Hiroshi Imada, Norihiko Hayazawa or Yousoo Kim.

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Peer review information Nature Nanotechnology thanks Patrick (Z.) El-Khoury and the other, anonymous, reviewers for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Comparison between STM-TERS spectra with micro-Raman spectra and DFT calculations.

The observed peaks in the STM-TERS correspond well to DFT calculated vibrational modes and the powder Raman spectrum taken at room temperature (see Table S1). STM-TERS spectrum was taken using 738 nm laser with 1 mW and 30 s exposure time at Vb = 1 V and It = 50 pA. Powder Raman spectrum was taken using a homebuilt Raman microscope with 532 nm excitation at 1 mW power and 30 s exposure time.

Extended Data Fig. 2 STM topography and DFT calculated molecular orbitals.

Figure shows the STM topography (a) and (b) of the CuNc molecule and the DFT calculated molecular orbitals (c)–(e). The STM topography at HOMO a, was taken at Vb = -1.85 V and It = 10 pA while LUMO image b, was taken at Vb = 0.8 V and It = 10 pA. The STM image of the HOMO level is identical in shape to the DFT calculated HOMO c, Meanwhile, the DFT calculated LUMO is degenerated into LUMOα and LUMOβ ((d) and e, respectively). Considering that the STM can image the degenerated LUMO, of the molecule simultaneously, the STM image the STM image correspond well to the spatial distribution of the density ρ = |LUMOα|2 + |LUMOβ|2 shown in f. Since the STM image of CuNc on NaCl/Ag(111) mimics the DFT calculated molecular orbitals of a free molecule, we can argue that the NaCl is effective in electronically decoupling the CuNc molecule from the Ag(111) surface.

Extended Data Fig. 3 All data of wavelength dependence of the Raman signals.

a, STA of the molecule showing the different excitation wavelengths used as coloured lines according to the colours in (b) and (c), STA shown is the same as Fig. 2c of the main text. In (b) and (c), the labels correspond to the wavelength used for the particular spectrum. b, Wavelength dependence of the Raman spectrum with wavelength as x-axis. The spectra were clipped from 755 nm for the data taken using 720 - 739 nm pump and from 790 nm for the those taken using 742 nm and above to account for the long pass filter response. The small lines at the left part of each spectrum correspond to the position of the excitation laser per spectrum. c, Wavelength dependence of the Raman spectrum with wavenumber as x-axis. Raman data were taken using 1 V, 50 pA, 30 s exposure time, and 1 mW laser power. The spectra in (b) and (c) were shifted vertically for clarity.

Extended Data Fig. 4 Resonance TERS mapping of a single molecule.

Figure shows the intensity plots of individual vibrational modes taken at 1 s integration time, Vb = 1 V, It = 50 pA and 1 angstrom / pixel step size (40 pixels × 40 pixels). A complete Raman spectrum is taken per pixel simultaneously with the STM topography also shown here. Apart from one peak (1211 cm-1, see Supplementary Table 1), all experimental TERS peaks can be assigned unambiguously to calculated resonance Raman vibrational modes. A table comparing the DFT and experimental results is shown in Supplementary Table 1. Three image profiles can be seen and their appearance are due to the symmetry of the assigned vibrational modes as discussed in the main text.

Extended Data Fig. 5 Parity rule and the molecular orbital.

Figure shows the calculated molecular orbital of the CuNc at the x-y (a–c) and x-z (d–f) planes. For a centrosymmetric molecule like CuNc, HOMO-LUMO transitions are only allowed when there is a change in the parity as invoked by the parity rule. As viewed from the x-y plane, the molecular orbital show odd parity for the HOMO a, and an even parity for the LUMO b, c. This implies that HOMO-LUMO transitions with excitation along the x-y plane are parity allowed according to the Laporte rule. On the other hand, as viewed from the x-z plane, the molecular orbitals shows an odd parity for both the HOMO (d) and the LUMO e, f, suggesting that, HOMO-LUMO transitions with excitation along the z-axis are parity forbidden according to the Laporte rule.

Extended Data Fig. 6 Induced dipole moment and vibrational symmetry.

Figure shows the direction of the induced dipole moment vector represented by the blue arrow for different vibrational symmetries and tip positions. The tip positions are at the phenyl ring (a) and (c) and in between two phenyl rings b, as indicated by the red dot. The dipole moment vector was obtained using pρ(ωL± ων) = αρσEσ(ωL) where pρ, Eσ, ωL and ων are the dipole moment vector, incident electric field vector of the plasmonic nanocavity, frequency of the laser and the frequency of the vibrational mode respectively, and αρσ is the Raman tensor given by equation 1 in the main text. The cartesian coordinate axes x, y, and z are represented by the subscripts ρ and σ. The vector of the plasmonic nanocavity at three different tip positions (red dot) is represented by the grey arrow.

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Supplementary information

Supplementary Figures 1–13 and Tables 1–3.

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Jaculbia, R.B., Imada, H., Miwa, K. et al. Single-molecule resonance Raman effect in a plasmonic nanocavity. Nat. Nanotechnol. 15, 105–110 (2020). https://doi.org/10.1038/s41565-019-0614-8

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