Intramolecular insight into adsorbate-substrate interactions via low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy

Jordan M. Klingsporn, Nan Jiang, Eric A. Pozzi, Matthew D. Sonntag, Dhabih Chulhai, Tamar Seideman, Lasse Jensen, Mark C. Hersam, Richard P. Van Duyne

Research output: Contribution to journalArticle

83 Citations (Scopus)

Abstract

Tip-enhanced Raman spectroscopy (TERS) provides chemical information for adsorbates with nanoscale spatial resolution, single-molecule sensitivity, and, when combined with scanning tunneling microscopy (STM), Ångstrom-scale topographic resolution. Performing TERS under ultrahigh-vacuum conditions allows pristine and atomically smooth surfaces to be maintained, while liquid He cooling minimizes surface diffusion of adsorbates across the solid surface, allowing direct STM imaging. Low-temperature TER (LT-TER) spectra differ from room-temperature TER (RT-TER), RT surface-enhanced Raman (SER), and LT-SER spectra because the vibrational lines are narrowed and shifted, revealing additional chemical information about adsorbate-substrate interactions. As an example, we present LT-TER spectra for the rhodamine 6G (R6G)/Ag(111) system that exhibit such unique spectral shifts. The high spectral resolution of LT-TERS provides intramolecular insight in that the shifted modes are associated with the ethylamine moiety of R6G. LT-TERS is a promising approach for unraveling the intricacies of adsorbate-substrate interactions that are inaccessible by other means.

Original languageEnglish (US)
Pages (from-to)3881-3887
Number of pages7
JournalJournal of the American Chemical Society
Volume136
Issue number10
DOIs
StatePublished - Mar 12 2014

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Raman Spectrum Analysis
Ultrahigh vacuum
Adsorbates
Vacuum
Raman spectroscopy
Scanning Tunnelling Microscopy
Temperature
Scanning tunneling microscopy
Substrates
Surface diffusion
Spectral resolution
Raman scattering
Cooling
Imaging techniques
Molecules
Liquids
rhodamine 6G

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Klingsporn, J. M., Jiang, N., Pozzi, E. A., Sonntag, M. D., Chulhai, D., Seideman, T., ... Van Duyne, R. P. (2014). Intramolecular insight into adsorbate-substrate interactions via low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy. Journal of the American Chemical Society, 136(10), 3881-3887. https://doi.org/10.1021/ja411899k
Klingsporn, Jordan M. ; Jiang, Nan ; Pozzi, Eric A. ; Sonntag, Matthew D. ; Chulhai, Dhabih ; Seideman, Tamar ; Jensen, Lasse ; Hersam, Mark C. ; Van Duyne, Richard P. / Intramolecular insight into adsorbate-substrate interactions via low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 10. pp. 3881-3887.
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Klingsporn, JM, Jiang, N, Pozzi, EA, Sonntag, MD, Chulhai, D, Seideman, T, Jensen, L, Hersam, MC & Van Duyne, RP 2014, 'Intramolecular insight into adsorbate-substrate interactions via low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy', Journal of the American Chemical Society, vol. 136, no. 10, pp. 3881-3887. https://doi.org/10.1021/ja411899k

Intramolecular insight into adsorbate-substrate interactions via low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy. / Klingsporn, Jordan M.; Jiang, Nan; Pozzi, Eric A.; Sonntag, Matthew D.; Chulhai, Dhabih; Seideman, Tamar; Jensen, Lasse; Hersam, Mark C.; Van Duyne, Richard P.

In: Journal of the American Chemical Society, Vol. 136, No. 10, 12.03.2014, p. 3881-3887.

Research output: Contribution to journalArticle

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T1 - Intramolecular insight into adsorbate-substrate interactions via low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy

AU - Klingsporn, Jordan M.

AU - Jiang, Nan

AU - Pozzi, Eric A.

AU - Sonntag, Matthew D.

AU - Chulhai, Dhabih

AU - Seideman, Tamar

AU - Jensen, Lasse

AU - Hersam, Mark C.

AU - Van Duyne, Richard P.

PY - 2014/3/12

Y1 - 2014/3/12

N2 - Tip-enhanced Raman spectroscopy (TERS) provides chemical information for adsorbates with nanoscale spatial resolution, single-molecule sensitivity, and, when combined with scanning tunneling microscopy (STM), Ångstrom-scale topographic resolution. Performing TERS under ultrahigh-vacuum conditions allows pristine and atomically smooth surfaces to be maintained, while liquid He cooling minimizes surface diffusion of adsorbates across the solid surface, allowing direct STM imaging. Low-temperature TER (LT-TER) spectra differ from room-temperature TER (RT-TER), RT surface-enhanced Raman (SER), and LT-SER spectra because the vibrational lines are narrowed and shifted, revealing additional chemical information about adsorbate-substrate interactions. As an example, we present LT-TER spectra for the rhodamine 6G (R6G)/Ag(111) system that exhibit such unique spectral shifts. The high spectral resolution of LT-TERS provides intramolecular insight in that the shifted modes are associated with the ethylamine moiety of R6G. LT-TERS is a promising approach for unraveling the intricacies of adsorbate-substrate interactions that are inaccessible by other means.

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