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

91 Scopus citations

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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    Klingsporn, J. M., Jiang, N., Pozzi, E. A., Sonntag, M. D., Chulhai, D., Seideman, T., Jensen, L., Hersam, M. C., & 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