Ultrahigh vacuum tip-enhanced raman spectroscopy with picosecond excitation

Eric A. Pozzi, Matthew D. Sonntag, Nan Jiang, Naihao Chiang, Tamar Seideman, Mark C Hersam, Richard P. Van Duyne

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Tip-enhanced Raman spectroscopy (TERS) provides chemical information about adsorbates with nanoscale spatial resolution, but developments are still required in order to incorporate ultrafast temporal resolution. In this Letter, we demonstrate that a reliable TER signal of rhodamine 6G (R6G) using picosecond (ps)-pulsed excitation can be obtained in ultrahigh vacuum (UHV). In contrast to our previous observation of irreversible signal loss in ambient TERS (Klingsporn, J. M.; Sonntag, M. D.; Seideman, T.; Van Duyne, R. P. J. Phys. Chem. Lett. 2014, 5, 106-110), we demonstrate that the UHV environment decreases irreversible signal degradation. As a complement to the TERS experiments, we examined the rate of surface-enhanced Raman (SER) signal decay under picosecond irradiation and found that it is also slowed in UHV compared to that in ambient. Signal decay kinetics suggest that the predominant mechanism responsible for signal loss in ps SERS of R6G is surface diffusion. Both diffusive and reactive phenomena can lead to pulsed excitation TER signal loss, and a UHV environment is advantageous in either scenario.

Original languageEnglish
Pages (from-to)2657-2661
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume5
Issue number15
DOIs
Publication statusPublished - Aug 7 2014

Fingerprint

Ultrahigh vacuum
ultrahigh vacuum
Raman spectroscopy
excitation
rhodamine
Surface diffusion
Adsorbates
Irradiation
Degradation
decay
Kinetics
surface diffusion
temporal resolution
complement
spatial resolution
degradation
Experiments
irradiation
kinetics
rhodamine 6G

Keywords

  • kinetics
  • plasmonics
  • tip-enhanced Raman spectroscopy
  • ultrafast spectroscopy
  • ultrahigh vacuum

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Pozzi, E. A., Sonntag, M. D., Jiang, N., Chiang, N., Seideman, T., Hersam, M. C., & Van Duyne, R. P. (2014). Ultrahigh vacuum tip-enhanced raman spectroscopy with picosecond excitation. Journal of Physical Chemistry Letters, 5(15), 2657-2661. https://doi.org/10.1021/jz501239z

Ultrahigh vacuum tip-enhanced raman spectroscopy with picosecond excitation. / Pozzi, Eric A.; Sonntag, Matthew D.; Jiang, Nan; Chiang, Naihao; Seideman, Tamar; Hersam, Mark C; Van Duyne, Richard P.

In: Journal of Physical Chemistry Letters, Vol. 5, No. 15, 07.08.2014, p. 2657-2661.

Research output: Contribution to journalArticle

Pozzi, EA, Sonntag, MD, Jiang, N, Chiang, N, Seideman, T, Hersam, MC & Van Duyne, RP 2014, 'Ultrahigh vacuum tip-enhanced raman spectroscopy with picosecond excitation', Journal of Physical Chemistry Letters, vol. 5, no. 15, pp. 2657-2661. https://doi.org/10.1021/jz501239z
Pozzi, Eric A. ; Sonntag, Matthew D. ; Jiang, Nan ; Chiang, Naihao ; Seideman, Tamar ; Hersam, Mark C ; Van Duyne, Richard P. / Ultrahigh vacuum tip-enhanced raman spectroscopy with picosecond excitation. In: Journal of Physical Chemistry Letters. 2014 ; Vol. 5, No. 15. pp. 2657-2661.
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