Molecular-Resolution Interrogation of a Porphyrin Monolayer by Ultrahigh Vacuum Tip-Enhanced Raman and Fluorescence Spectroscopy

Naihao Chiang, Nan Jiang, Dhabih V. Chulhai, Eric A. Pozzi, Mark C Hersam, Lasse Jensen, Tamar Seideman, Richard P. Van Duyne

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Tip-enhanced Raman scattering (TERS) and optically excited tip-enhanced fluorescence (TEF) of a self-assembled porphyrin monolayer on Ag(111) are studied using an ultrahigh vacuum scanning tunneling microscope (UHV-STM). Through selectively exciting different Q-bands of meso-tetrakis- (3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP), chemical information regarding different vibronic excited states is revealed by a combination of theory and experiment; namely, TERS and time-dependent density functional theory (TDDFT) simulations. The observed TEF spectra suggest a weak coupling of H2TBPP to the substrate due to the bulky t-butyl groups and a possible alternative excited state decay path. This work demonstrates the potential of combining TERS and TEF for studying surface-mounted porphyins on substrates, thus providing insight into porphyrin-sensitized solar cells and catalysis. (Figure Presented).

Original languageEnglish
Pages (from-to)4114-4120
Number of pages7
JournalNano Letters
Volume15
Issue number6
DOIs
Publication statusPublished - Jun 10 2015

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interrogation
Porphyrins
Fluorescence spectroscopy
Ultrahigh vacuum
porphyrins
ultrahigh vacuum
Raman spectroscopy
Raman scattering
Monolayers
Fluorescence
Excited states
fluorescence
spectroscopy
Substrates
Raman spectra
Catalysis
Density functional theory
Solar cells
Microscopes
Scanning

Keywords

  • time-dependent density functional theory (TDDFT)
  • tip-enhanced fluorescence (TEF)
  • tip-enhanced Raman spectroscopy (TERS)
  • ultrahigh vacuum scanning tunneling microscopy (UHV-STM)

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Bioengineering
  • Chemistry(all)
  • Materials Science(all)
  • Mechanical Engineering

Cite this

Molecular-Resolution Interrogation of a Porphyrin Monolayer by Ultrahigh Vacuum Tip-Enhanced Raman and Fluorescence Spectroscopy. / Chiang, Naihao; Jiang, Nan; Chulhai, Dhabih V.; Pozzi, Eric A.; Hersam, Mark C; Jensen, Lasse; Seideman, Tamar; Van Duyne, Richard P.

In: Nano Letters, Vol. 15, No. 6, 10.06.2015, p. 4114-4120.

Research output: Contribution to journalArticle

Chiang, Naihao ; Jiang, Nan ; Chulhai, Dhabih V. ; Pozzi, Eric A. ; Hersam, Mark C ; Jensen, Lasse ; Seideman, Tamar ; Van Duyne, Richard P. / Molecular-Resolution Interrogation of a Porphyrin Monolayer by Ultrahigh Vacuum Tip-Enhanced Raman and Fluorescence Spectroscopy. In: Nano Letters. 2015 ; Vol. 15, No. 6. pp. 4114-4120.
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