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

44 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 (US)
Pages (from-to)4114-4120
Number of pages7
JournalNano Letters
Volume15
Issue number6
DOIs
StatePublished - Jun 10 2015

Fingerprint

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

All Science Journal Classification (ASJC) codes

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

Cite this

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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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

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AU - Chiang, Naihao

AU - Jiang, Nan

AU - Chulhai, Dhabih V.

AU - Pozzi, Eric A.

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AU - Van Duyne, Richard P.

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N2 - 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).

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