Tip-enhanced Raman spectroscopy of 4,4′-bipyridine and 4,4′-bipyridine N,N'-dioxide adsorbed on gold thin films

Izabela Irena Rzeznicka, H. Horino, N. Kikkawa, S. Sakaguchi, A. Morita, S. Takahashi, T. Komeda, H. Fukumura, T. Yamada, M. Kawai

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

A tip-enhanced Raman spectroscopy (TERS) set-up added on a scanning tunneling microscope (STM) was constructed and was used to study the molecular arrangement of 4,4′-bipyridine (4,4′-BiPy) and 4,4′-bipyridine N,N'-dioxide (4,4′-BiPyO2) adsorbed on Au(111). Over a monolayer of 4,4′-BiPy, in the ambient atmosphere, intense TERS signals were recorded, involving AuN stretching vibration at 185 cm- 1. At the early stage of 4,4′-BiPy adsorption, the AuN stretching signal was not detected. By the aid of the theoretical calculations of the Raman scattering intensities for each vibrational normal mode, a standing-up, tilted orientation at monolayer coverage and a vertical orientation with the longitudinal molecular axis parallel to the surface at low surface coverage was concluded. Adsorption of 4,4′-BiPyO2 on Au(111) resulted in formation of a (6 × 9) adlattice. Moderately intense TERS signals were observed, containing the NO stretching modes and the in-plane ring vibrational modes. Neither AuO nor AuN stretching modes were observed. 4,4′-BiPyO2 was laid with the longitudinal axis parallel to the surface, and the molecular plane vertical to the surface. These results demonstrate that STM-TERS is an effective method for simultaneous imaging and vibrational analysis, facilitating identification of the adsorbed layers with the nanometer-scale spatial resolution and monolayer sensitivity.

Original languageEnglish
Pages (from-to)1-9
Number of pages9
JournalSurface Science
Volume617
DOIs
Publication statusPublished - 2013 Nov
Externally publishedYes

Fingerprint

dioxides
Gold
Stretching
Raman spectroscopy
gold
Monolayers
Thin films
thin films
Microscopes
microscopes
vertical orientation
Scanning
Adsorption
adsorption
scanning
Raman scattering
vibration mode
spatial resolution
Raman spectra
Imaging techniques

Keywords

  • 4,4′-bipyridine
  • 4,4′-bipyridine N
  • N'-dioxide Au(111)
  • Raman tensor
  • Tip-enhanced Raman spectroscopy

ASJC Scopus subject areas

  • Surfaces and Interfaces
  • Condensed Matter Physics
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

Tip-enhanced Raman spectroscopy of 4,4′-bipyridine and 4,4′-bipyridine N,N'-dioxide adsorbed on gold thin films. / Rzeznicka, Izabela Irena; Horino, H.; Kikkawa, N.; Sakaguchi, S.; Morita, A.; Takahashi, S.; Komeda, T.; Fukumura, H.; Yamada, T.; Kawai, M.

In: Surface Science, Vol. 617, 11.2013, p. 1-9.

Research output: Contribution to journalArticle

Rzeznicka, II, Horino, H, Kikkawa, N, Sakaguchi, S, Morita, A, Takahashi, S, Komeda, T, Fukumura, H, Yamada, T & Kawai, M 2013, 'Tip-enhanced Raman spectroscopy of 4,4′-bipyridine and 4,4′-bipyridine N,N'-dioxide adsorbed on gold thin films', Surface Science, vol. 617, pp. 1-9. https://doi.org/10.1016/j.susc.2013.08.010
Rzeznicka, Izabela Irena ; Horino, H. ; Kikkawa, N. ; Sakaguchi, S. ; Morita, A. ; Takahashi, S. ; Komeda, T. ; Fukumura, H. ; Yamada, T. ; Kawai, M. / Tip-enhanced Raman spectroscopy of 4,4′-bipyridine and 4,4′-bipyridine N,N'-dioxide adsorbed on gold thin films. In: Surface Science. 2013 ; Vol. 617. pp. 1-9.
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abstract = "A tip-enhanced Raman spectroscopy (TERS) set-up added on a scanning tunneling microscope (STM) was constructed and was used to study the molecular arrangement of 4,4′-bipyridine (4,4′-BiPy) and 4,4′-bipyridine N,N'-dioxide (4,4′-BiPyO2) adsorbed on Au(111). Over a monolayer of 4,4′-BiPy, in the ambient atmosphere, intense TERS signals were recorded, involving AuN stretching vibration at 185 cm- 1. At the early stage of 4,4′-BiPy adsorption, the AuN stretching signal was not detected. By the aid of the theoretical calculations of the Raman scattering intensities for each vibrational normal mode, a standing-up, tilted orientation at monolayer coverage and a vertical orientation with the longitudinal molecular axis parallel to the surface at low surface coverage was concluded. Adsorption of 4,4′-BiPyO2 on Au(111) resulted in formation of a (6 × 9) adlattice. Moderately intense TERS signals were observed, containing the NO stretching modes and the in-plane ring vibrational modes. Neither AuO nor AuN stretching modes were observed. 4,4′-BiPyO2 was laid with the longitudinal axis parallel to the surface, and the molecular plane vertical to the surface. These results demonstrate that STM-TERS is an effective method for simultaneous imaging and vibrational analysis, facilitating identification of the adsorbed layers with the nanometer-scale spatial resolution and monolayer sensitivity.",
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AU - Horino, H.

AU - Kikkawa, N.

AU - Sakaguchi, S.

AU - Morita, A.

AU - Takahashi, S.

AU - Komeda, T.

AU - Fukumura, H.

AU - Yamada, T.

AU - Kawai, M.

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AB - A tip-enhanced Raman spectroscopy (TERS) set-up added on a scanning tunneling microscope (STM) was constructed and was used to study the molecular arrangement of 4,4′-bipyridine (4,4′-BiPy) and 4,4′-bipyridine N,N'-dioxide (4,4′-BiPyO2) adsorbed on Au(111). Over a monolayer of 4,4′-BiPy, in the ambient atmosphere, intense TERS signals were recorded, involving AuN stretching vibration at 185 cm- 1. At the early stage of 4,4′-BiPy adsorption, the AuN stretching signal was not detected. By the aid of the theoretical calculations of the Raman scattering intensities for each vibrational normal mode, a standing-up, tilted orientation at monolayer coverage and a vertical orientation with the longitudinal molecular axis parallel to the surface at low surface coverage was concluded. Adsorption of 4,4′-BiPyO2 on Au(111) resulted in formation of a (6 × 9) adlattice. Moderately intense TERS signals were observed, containing the NO stretching modes and the in-plane ring vibrational modes. Neither AuO nor AuN stretching modes were observed. 4,4′-BiPyO2 was laid with the longitudinal axis parallel to the surface, and the molecular plane vertical to the surface. These results demonstrate that STM-TERS is an effective method for simultaneous imaging and vibrational analysis, facilitating identification of the adsorbed layers with the nanometer-scale spatial resolution and monolayer sensitivity.

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