Tip-enhanced Raman spectroscopic imaging shows segregation within binary self-assembled thiol monolayers at ambient conditions

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Author(s) Lin, Wang-Ing, Shao, Feng, Stephanidis, Bruno, Zenobi, Renato
Publication Type Journal Items, Publication Status: Published
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Title Tip-enhanced Raman spectroscopic imaging shows segregation within binary self-assembled thiol monolayers at ambient conditions
Author(s) Lin, Wang-Ing
Shao, Feng
Stephanidis, Bruno
Zenobi, Renato
Journal or Series Title Analytical and bioanalytical chemistry
Volume Number 407
Issue Number 27
Start Page 8197
End Page 8204
ISSN 1618-2642
1618-2650
Publisher Springer
Publication Place Berlin
Publication Date 2015
Keyword(s) Thiols
Raman spectroscopy
Imaging
Self-assembled monolayers
TERS
Segregation
Abstract Phase segregation of coadsorbed thiol molecules on a gold surface was investigated with nanoscale chemical imaging using tip-enhanced Raman spectroscopy (TERS). Samples were prepared using mixed solutions containing thiophenol (PhS) and an oligomeric phenylene-ethynylene (OPE) thiol, with 10:1, 2:1, and 1:1 molar ratios. Phase segregation into domains with sizes from a parts per thousand 30 to 240 nm is observed with these molar ratios. A comparison of TERS images with different pixel sizes indicates that a pixel size bigger than 15 nm is not reliable in defining nanodomains, because of undersampling. In this study, the formation of nanodomains was clearly evident based on the molecular fingerprints provided by TERS, while ambient scanning tunneling microscopy (STM) was not capable of discerning individual domains via their apparent height difference. TERS therefore allows to image nanodomains in binary self-assembled monolayers, which are invisible to methods solely relying on topographic or electron density characteristics of self-assembled monolayers. Moreover, TERS mapping provides statistical data to describe the distribution of molecules on the sample surface in a well-defined manner. Peak ratio histograms of selected TERS signals from samples prepared with different mixing ratios give a better understanding of the adsorption preference of the thiols studied, and the relationship of their mixing ratio in solution and adsorbed on the surface.
DOI 10.1007/s00216-015-8840-x
Document Type Article
Publication Status Published
Language English
Assigned Organisational Unit(s) 03430
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NEBIS System Number 004239219
Source Database ID WOS-000362974100005
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@article{Ln2015,
  author = "Lin, Wang-Ing and Shao, Feng and Stephanidis, Bruno and Zenobi, Renato",
  title = "{T}ip-enhanced {R}aman spectroscopic imaging shows segregation within binary self-assembled thiol monolayers at ambient conditions",
  journal = "Analytical and bioanalytical chemistry",
  year = 2015,
  volume = "407",
  number = "27",
  pages = "8197--8204",
}


E-Citations record created: Tue, 10 Nov 2015, 12:31:16 CET