Homogeneous Dispersion of Aromatic Thiolates in the Binary Self-Assembled Monolayer on Au(111) via Displacement Revealed by Tip-Enhanced Raman Spectroscopy

2020 ◽  
Vol 124 (24) ◽  
pp. 13141-13149 ◽  
Author(s):  
Misun Hong ◽  
Yasuyuki Yokota ◽  
Norihiko Hayazawa ◽  
Emiko Kazuma ◽  
Yousoo Kim
Keyword(s):  
Raman Spectroscopy ◽  
Self Assembled Monolayer ◽  
Homogeneous Dispersion ◽  
Self Assembled ◽  
Tip Enhanced Raman Spectroscopy

Tip enhanced Raman spectroscopy on azobenzene thiol self-assembled monolayers on Au(111)

2009 ◽  
Vol 40 (10) ◽  
pp. 1407-1412 ◽  
Author(s):  
Gennaro Picardi ◽  
Marc Chaigneau ◽  
Razvigor Ossikovski ◽  
Christophe Licitra ◽  
Guillame Delapierre
Keyword(s):  
Raman Spectroscopy ◽  
Self Assembled Monolayers ◽  
Assembled Monolayers ◽  
Self Assembled ◽  
Tip Enhanced Raman Spectroscopy

scholarly journals Nanoscale Chemical Imaging of Coadsorbed Thiolate Self-assembled Monolayers on Au(111) by Tip-Enhanced Raman Spectroscopy

2022 ◽  
Author(s):  
Feng Shao ◽  
Liqing Zheng ◽  
Jinggang Lan ◽  
Renato Zenobi
Keyword(s):  
Raman Spectroscopy ◽  
Dft Calculations ◽  
Adsorption Energy ◽  
Density Functional ◽  
Phase Segregation ◽  
Self Assembled Monolayers ◽  
Ambient Conditions ◽  
Assembled Monolayers ◽  
Self Assembled ◽  
Tip Enhanced Raman Spectroscopy

Self-assembled monolayers (SAMs) of thiolates on metal surfaces are of key importance for engineering surfaces with tunable properties. However, it remains challenging to understand binary thiolate SAMs on metals at the nanoscale under ambient conditions. Here we employ tip-enhanced Raman spectroscopy (TERS) and density functional theory (DFT) calculations to investigate local information of binary SAMs on Au(111) coadsorbed from an equimolar mixture of p-cyanobenzenethiol (pCTP) and p-aminothiophenol (pATP), including chemical composition, coadsorption behavior, phase segregation, plasmon-induced photocatalysis, and solvation effects. We found that upon competitive adsorption of pCTP and pATP on Au(111) from a methanolic solution, the coadsorption initially occurs randomly and homogeneously; eventually, pATP is replaced by pCTP through gradual growth of pCTP nanodomains. TERS imaging also allows for visualization of the plasmon-induced coupling of pATP to p,p’-dimercaptoazobenzene (DMAB) and the solvation-induced phase segregation of the binary SAMs into nanodomains, with a spatial resolution of ~9 nm under ambient conditions. According to DFT calculations, these aromatic thiolates differing only in their functional groups, -CN versus –NH2, show different adsorption energy on Au(111) in vacuum and methanol, and thus the solvation effect on adsorption energy of these thiolates in methanol can determine the dispersion state and replacement order of the binary thiolates on Au(111).

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