Abstract
Improvement in stability of self-assembled monolayers (SAMs) has been demonstrated by using an underpotentially deposited (upd) interlayer between the SAMs and gold substrate. In this study, we show that the upd adlayers can be applied to improve the packing density of thiophenol SAMs due to controlling the binding scheme of the sulfur headgroup from an sp3 to an sp hybridization configuration. Examined here are the structures of SAMs on gold substrate pre-modified by four types of upd adatoms that are electrodeposited at several coverages representing the finish of distinct upd processes. The SAM structures of a homologous series of n-alkanethiols (CH3(CH2)nSH, n = 4−11 and 13−15) are characterized by contact angle measurements and infrared reflectance absorption spectroscopy. The results show the odd−even effect that the orientation of the terminal methyl group is alternatively associated with the number of methylene units, indicating that sulfur headgroup adopts an sp3 hybridization on Au/Bi(upd) and a...
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