Characterization and protonation behavior of bipyridine thiol self-assembled monolayer on Au(111) studied using X-ray photoelectron spectroscopy and scanning tunneling microscopy

Abstract The adsorption process, molecular arrangement and protonation behavior of self-assembled monolayers (SAMs) of bipyridine thiol on Au(1 1 1) were investigated using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), with a view towards constructing a molecular ion sensor. When the bipyridine SAMs were immersed in a strong CF 3 SO 3 H solution for protonation of the bipyridine group, additional N(1s) XPS peaks were generated at higher binding peak positions where the origin of the peak was considered to be the N–H species. We further investigated the relationship between the immersion time for the SAMs and the probability of protonation. We observed a decrease in the probability of protonation with a longer immersion time for the SAMs. We consider that both the bipyridine molecular arrangements and the molecular density on the Au surface are crucial for controlling the probability of protonation based on the STM and XPS data.