Surface Structure, Adsorption, and Thermal Desorption Behaviors of Methaneselenolate Monolayers on Au(111) from Dimethyl Diselenides

To understand the effect of headgroups (i.e., sulfur and selenium) on surface structure, adsorption states, and thermal desorption behaviors of self-assembled monolayers (SAMs) on Au(111), we examined methanethiolate (CH₃–S, MS) and metheneselenolate (CH₃–Se, MSe) monolayers formed from dimethyl disulfide (DMDS) and dimethyl diselenide (DMDSe) molecules by ambient vapor-phase deposition. Scanning tunneling microscopy imaging revealed that DMDS molecules on Au(111) after a 1 h deposition form MS monolayers containing a disordered phase and an ordered row phase with an inter-row spacing of 1.51 nm, whereas DMDSe molecules form long-range-ordered MSe monolayers with a (√3 × 3√3)<i>R</i>30° structure. X-ray photoelectron spectroscopy measurements showed that MS or MSe monolayers chemisorbed on Au(111) were formed via S–S bond cleavage of DMDS or Se–Se bond cleavage of DMDSe. On the other hand, we monitored three main desorption fragments for MS and MSe monolayers using TDS monomers (CH₃S⁺, CH₃Se⁺), parent mass species (CH₃SH⁺, CH₃SeH⁺), and dimers (CH₃S–SCH₃⁺, CH₃Se–SeCH₃⁺). Interestingly, we found that thermal desorption behaviors of MSe monolayers were markedly different from those of MS monolayers. All desorption peaks for MSe monolayers were observed at a higher temperature compared with MS monolayers, suggesting that the adsorption affinity of selenium atoms for the Au(111) surface is stronger than that of sulfur atoms. In addition, the desorption intensity of dimer fragments for MSe monolayers was much lower than for MS monolayers, indicating that selenolate SAMs on Au(111) did not undergo their dimerization efficiently during thermal heating compared with thiolate SAMs. Our results provide new insight into understanding the surface structure and thermal desorption behavior of MSe monolayers on Au(111) surface by comparing those of MS monolayers