Structural Stability and Phase Transitions of Octanethiol Self-Assembled Monolayers on Au(111) in Ultrahigh Vacuum

To understand the structural stability of as-prepared octanethiol (OT) self-assembled monolayers (SAMs) with a fully covered c(4 x 2) phase on Au(111) in ultrahigh vacuum (UHV) conditions of 3 x 10(-7) Pa at room temperature, we examined OT SAM samples obtained as a function of storage period using scanning tunneling microscopy (STM). STM imaging revealed that phase transition of OT SAMs after storage in UHV for 3 days occurs from the c(4 x 2) phase to the mixed phase containing ordered c(4 x 2) and disordered phases. It was also observed that the disordered phase was mainly located at around vacancy islands and near step edges of Au(111) terraces, implying that desorption of OT molecules chemisorbed on Au(111) in UHV occurs more quickly in these regions compared with in the closely packed and ordered domains. After a longer storage in UHV for 6 days, OT SAMs with the c(4 x 2) phase were changed to the disordered phase containing a partially ordered domain with a row structure. From this study, we clearly demonstrated that OT molecules in SAMs on Au(111) are desorbed spontaneously in UHV at room temperature, resulting in the formation of disordered and row phases.