Formation of Ordered 4-Fluorobenzenethiol Self-Assembled Monolayers on Au(111) from Vapor Phase Deposition.

Self-assembled monolayers (SAMs) were formed by the spontaneous adsorption of 4-fluorobenzenethiol (4-FBT) on Au(111) using both solution and ambient-pressure vapor deposition methods at room temperature. The surface structure and thermal desorption properties of 4-FBT SAMs were examined by scanning tunneling microscopy (STM) and thermal desorption spectroscopy (TDS). STM imaging showed that 4-FBT SAMs formed in solution at room temperature mainly contained disordered phase with gold adatom islands, while those formed by ambient-pressure vapor deposition had well-ordered phase, which can be described as a (2 x 2√13)R45 degrees structure. In addition, thermal desorption spectroscopy (TDS) measurements showed that strong desorption peak for parent mass fragment (m/z = 128, FC6H5SH+) for 4-FBT SAMs on Au(111) was observed at 460 K, as a result of hydrogen abstract reaction of chemisorbed thiolates during desorption.