Structural Investigation of 1,1 '-Biphenyl-4-thiol Self-Assembled Monolayers on Au(111) by Scanning Tunneling Microscopy and Low-Energy Electron Diffraction

Matei D, Muzik H, Gölzhäuser A, Turchanin A. Structural Investigation of 1,1 '-Biphenyl-4-thiol Self-Assembled Monolayers on Au(111) by Scanning Tunneling Microscopy and Low-Energy Electron Diffraction. Langmuir. 2012;28(39):13905-13911.Self-assembled monolayers (SAMs) of 1,1'-biphenyl-4-thiol (H-(C6H4)(2)-SH) on Au(111) were prepared from solution or via vapor deposition in ultrahigh vacuum and characterized by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). In contrast to the typically observed for densely packed alkane-thiol SAMs on Au(111) (root 3 x root 3)R30 degrees structure, the densely packed aromatic biphenylthiol SAMs prepared by both methods exhibit an unusual hexagonal (2 x 2) structure. Upon annealing at 100 degrees C, this structure evolves into the (2 x 7 root 3) structure resulting in the formation of highly ordered pinstripes oriented along the directions. Lower density SAMs, prepared by vapor deposition in vacuum, show mixed structures comprising the hexagonal (2 x 2) structure and two rectangular arrangements with the unit cells of (3 root 3 x 9) and (2 root 3 x 8). An extinction of the (3 root 3 x 9) structure in the favor of the (2 root 3 x 8) structure is observed upon annealing at temperatures of similar to 100 degrees C