Molecular electrostatics of conjugated self-assembled monolayers on Au(111) using electrostatic force microscopy

The electrostatic potential produced by a variety of self-assembled monolayers on Au(111) is measured using scanning probe techniques. The molecules chosen for this study contain thiol-terminated end groups and pi-conjugated orbitals, making them suitable for molecular electronics applications. We have measured the surface potential of molecules having a symmetric structure and compared these results to those obtained from similar nonsymmetric molecules. The measured potential for nonsymmetric molecules scales with the dipole moment of the molecule comprising the monolayer. For symmetric molecules, the measured surface potential is essentially the same as the substrate. This result suggests that the dipole moment formed by the Au-S bond makes a small contribution to the measured surface potential. The dipole moment of a strong electron accepting molecule was intentionally modified by reaction with a strong electron acceptor. In this case, the surface potential produced by the self-assembled monolayer was found to change polarity after the formation of the charge-transfer complex.