A new azobenzene-thiophene molecular switch is designed, synthesized and used to form self-assembled monolayers (SAM) on gold. An on/off conductance ratio up to 7x1E3 (with an average value of 1.5x1E3) is reported. The on conductance state is clearly identified to the cis isomer of the azobenzene moiety. The high on/off ratio is explained in terms of photo-induced, configuration-related, changes in the electrode-molecule interface energetics (changes in the energy position of the molecular orbitals with respect to the Fermi energy of electrodes) in addition to changes in the tunnel barrier length (length of the molecules). First principles DFT calculations demonstrate a better delocalization of the frontier orbitals, as well as a stronger electronic coupling between the azobenzene moiety and the electrode for the cis configuration over the trans one. Measured photoionization cross-sections for the molecules in the SAM are close to the known values for azobenzene derivatives in solution.
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