Understanding the electronic properties of molecule/metal junctions: the case study of thiols on gold

In this work, I review our recent results on the electronic properties of thiolate/metal interface. Work function change, molecular level alignment and interfacial state formation of the methylthiolate/ Au(1 1 1) and dimethyl-disulfide/Au(1 1 1) interfaces are investigated by means of UPS and XPS. A complete picture of the electronic properties of both the dimethyl-disulfide (DMDS) weakly-adsorbed and the methylthiolate (MT) chemisorbed phases is obtained by direct quantitative comparison between the experiment and theory. The modifications of the electronic properties of the DMDS thin film, induced by a MT buffer layer are also discussed. Moreover, the cysteine/Au(1 1 1) system is investigated as an example of interface formed by molecules with large intrinsic dipole moment. Finally, surface inhomogeneity and its influence on the interface electronic properties is briefly discussed, in light of the important concept of local work function.