Electron transport through rectifying self-assembled monolayer diodes on silicon: Fermi level pinning at the molecule-metal interface

We report the synthesis and characterization of molecular rectifying diodes on silicon using sequential grafting of self-assembled monolayers of alkyl chains bearing a pi group at their outer end (Si/sigma-pi/metal junctions). We investigate the structure-performance relationships of these molecular devices and we examine to what extent the nature of the pi end-group (change in the energy position of their molecular orbitals) drives the properties of these molecular diodes. For all the pi-groups investigated here, we observe rectification behavior. These results extend our preliminary work using phenyl and thiophene groups (S. Lenfant et al., Nano Letters 3, 741 (2003)).The experimental current-voltage curves are analyzed with a simple analytical model, from which we extract the energy position of the molecular orbital of the pi-group in resonance with the Fermi energy of the electrodes. We report the experimental studies of the band lineup in these silicon/alkyl-pi conjugated molecule/metal junctions. We conclude that Fermi level pinning at the pi-group/metal interface is mainly responsible for the observed absence of dependence of the rectification effect on the nature of the pi-groups, even though they were chosen to have significant variations in their electronic molecular orbitals