Tuning the thickness of electrochemically grafted layers in large area molecular junctions

Abstract

We have investigated the thickness, the surface roughness, and the transport properties of oligo(1-(2-bisthienyl)benzene) (BTB) thin films grafted on evaporated Au electrodes, thanks to a diazonium-based electro-reduction process. The thickness of the organic film is tuned by varying the number of electrochemical cycles during the growth process. Atomic force microscopy measurements reveal the evolution of the thickness in the range of 2–27 nm. Its variation displays a linear dependence with the number of cycles followed by a saturation attributed to the insulating behavior of the organic films. Both ultrathin (2 nm) and thin (12 and 27 nm) large area BTB-based junctions have then been fabricated using standard CMOS processes and finally electrically characterized. The electronic responses are fully consistent with a tunneling barrier in case of ultrathin BTB film whereas a pronounced rectifying behavior is reported for thicker molecular films.