In Situ Tuning of the Charge-Carrier Polarity in Imidazole-Linked Single-Molecule Junctions

Manipulating the nature of the charge carriers at the single-molecule level is one of the major challenges of molecular electronics. Using first-principles quantum transport calculations, we have investigated the electronic transport properties of imidazole-linked single-molecule junctions and identified the hydrogen atom bonded to the pyrrole-like nitrogen in imidazole as a switch to tune the polarity of the charge carriers. Our calculations show that the chemical nature of the imidazole anchors is dramatically altered by dehydrogenation, which changes the dominant charge carriers from electrons to holes. It is also revealed that upon dehydrogenation the interfacial Au-N bonds are modified from donor-acceptor-like to covalent, along with a significant promotion of the low-bias conductance and the junction stability. At variance with other traditional methods that always require drastic modifications of the junction structure, our findings provide a promising approach to tailor in situ the polarity of charge carriers in molecular electronic devices.