Tuning the polarity of charge carriers in N-heterocyclic carbene-based single-molecule junctions via atomic manipulation

Tuning the polarity of charge carriers at a single-molecular level is essential for designing complementary logic circuits in the field of molecular electronics. Herein, the transport properties of N-heterocyclic carbene (NHC)-linked single-molecule junctions are investigated using the ab initio quantum transport approach. The results reveal that the hydrogen atoms in NHCs function as a switch for regulating the polarity of charge carriers. Dehydrogenation changes the chemical nature of NHC anchors, thereby rendering holes as the major charge carriers rather than electrons. Essentially, dehydrogenation changes the anchoring group from electron-rich to electron-deficient. The electrons transferred to molecules from the electrodes raise the molecular level closer to the Fermi level, thus resulting in charge carrier polarity conversion. This conversion is influenced by the position and number of hydrogen atoms in the NHC anchors. To efficiently and decisively alter charge carrier polarity via atomic manipulation, a methyl substitution approach is developed and verified. These results confirm that atomic manipulation is a significant method for modulating the polarity of charge carriers in NHC-based single-molecule devices.