Abstract:

In single-molecule junctions, anchoring groups that connect the central molecule to the electrodes have profound effects on the mechanical and electrical properties of devices. The mechanical strength of the anchoring groups affects the device stability, while their electronic coupling strength influences the junction conductance and the conduction polarity. To design and fabricate high-performance single-molecule devices with graphene electrodes, it is highly desirable to explore robust anchoring groups that bond the central molecule to the graphene electrodes. Condensation of ortho-phenylenediamine terminated molecules with ortho-quinone moieties at the edges of graphene generates graphene-conjugated pyrazine units that can be employed as anchoring groups for the construction of molecular junctions with graphene electrodes. In this study, we investigated the fabrication and electrical characterization of single-molecule field-effect transistors (FETs) with graphene as the electrodes, pyrazine as the anchoring groups, and a heavily doped silicon substrate as the back-gate electrode. Graphene nano-gaps were fabricated by a high-speed feedback-controlled electro-burning method, and their edges were fully oxidized; thus, there were many ortho-quinone moieties at the edges. After the deposition of phenazine molecules with ortho-phenylenediamine terminals at both ends, a large current increase was observed, indicating that molecular junctions were formed with covalent pyrazine anchoring groups. The yield of the single-molecule devices was as high as 26%, demonstrating the feasibility of pyrazine as an effective anchoring group for graphene electrodes. Our electrical measurements show that the ten fabricated devices exhibited a distinct gating effect when a back-gate voltage was applied. However, the gate dependence of the conductance varied considerably from device to device, and three types of different gate modulation behaviors, including p-type, ambipolar, and n-type conduction, were observed. Our observations can be understood using a modified single-level model that takes into account the linear dispersion of graphene near the Dirac point; the unique band structure of graphene and the coupling strength of pyrazine with the graphene electrode both crucially affect the conduction polarity of single-molecule FETs. When the coupling strength of pyrazine with the graphene electrode is weak, the highest occupied molecular orbital (HOMO) of the central molecule dominates charge transport. Depending on the gating efficiencies of the HOMO level and the graphene states, devices can exhibit p-type or ambipolar conduction. In contrast, when the coupling is strong, the redistribution of electrons around the central molecule and the graphene electrodes leads to a realignment of the molecular levels, resulting in the lowest unoccupied molecular orbital (LUMO)-dominated n-type conduction. The high yield and versatility of the pyrazine anchoring groups are beneficial for the construction of single-molecule devices with graphene electrodes.

Key words: Molecular electronics, Graphene electrode, Pyrazine anchoring group, Single-molecule field-effect transistor, Coupling strength