The nitrogen doping of graphene leads to graphene heterojunctions with a tunable bandgap, suitable for electronic, electrochemical, and sensing applications. However, the microscopic nature and charge transport properties of atomic-level nitrogen-doped graphene are still unknown, mainly due to the multiple doping sites with topological diversities. In this work, we fabricated atomically well-defined N-doped graphene heterojunctions and investigated the cross-plane transport through these heterojunctions to reveal the effects of doping on their electronic properties. We found that a different doping number of nitrogen atoms leads to a conductance difference of up to ∼288%, and the conductance of graphene heterojunctions with nitrogen-doping at different positions in the conjugated framework can also lead to a conductance difference of ∼170%. Combined ultraviolet photoelectron spectroscopy measurements and theoretical calculations reveal that the insertion of nitrogen atoms into the conjugation framework significantly stabilizes the frontier molecular orbitals, leading to a change in the relative positions of the HOMO and LUMO to the Fermi level of the electrodes. Our work provides a unique insight into the role of nitrogen doping in the charge transport through graphene heterojunctions and materials at the single atomic level.
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