Unimolecular current rectifiers are fundamental building blocks in organic electronics. Rectifying behavior has been identified in numerous organic systems due to electron-hole asymmetries of orbital levels interfaced by a metal electrode. As a consequence, the rectifying ratio (RR) determining the diode efficiency remains fixed for a chosen molecule-metal interface. Here, a mechanically tunable molecular diode exhibiting an exceptionally large rectification ratio (>105) and reversible direction is presented. The molecular system comprises a seven-armchair graphene nanoribbon (GNR) doped with a single unit of substitutional diboron within its structure, synthesized with atomic precision on a gold substrate by on-surface synthesis. The diboron unit creates half-populated in-gap bound states and splits the GNR frontier bands into two segments, localizing the bound state in a double barrier configuration. By suspending these GNRs freely between the tip of a low-temperature scanning tunneling microscope and the substrate, unipolar hole transport is demonstrated through the boron in-gap state's resonance. Strong current rectification is observed, associated with the varying widths of the two barriers, which can be tuned by altering the distance between tip and substrate. This study introduces an innovative approach for the precise manipulation of molecular electronic functionalities, opening new avenues for advanced applications in organic electronics.
Keywords: STM; electronic transport; graphene nanoribbon; molecular diode.
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