Boron‐Doped Single‐Molecule van der Waals Diode

Single‐molecule diode was the first proposed device in molecular electronics. Despite the great efforts and advances over 50 years, the reported rectification ratios, the most critical parameter of a diode, remain moderate for the single‐molecule diode. Herein, we report an approach to achieve a larger rectification ratio by adopting the combined strategies of p‐type boron doping, the single‐layer graphene nodes, and the van der Waals layer‐by‐layer architecture. Measured current‐voltage curves showed one of the as‐fabricated single‐molecule diodes hit an unprecedented large rectification ratio of 457 at ±1 V. Break junction operations and spectroscopic measurements revealed the three‐atom‐thick configuration of the single‐molecule diodes. With the experimental and theoretical calculation results, we demonstrated the doped boron atoms induced holes to redistribute the electron density, making the asymmetric coupling at positive and negative biases, and the van der Waals interaction promoted asymmetric coupling and significantly boosted diode performance.