Atomic-Level Electronic Properties of Carbon Nitride Monolayers

Heteroatom-doped carbon-based materials are of significance for clean energy conversion and storage because of their fascinating electronic properties, low cost, high durability, and environmental friendliness. Atomically precise fabrication of carbon-based materials with well-defined heteroatom-dopant positions and atomic-scale understanding of their atomic-level electronic properties is a challenge. Herein, we demonstrate the bottom-up on-surface synthesis of 1D and 2D monolayer carbon nitride nanostructures with precise control of the nitrogen-atom doping sites and pore sizes. We also observe an electronic band offset at the C–N heterojunction. Using high-resolution scanning tunneling microscopy, the atomic structure of the as-prepared carbon nitride nanoporous monolayers are revealed, indicating successful and precise control of the structures and N atom doping sites. Furthermore, corroborated by theoretical calculations, scanning tunneling spectroscopy measurements reveal a valence band shift of 140 meV that results in an electric field of 2.9 × 108 V m–1 at the C–N heterojunction, indicating efficient separation of the electron–hole pair at the N doping site. Our finding offers direct atomic-level insights into the local electronic structure of the heteroatom-doped carbon-based materials.