Commensurate Assembly of C₆₀ on Black Phosphorus for Mixed‐Dimensional van der Waals Transistors

Abstract 2D crystals can serve as templates for the realization of new van der Waals (vdW) heterostructures via controlled assembly of low‐dimensional functional components. Among available 2D crystals, black phosphorus (BP) is unique due to its puckered atomic surface topography, which may lead to strong epitaxial phenomena through guided vdW assembly. Here, it is demonstrated that a BP template can induce highly oriented assembly of C₆₀ molecular crystals. Transmission electron microscopy and theoretical analysis of the C₆₀/BP vdW heterostructure clearly confirm that the BP template results in oriented C₆₀ assembly with higher‐order commensurism. Lateral and vertical devices with C₆₀/BP junctions are fabricated via a lithography‐free clean process, which allows one to investigate the ideal electrical properties of pristine C₆₀/BP junctions. Effective tuning of the C₆₀/BP junction barrier from 0.2 to 0.5 eV and maximum on‐current density higher than 10⁴ mA cm⁻² are achieved with graphite/C₆₀/BP vertical vdW transistors. Due to the formation of high‐quality C₆₀ film and the semitransparent graphite top‐electrode, the vertical transistors show high photoresponsivities up to ≈100 A W⁻¹ as well as a fast response time under visible light illumination.