A van der Waals pn heterojunction with organic/inorganic semiconductors

van der Waals (vdW) heterojunctions formed by two-dimensional (2D) materials have attracted tremendous attention due to their excellent electrical/optical properties and device applications. However, current 2D heterojunctions are largely limited to atomic crystals, and hybrid organic/inorganic structures are rarely explored. Here, we fabricate the hybrid 2D heterostructures with p-type dioctylbenzothienobenzothiophene (C₈-BTBT) and n-type MoS₂. We find that few-layer C₈-BTBT molecular crystals can be grown on monolayer MoS₂ by vdW epitaxy, with pristine interface and controllable thickness down to monolayer. The operation of the C₈-BTBT/MoS₂ vertical heterojunction devices is highly tunable by bias and gate voltages between three different regimes: interfacial recombination, tunneling, and blocking. The pn junction shows diode-like behavior with rectifying ratio up to 10⁵ at the room temperature. Our devices also exhibit photovoltaic responses with a power conversion efficiency of 0.31% and a photoresponsivity of 22 mA/W. With wide material combinations, such hybrid 2D structures will offer possibilities for opto-electronic devices that are not possible from individual constituents.