High-quality two-dimensional atomic layered p–n heterostructures are essential for high-performance integrated optoelectronics. The studies to date have been largely limited to exfoliated and restacked flakes, and the controlled growth of such heterostructures remains a significant challenge. Here we report the direct van der Waals epitaxial growth of large-scale WSe₂/SnS₂ vertical bilayer p–n junctions on SiO₂/Si substrates, with the lateral sizes reaching up to millimeter scale. Multi-electrode field-effect transistors have been integrated on a single heterostructure bilayer. Electrical transport measurements indicate that the field-effect transistors of the junction show an ultra-low off-state leakage current of 10⁻¹⁴ A and a highest on–off ratio of up to 10⁷. Optoelectronic characterizations show prominent photoresponse, with a fast response time of 500 μs, faster than all the directly grown vertical 2D heterostructures. The direct growth of high-quality van der Waals junctions marks an important step toward high-performance integrated optoelectronic devices and systems.

Recombination dynamics during photoluminescence (PL) in two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) are complicated and can be easily affected by the surroundings because of their atomically thin structures. Herein, we studied the excitation power and temperature dependence of the recombination dynamics on the chemical vapor deposition-grown monolayer WS₂via a combination of Raman, PL, and time-resolved PL spectroscopies. We found a red shift and parabolic intensity increase in the PL emission of the monolayer WS₂ with the increasing excitation power and the decay time constants corresponding to the recombination of trions and excitons from transient PL dynamics. We attributed the abovementioned nonlinear changes in the PL peak positions and intensities to the combination of increasing carrier interaction and band structure renormalization rather than to the thermal effect from a laser. Furthermore, the excitation power-dependent Raman measurements support our conclusion. These findings and understanding will provide important information for the development of TMD-based optoelectronics and photonics.