Two‐dimensional (2D) transition metal dichalcogenides (TMDCs) with unique electrical properties are fascinating materials used for future electronics. However, the strong Fermi level pinning effect at the interface of TMDCs and metal electrodes always leads to high contact resistance, which seriously hinders their application in 2D electronics. One effective way to overcome this is to use metallic TMDCs or transferred metal electrodes as van der Waals (vdW) contacts. Alternatively, using highly conductive doped TMDCs will have a profound impact on the contact engineering of 2D electronics. Here, a novel chemical vapor deposition (CVD) using mixed molten salts is established for vapor–liquid–solid growth of high‐quality rhenium (Re) and vanadium (V) doped TMDC monolayers with high controllability and reproducibility. A tunable semiconductor to metal transition is observed in the Re‐ and V‐doped TMDCs. Electrical conductivity increases up to a factor of 10⁸ in the degenerate V‐doped WS₂ and WSe₂. Using V‐doped WSe₂ as vdW contact, the on‐state current and on/off ratio of WSe₂‐based field‐effect transistors have been substantially improved (from ≈10^–8 to 10^–5 A; ≈10⁴ to 10⁸), compared to metal contacts. Future studies on lateral contacts and interconnects using doped TMDCs will pave the way for 2D integrated circuits and flexible electronics.

Excitons, as bound electron-hole paired quasiparticle, play an essential role in the energy transport in the optical-electric properties of semiconductors. Their momentum-energy dispersion relation is a fundamental physical property of great significance to understand exciton dynamics. However, this dispersion is seldom explored especially in two-dimensional transition metal dichalcogenides with rich valleytronic properties. In this work, momentum resolved electron energy-loss spectroscopy was used to measure the dispersions of excitons in freestanding monolayer ${\mathrm{WSe}}_2$. Besides the parabolically dispersed valley excitons, a subgap dispersive exciton was observed at nonzero momenta for the first time, which can be introduced by the prolific Se vacancies. Our work provides a paradigm to directly probe exciton dispersions in 2D semiconductors and could be generalized to many low-dimensional systems.