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Metal–insulator–semiconductor/MIS-based photoelectrochemical (PEC) water splitting provides a scalable and integrated platform to harness renewable solar energy for green hydrogen production. 

Wafer-scale synthesis of p-type TMD films is critical for its commercialization in next-generation electro/optoelectronics. In this work, wafer-scale intrinsic n-type WS₂films and in situ Nb-doped p-type WS₂films were synthesized through atomic layer deposition (ALD) on 8-inchα-Al₂O₃/Si wafers, 2-inch sapphire, and 1 cm²GaN substrate pieces. The Nb doping concentration was precisely controlled by altering cycle number of Nb precursor and activated by postannealing. WS₂n-FETs and Nb-doped p-FETs with different Nb concentrations have been fabricated using CMOS-compatible processes. X-ray photoelectron spectroscopy, Raman spectroscopy, and Hall measurements confirmed the effective substitutional doping with Nb. The on/off ratio and electron mobility of WS₂n-FET are as high as 10⁵and 6.85 cm² V^-1 s^-1, respectively. In WS₂p-FET with 15-cycle Nb doping, the on/off ratio and hole mobility are 10 and 0.016 cm² V^-1 s^-1, respectively. The p-n structure based on n- and p- type WS₂films was proved with a 10⁴rectifying ratio. The realization of controllablein situNb-doped WS₂films paved a way for fabricating wafer-scale complementary WS₂FETs.