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Scalable substitutional doping of 2D transition metal dichalcogenides is a prerequisite to developing next-generation logic and memory devices based on 2D materials. To date, doping efforts are still nascent. Here, scalable growth and vanadium (V) doping of 2D WSe2 at front-end-of-line and back-end-of-line compatible temperatures of800 and 400 °C, respectively, is reported. A combination of experimental and theoretical studies confirm that vanadium atoms substitutionally replace tungsten in WSe2, which results in p-type doping via the introduction of discrete defect levels that lie close to the valence band maxima. The p-type nature of the V dopants is further verified by constructed field-effect transistors, where hole conduction becomes dominant with increasing vanadium concentration. Hence, this study presents a method to precisely control the density of intentionally introduced impurities, which is indispensable in the production of electronic-grade wafer-scale extrinsic 2D semiconductors. [ABSTRACT FROM AUTHOR]