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Doping asymmetry is a notable phenomenon with semiconductors and aparticularly longstanding challenge limiting the applications of mostwide-band-gap semiconductors, which are inherent of spontaneous heavy n- orp-type doping because of their extreme band edges. This study theoreticallyshows that by applying a proper external voltage on materials during theirgrowth or doping processes, we can largely tune the band edges and consequentlyreverse the doping asymmetry in semiconductor thin films. We take zinc oxide asa touchstone and computationally demonstrate that this voltage-assisted-dopingapproach efficiently suppresses the spontaneous n-type defects by around fourorders under three distinct growth conditions and successfully generates p-typezinc oxide up to the lowest acceptor levels. The proposed approach isinsensitive to materials, growth conditions, or defects origins, and thusoffers a general solution to the doping asymmetry in semiconductor thin films.

Reverse Doping Asymmetry in Semiconductor Thin Films Using External Voltage