Abstract The spectral response of Ga2O3 almost perfectly covers the 200~280 nm solar-blind ultraviolet wavelength range, making it an ideal semiconductor material for fabricating solar-blind ultraviolet photodetectors. However, due to the considerably deep valence band energy of Ga2O3 the construction of heterojunctions typically induces a significant valence band offset (EV). Herein, we present a band engineering approach to improve the performance of Ga2O3 bases photodetectors. This pronounced valence band barrier can strongly influence the transport of photo-generated charge carriers, especially the extraction of holes in the depletion region. By introducing nitrogen (N) during the growth process, we elevated the valence band of Ga2O3 by 0.43 eV. The organic high-molecular-weight material of PEDOT:PSS has been utilized in conjunction with Ga2O3 to construct heterojunction photodetectors. The photodetectors exhibit excellent self-powered characteristics, with responsivity, detectivity, and response time being nearly ten times higher than those of Ga2O3 photodetectors before band structure modulation. The investigation into modulating the band structure of Ga2O3 carried out in this study will lay the theoretical foundation and provide technical solutions for developing satisfactory self-powered photodetectors.
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