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P-type ZnO transparent semiconductor thin films were prepared on glass substrates by the sol-gel spin-coating process with N doping and Ga–N co-doping. Comparative studies of the microstructural features, optical properties, and electrical characteristics of ZnO, N-doped ZnO (ZnO:N), and Ga–N co-doped ZnO (ZnO:Ga–N) thin films are reported in this paper. Each as-coated sol-gel film was preheated at 300 °C for 10 min in air and then annealed at 500 °C for 1 h in oxygen ambient. X-ray diffraction (XRD) examination confirmed that these ZnO-based thin films had a polycrystalline nature and an entirely wurtzite structure. The incorporation of N and Ga–N into ZnO thin films obviously refined the microstructures, reduced surface roughness, and enhanced the transparency in the visible range. X-ray photoelectron spectroscopy (XPS) analysis confirmed the incorporation of N and Ga–N into the ZnO:N and ZnO:Ga–N thin films, respectively. The room temperature PL spectra exhibited a prominent peak and a broad band, which corresponded to the near-band edge emission and deep-level emission. Hall measurement revealed that the ZnO semiconductor thin films were converted from n-type to p-type after incorporation of N into ZnO nanocrystals, and they had a mean hole concentration of 1.83 × 1015 cm−3 and a mean resistivity of 385.4 Ω·cm. In addition, the Ga–N co-doped ZnO thin film showed good p-type conductivity with a hole concentration approaching 4.0 × 1017 cm−3 and a low resistivity of 5.09 Ω·cm. The Ga–N co-doped thin films showed relatively stable p-type conduction (>three weeks) compared with the N-doped thin films.

Enhanced Electrical Properties and Stability of P-Type Conduction in ZnO Transparent Semiconductor Thin Films by Co-Doping Ga and N