| Summary: | Ti-doped ZnO (TZO) and Bi<sub>2</sub>O<sub>3</sub> thin films were designed and deposited by magnetron sputtering successively on ITO glass substrate to form a Ti-doped ZnO/Bi<sub>2</sub>O<sub>3</sub> (TZO/Bi<sub>2</sub>O<sub>3</sub>) heterojunction. Microstructure and photoelectric properties of TZO, Bi<sub>2</sub>O<sub>3</sub>, and TZO/Bi<sub>2</sub>O<sub>3</sub> films were tested and characterized. The results showed that TZO film with a hexagonal wurtzite structure was preferentially grown along the crystal plane (002), had a good crystallization state, and was an N-type semiconductor film with high transmittance (90%) and low resistivity (4.68 × 10<sup>−3</sup> Ω·cm). However, the Bi<sub>2</sub>O<sub>3</sub> film sputtered in an oxygen-containing atmosphere and was a polycrystalline film that was preferentially grown along the crystal plane (111). It had a lower crystallization quality than TZO film and was a P-type semiconductor film with low transmittance (68%) and high resistance (1.71 × 10<sup>2</sup> Ω·cm). The I–V curve of TZO/Bi<sub>2</sub>O<sub>3</sub> composite films showed that it had an obvious heterojunction rectification effect, which indicates that the PN heterojunction successfully formed in TZO/Bi<sub>2</sub>O<sub>3</sub> films.
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