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The band offsets of heterojunctions formed between indium tin oxide (ITO) and amorphous gallium oxide (a-GaOx) of different stoichiometric ratios were measured by X-ray photoelectron spectroscopy (XPS) using the Kraut method. a-GaOx films with different stoichiometric ratios were deposited on commercial ITO/quartz substrates using radio frequency (RF) magnetron sputtering by varying the Ar/O2 flux ratio. With the increase of oxygen flux in the reaction gas, the VO concentration of a-GaOx decreases and its bandgap increases from 5.2 eV to 5.32 eV, while the valence band offset of ITO/a-GaOx heterojunction changes from 0.29 ± 0.07 eV to -0.74 ± 0.06 eV and conduction band offset changes from 0.95 ± 0.085 to 2.10 ± 0.075 eV. The results indicate that the band alignment of ITO/a-GaOx heterojunction can change from type I to type II with the variation of Ga/O stoichiometric ratio, which can provide guidance for the design of their corresponding high-performance heterostructured devices.

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