Al-doped zinc-oxide (AZO) thin films were prepared by RF magnetron sputtering at different oxygen partial pressures and substrate temperatures. The charge-carrier concentrations in the films decreased from 1.69 × 1021to 6.16 × 1017 cm−3with increased gas flow rate from 7 to 21 sccm. The X-ray diffraction (XRD) patterns show that the (002)/(103) peak-intensity ratio decreased as the gas flow rate increased, which was related to the increase of AZO thin film disorder. X-ray photoelectron spectra (XPS) of the O1s were decomposed into metal oxide component (peak A) and the adsorbed molecular oxygen on thin films (peak B). The area ratio of XPS peaks (A/B) was clearly related to the stoichiometry of AZO films; that is, the higher value of A/B showed the higher stoichiometric properties.