After the measurement of electrical property and structure property of AZO films by Hall system, XRD and AFM, XPS was applied to identify the change of chemical structure caused by substrate temperature and in order to find the elements changes in the AZO films. The O 1s spectra showing the chemical bonding state of oxygen shows asymmetric peaks, as shown in Fig. 4. The typical O 1speak could be consistently fitted by three nearly Gaussian. The lower binding energy (OL = 529.7– 529.9 eV) and middle binding energy (OM = 531.2–531.4eV) are associated with O2 ions in the ZnO matrix and oxygen deficiencies, respectively [21,22]. An additional high binding energy (OH = 532.5–532.7eV) results from O–H or C–O groups near the surface of the films [23]. The increase in substrate temperature from 0 to 400C increased the intensity of the Zn–O bond related OL peak and decreased the intensity of the oxygen-vacancy related OM peak. This indicates that the crystallinity of films is improved by increasing substrate temperatures, being agree with the XRD results. Also, the reduction of oxygen–vacancy decreases the carrier concentration and this is in accord with the electricalpropertiesofAZOfilms.Itwasalsoobservedthatsurfaceimpurity-relatedOH peakincreased as substrate temperature increased. This result does agree with the result of surface roughness in AZO film. The increase of the surface bonding raises the barrier potential which impedes the motion of carrier, resulting in decrease of mobility [24].