Silicon heterojunction solar cells have been studied by many research groups. In this work, silicon heterojunction solar cells having a simple structure of Ag/ZnO:Al/n type a-Si:H/p type c-Si/Al were fabricated. Samples were fabricated to investigate the effect of transparent conductive oxide growth conditions on the interface between ZnO:Al layer and a-Si:H layer. One sample was deposited by ZnO:Al at low working pressure. The other sample was deposited by ZnO:Al at alternating high working pressure and low working pressure. Electrical properties and chemical properties were investigated by light I-V characteristics and AES method, respectively. The light I-V characteristics showed better efficiency on sample deposited by ZnO:Al by alternating high working pressure and low working pressure. Atomic concentrations and relative oxidation states of Si, O, and Zn were analyzed by AES method. For poor efficiency samples, Si was diffused into ZnO:Al layer and O was diffused at the interface of ZnO:Al and Si. Differentiated O KLL spectra, Zn LMM spectra, and Si KLL spectra were used for interface reaction and oxidation state. According to AES spectra, sample deposited by high working pressure was effective at reducing the interface reaction and the Si diffusion. Consequently, the efficiency was improved by suppressing the SiOx formation at the interface.