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Silicon-based tandem solar cells incorporating low-cost, abundant, and non-toxic metal oxide materials can increase the conversion efficiency of silicon solar cells beyond their conventional limitations with obvious economic and environmental benefits. In this work, the electrical characteristics of a metal oxide thin-film heterojunction solar cell based on a cuprous oxide (Cu2O) absorber layer were investigated. Highly Al-doped n-type ZnO (AZO) and undoped p-type Cu2O thin films were prepared on quartz substrates by magnetron sputter deposition. The electrical and optical properties of these thin films were determined from Hall effect measurements and spectroscopic ellipsometry. After annealing the Cu2O film at 900 °C, the majority carrier (hole) mobility and the resistivity were measured at 50 cm2/V·s and 200 Ω·cm, respectively. Numerical modeling was carried out to investigate the effect of band alignment and interface defects on the electrical characteristics of the AZO/Cu2O heterojunction. The analysis suggests that the incorporation of a buffer layer can enhance the performance of the heterojunction solar cell as a result of reduced conduction band offset.