In recent years, developing dopant-free carrier-selective contacts, instead of heavily doped Si layer (either externally or internally), for crystalline silicon (c-Si) solar cells have attracted considerable interests with the aims to reduce parasitic light absorption and fabrication cost. However, the stability still remains a big challenge for dopant-free contacts, especially when thermal treatment is involved, which limits their industrial adoption. In this study, a perovskite material ZnTiO ₃ combining with an ultrathin (~1 nm) SiO ₂ film and Al layer is used as an electron-selective contact, forming an isotype heterojunction with n-type c-Si. The perovskite/c-Si heterojunction solar cells exhibit a performance-enhanced effect by post-metallization annealing when the annealing temperature is 200-350 °C. Thanks to the post-annealing treatment, an impressive efficiency of 22.0% has been demonstrated, which is 3.5% in absolute value higher than that of the as-fabricated solar cell. A detailed material and device characterization reveal that post annealing leads to the diffusion of Al into ZnTiO ₃ film, thus doping the film and reducing its work function. Besides, the coverage of SiO ₂ is also improved. Both these two factors contribute to the enhanced passivation effect and electron selectivity of the ZnTiO ₃-based contact, and hence improve the cell performance.