Tunnel oxide passivated contacts (TOPCon) embedding a thin oxide layer between polysilicon and base crystalline silicon have shown great potential in the development of solar cells with high conversion efficiency. In this study, we investigate the formation mechanism of hole-carrier selective contacts with TOPCon structure on n-type crystalline silicon wafers. We explore the thermal annealing effects on the passivation properties in terms of the stability of the thermally-formed silicon oxide layer and the deposition conditions of boron-doped polysilicon. To understand the underlying principle of the passivation properties, the active dopant in-diffusion profiles following the thermal annealing are investigated, combined with an analysis of the microscopic structure. Based on PC1D simulation, we find that shallow in-diffusion of boron across a robust tunnel oxide forms a p–n junction and improves the passivation properties. Our findings can provide a pathway to understanding and designing high-quality hole-selective contacts based on the TOPCon structure for the development of highly efficient crystalline silicon solar cells.