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Recombination of charge carriers at silicon surfaces is one of the biggest loss mechanisms in crystalline silicon (c-Si) solar cells. Hafnium oxide (HfO2) has attracted much attention as a passivation layer for n-type c-Si because of its positive fixed charges and thermal stability. In this study, HfO2 films are deposited on n-type c-Si using remote plasma atomic layer deposition (RP-ALD). Post-annealing is performed using a rapid thermal processing system at different temperatures in nitrogen ambient for 10 min. The effects of post-annealing temperature on the passivation properties of the HfO2 films on c-Si are investigated. Personal computer one dimension numerical simulation for the passivated emitter and rear contact (PERC) solar cells with the HfO2 passivation layer is also presented. By means of modeling and numerical computer simulation, the influence of different front surface recombination velocity (SRV) and rear SRV on n-type silicon solar cell performance was investigated. Simulation results show that the n-type PERC solar cell with HfO2 single layer can have a conversion efficiency of 22.1%. The PERC using silicon nitride/HfO2 stacked passivation layer can further increase efficiency to 23.02% with an open-circuit voltage of 689 mV.