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Al2O3/TiO2 stacks formed by atomic layer deposition are known to provide a high level of passivation for boron-doped silicon. In previous works, the TiO2 layer was deposited on a pre-annealed Al2O3 layer, however this stack showed passivation degradation after post-deposition annealing. This work presents an alternative to using the as-deposited Al2O3 for the Al2O3/TiO2 stack, which shows no degradation of passivation after post-deposition annealing up to 400 °C. This approach simplifies the processing, allowing continuous layer deposition, and eliminates the undesirable vacuum breaking. This simplified processing leads to better thermal stability of the Al2O3/TiO2 stacks and a low emitter saturation current density. In order to understand the underlying mechanism of surface passivation, an investigation on the effect of thermal SiO2 on the passivation of the Al2O3/TiO2 stack was performed, which indicates that the TiO2 capping layer enhances the field-effect passivation for both the Si/Al2O3 and SiO2/Al2O3 structures.