Silicon oxynitride that can be deposited two times faster than general SiNx:H layer was applied to fabricate the passivation protection layer of atomic layer deposition (ALD) Al2O3. The protection layer is deposited by plasma-enhanced chemical vapor deposition to protect Al2O3 passivation layer from a high temperature metallization process for contact firing in screen-printed silicon solar cell. In this study, we studied passivation performance of ALD Al2O3 film as functions of process temperature and RF plasma effect in plasma-enhanced chemical vapor deposition system. Al2O3/SiON stacks coated at 400 oC showed higher lifetime values in the as-stacked state. In contrast, a high quality Al2O3/SiON stack was obtained with a plasma power of 400 W and a capping-deposition temperature of 200 oC after the firing process. The best lifetime was achieved with stack films fired at 850 oC. These results demonstrated the potential of the Al2O3/SiON passivated layer for crystalline silicon solar cells.