| Summary: | <p>Understanding surface passivation arising from aluminium oxide (Al<sub>2</sub>O<sub>3</sub>) films is of significant relevance for silicon-based solar cells and devices that require negligible surface recombination. This study aims to understand the competing bulk and surface lifetime effects which occur during the activation of atomic layer deposited Al<sub>2</sub>O<sub>3</sub>. We demonstrate that maximum passivation is achieved on <em>n</em>- and <em>p</em>-type silicon with activation at ∼ 450 °C, irrespective of annealing ambient. Upon stripping the Al<sub>2</sub>O<sub>3</sub> films and re-passivating the surface using a superacid-based technique, we find the bulk lifetime of float-zone and Czochralski silicon wafers degrade at annealing temperatures > 450 °C. By accounting for this bulk lifetime degradation, we demonstrate that the chemical passivation component associated with Al<sub>2</sub>O<sub>3</sub> remains stable at activation temperatures of 450─500 °C, achieving an SRV of < 1 cm/s on <em>n</em>- and <em>p</em>-type silicon. In conjunction with the thermal stability, we show that films in the range of 3–30 nm maintain an SRV of < 1 cm/s when annealed at 450 °C. From atomic-level energy dispersive X-ray analysis, we demonstrate that, post deposition, the interface has a structure of Si/SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub>. After activation at > 300 °C, the interface becomes Si/Si<sub>x</sub>Al<sub>y</sub>O<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> due to diffusion of aluminium into the thin silicon oxide layer.</p>
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