We carefully evaluate how porous silicon (pSi) surface oxidation by ozone (O<sub>3</sub>) and the resulting changes in nanocrystallite surface chemistries (e.g., SiOSi, SiH<sub>x</sub> (<i>x</i> = 1-3), O<sub>y</sub>SiH (<i>y</i> = 1-2), and SiOH) influence the pSi photoluminescence (PL). We discover a relationship between the pSi PL and the O<sub>2</sub>SiH band amplitude.

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