We carefully tailored a porous silicon (pSi) surface by oxidation with hydrogen peroxide (H2O2) to determine the time-dependent changes in nanocrystallite surface chemistries (e.g., Si-O-Si, SiH(x) [x = 1, 2], OySiH [y = 2, 3], and SiOH/H2O) and their influence on the pSi photoluminescence (PL). The relationship between infrared band amplitudes and PL intensity were evaluated under H2O2 and O3 (previously studied) oxidation. The pSi surface composition under O3 and H2O2 oxidation conditions tended to, save the O(y)SiH (y = 2, 3) species, approach similar values at the longest oxidation times studied, but they took very different paths in reaching these end points. Furthermore, the pSi surface compositions that exhibit maximum/minimum PL under each oxidant are very different.
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