We show by scanning tunneling microscopy (STM) imaging that native oxide growth in moist air on hydrogen terminated Si(111) 1×1 surfaces begins by continuing formation of small oxide nuclei, 10–20 Å in diameter, in the topmost Si layer. Their statistical distribution on the flat terraces points to a homogeneous nucleation process. Oxidation is extremely slow; after about 800 h only one complete monolayer is oxidized. In addition, a small number of three‐dimensional oxide nuclei, several layers deep and 50–100 Å in width, are formed at step edges as a minority species, which may be related to surface defects or contaminations.
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