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The defect transformation under growth of submonolayer oxides on silicon surfaces is studied in situ on reconstructed Si(100)-2x1 and Si(111)-7x7 surfaces and on hydrogenated Si surfaces of Si nanocrystallites. The methods of the quenching of the photoluminescence of bulk c-Si due to surface recombination and of the infrared free carriers absorption in mesoporous Si are used. It is shown that dangling bonds at Si-Si dimers are not recombination active. Non-radiative surface defects are generated during the earliest stages of oxidation. The generation of hole traps is tightly related to an increase of physisorbed H 2 O at hydrogenated Si surfaces during the native oxidation.