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It is known that a higher concentration of free carriers leads to a higheroxide growth rate in the thermal oxidation of silicon. However, the role ofelectrons and holes in oxidation chemistry is not clear. Here, we reportreal-time second-harmonic-generation data on the oxidation of H-terminated(111)Si that reveal that high concentrations of electrons increase the chemicalreactivity of the outer-layer Si-Si back bonds relative to the Si-H up bonds.However, the thicknesses of the natural oxides of all samples stabilize near 1nm at room temperature, regardless of the chemical kinetics of the differentbonds.

Bond-specific reaction kinetics during the oxidation of (111) Si: Effect of n-type doping