Damage-free selective etching of Si native oxides against Si has been achieved by NH3/NF3 and SF6/H2O down-flow etching. In the NH3/NF3 etching, the wafer was covered with a film, and after its removal by heating above 100 °C, only SiO2 was found to be etched with an extremely high selectivity with respect to Si. Selective etching of Si oxides has also been obtained for SF6/H2O microwave discharge. In this case, a film of liquid solution containing HF and H2SOx is considered to form on the wafer surface. The selective etching of SiO2 takes place by the dissolved HF just as in the wet etching by an HF solution. The mechanisms of these selective reactions are discussed in detail based on the covalency of Si and SiO2 bondings.
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Nishino et al. (1993) studied this question.
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