Al thin films evaporated on Si were oxidized in a microwave excited O
2 + H
2 mixture and O
2 + N
2 mixture plasmas, where H
2 or N
2 was added as a catalytic gas. The compositional variation of each element with depth and the chemical structure of the film were analyzed by means of IMA and XPS with Ar-ion sputtering. In O
2 + N
2 mixture plasma, an evident interfacial oxide layer was observed at the interface. In O
2 + H
2 mixture plasma, the inner SiO
2 layer was not recognized. To explain these experimental findings, a tentative model of oxidation process is proposed taking into account of electronegativity.
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