Low Temperature Plasma Anodization of Silicides

Abstract

In the first time, hundreds nm thick oxide layers were formed by room temperature plasma anodization of some refractory disilicides. Nuclear microanalysis and Rutherford backscattering techniques were used to study the anodic oxidation of various metal silicides (Hf, Ti and Zr) in a multipolar oxygen plasma set-up. We have found that the low temperature (<100 °C) plasma anodization kinetics of Hf or Zr silicides is two orders of magnitude higher than that of Ti silicide although their thermodynamic and physicochemical behaviour are very similar. 200 nm thick Hf (or Zr) and Si mixed oxide layers have been obtained in one hour plasma anodization. Analysis of RBS spectra indicates that the ratio of Si to metal cation concentration in the bulk of oxide grownis the same than the silicide (HfSi₂ or ZrSi₂), while in the near surface region of oxide (20 to 30 nm) there is an enrichment in metallic oxide leading to a Si to Hf (or Zr) concentration ratio equal to unity. The spectacular difference between the anodization rates in oxygen plasma of Hf (and Zr) silicides comparing to Ti silicides can be related to the catalytic effect on plasma anodization of the Hf and Zr oxides.