Oxidation and formation mechanisms in disilicides: VSi₂ and CrSi₂, inert marker experiments and interpretation

Abstract

The process of atomic transport in the silicide during oxidation of silicide layers formed on Si substrates has been analyzed by means of implanted inert markers. The results confirm that CrSi2 oxidizes via the diffusion of Cr atoms towards the Si substrate, and reveal that the same type of transport occurs in VSi2, which is in opposition to the growth of these disilicides that proceeds via Si motion. Moreover during the oxidation of both VSi2 and CrSi2, the diffusing metal atoms are accompanied by a large proportion of the Si atoms from the silicide which also diffuse towards the substrate. Thus, the experimental evidence now available reveals that all the silicon-rich silicides, in increasing atomic numbers from TiSi2 to NiSi2, oxidize with the formation of metal-free SiO2 in a process that involves the diffusion of both metal and Si regardless of the predominant moving species during silicide formation. In CrSi2, VSi2, as well as TiSi2, with similar structures, examination of the structure shows that diffusion should occur via a vacancy mechanism. The thermodynamic conditions that prevail during oxidation lead indifferently to metal diffusion in one direction or Si diffusion in the other. Any selection between one mechanism or the other has to be dictated by kinetic conditions relating to the relative mobilities of the two atomic species. What is known about this is discussed in detail. Finally it is proposed that the observed dual, parallel diffusion of metal and Si, results from the very nature of the oxidation process which modifies the chemical potential of the atoms at the surface being oxidized. Thus is created a force that drives some of the atoms away from the surface, into the inside of the samples. The best known example of this behavior is the often observed "injection" of interstitials during Si oxidation, but a similar process is at work in silicide oxidation, with somewhat similar results. Volume effects, thought to play an important role in solid state chemical reactions, are remarkably well illustrated by the oxidation of silicides.