Oxidation of titanium, manganese, iron, and niobium silicides: Marker experiments

The mechanism of atomic transport inside the silicide during thermal oxidation of silicide layers on Si substrates has been analyzed by means of inert gas markers implanted in TiSi2, Mn11Si19, FeSi2, and NbSi2. Oxidation was carried out in dry oxygen. The marker displacement reveals that the growth of metal-free SiO2 over the first three of these compounds occurs via the reverse motion of metal atoms, from the silicide/oxide to the silicon/silicide interface, rather than through the direct diffusion of Si atoms from the substrate to the oxide. Moreover, analysis of the marker position indicates that the total amount of Si between the marker and the free surface decreases during oxidation, as had been previously observed in the oxidation of NiSi2, CoSi2, and CrSi2. Although this could occur via the formation and evaporation of SiO, it is believed that the loss of Si is due to the motion of Si atoms, also in the "reverse" direction as for the metal atoms, across the silicide layer. The experiment conducted with NbSi2 shows that this silicide oxidizes via the direct motion of Si from the substrate to the oxide as anticipated. With TiSi2 the initial state of oxidation occurs as described, but the experimental observations imply that thick oxide layers grow via the direct motion of Si from the substrate to the oxide.