The effective heat of formation model allows heats of formation to be calculated as a function of the concentration of the reactants at the growth interface. The effective concentration is taken to be the concentration of the liquidus minimum for the relevant binary system. Using this model, the anomalous and contradictory results for initial formation of titanium silicide phases are ascribed to the two eutectics at 14 and 84 at.% silicon (both at 1330 °C) for the Ti-Si binary system. The native oxide layer usually present on silicon surfaces and the affinity of Ti for oxygen further affect the effective concentration, thereby adding to the contradictory experimental results that have been found. In the Ni-Si system our measurements show that a sufficiently high concentration of oxygen in amorphous silicon can lead to formation of NiSi instead of Ni2Si, which is normally the first phase to form. This observation, as well as the formation of NiSi2 as the first phase in the presence of diffusion barriers, is also explained in terms of the effective heat of formation model.
The redistribution and the effect of oxygen on Co and Ni silicide formation were measured as a function of concentration and initial location by RBS, resonant scattering, AES and SIMS. RBS depth profiling was also used to study the effect of gold on Co silicide formation.
The growth kinetics of CoSi2 formation has been studied in the presence and absence of Au. Very small amounts of Au (as little as 14 Å at the SiCo interface) were found to increase the growth rate of CoSi2 dramatically and also caused a decrease in the activation energy from 2.3 to 1.2 eV. A change in phase sequence and growth mechanism was also observed.