Kinetics of silicide formation over a wide range of heating rates spanning six orders of magnitude

Kinetic processes involving intermediate phase formation are often assumed to follow an Arrhenius temperature dependence. This behavior is usually inferred from limited data over narrow temperature intervals, where the exponential dependence is generally fully satisfied. However, direct evidence over wide temperature intervals is experimentally challenging and data are scarce. Here, we report a study of silicide formation between a 12 nm film of palladium and 15 nm of amorphous silicon in a wide range of heating rates, spanning six orders of magnitude, from 0.1 to 10⁵K/s, or equivalently more than 300 K of variation in reaction temperature. The calorimetric traces exhibit several distinct exothermic events related to interdiffusion, nucleation of Pd₂Si, crystallization of amorphous silicon, and vertical growth of Pd₂Si. Interestingly, the thickness of the initial nucleation layer depends on the heating rate revealing enhanced mass diffusion at the fastest heating rates during the initial stages of the reaction. In spite of this, the formation of the silicide strictly follows an Arrhenius temperature dependence over the whole temperature interval explored. A kinetic model is used to fit the calorimetric data over the complete heating rate range. Calorimetry is complemented by structural analysis through transmission electron microscopy and both standard and in-situ synchrotron X-ray diffraction.