Annealing of nanoindentation-induced high pressure crystalline phases created in crystalline and amorphous silicon

Thermally induced phase transformation of Si-III/Si-XII zones formed by nanoindentation has been studied during low temperature (200<T<300 °C) thermal annealing by Raman microspectroscopy and transmission electron microscopy. Two sizes of spherical indenter tips have been used to create substantially different volumes of phase transformed zones in both crystalline (c-Si) and amorphous silicon (a-Si) to study the zone size and starting matrix effects. The overall transformation is from Si-III/XII to poly- or nanocrystalline Si-I through intermediate phases of Si-XIII and Si-IV. Attempts have been made to determine the exact transformation pathways. Two scenarios are possible: either Si-XII first transforms to Si-III before transforming to Si-I through the intermediate phases or that Si-XII goes through the intermediate phases while Si-III transforms directly to Si-I. Finally, the phase transformations are slower in the larger indents and the starting matrix (crystalline or amorphous) has a substantial effect on the transformation kinetics of the small indents compared to the larger ones. We attribute this increased stability to both matrix effects (nucleation) and a difference in overall residual stress in indents made in a-Si compared to c-Si.