Microstructural characterisation and compound formation in rapidly solidified SiGe alloy

Severe Ge segregation to grain boundaries was observed in a Si–14.2 at% Ge thermoelectric alloy rapidly solidified using a drop-tube facility, manifesting itself as a series of regions with uniform stoichiometric compositions. The step change in composition at the interface between adjacent regions was ascribed to the formation of different SiGe pseudocompounds and contradicted the accepted thermodynamic description of the SiGe system as a continuous random solid solution. Rapid solidification increased, rather than decreased, the inhomogeneity degree of the solid product, and the Ge content of the most Ge-rich regions was positively correlated with the cooling rate, which suggested the absence of solute trapping. The transmission electron microscopy/selected area electron diffraction analysis of the most Ge-rich regions revealed superlattice spots indicative of chemical ordering. However, simple chemical ordering within a single diamond cubic unit cell could not explain the fact that most stoichiometries had compositions that were multiples of 5 at% Ge, which indicated the presence of superstructural ordering.