High-quality, uniform, Si/NiSi2/Si(100) structures were demonstrated b
y a combination of molecular-beam epitaxy and postgrowth, high-tempera
ture annealing. A Si template technique ensures the epitaxial orientat
ion of the Si overlayer. The unusual inverse Volmer-Weber mode observe
d during the growth of Si on NiSi2(100) is shown to be a result of int
erface and surface energetics. The evolution of the interface morpholo
gy of the double-heteroepitaxial structures is discussed in terms of t
hermodynamics.