A new type of phase transformation at the interface is described in CoSi2/Si(111) B (i.e. twinned) epilayers. Thin (25Å) CoSi2 films are codeposited at room temperature on Si (111) with a Si-rich surface layer, and subsequently annealed. Plan-view transmission electron microscopy (TEM) shows that these films have low symmetry, the interface being characterised by a shift “R” between (220) planes in CoSi2 and Si. X-ray diffraction from “R” films differs from otherwise identical films either grown without Si-rich surface layer, or not annealed, which have the conventional cubic structure (“C”); R-CoSi2 cannot be indexed on a single reciprocal lattice. Cross-section high-resolution TEM suggests the presence of a separate (non-cubic) layer ≈9Å thick at the interface in these films. Annealing of R-CoSi2
in-situ in the TEM shows a reversible transformation R⇔C occuring at temperatures varying from 180°C to 150K, depending on layer stoichiometry. Rt⇔C is thus a quasi-equilibrium, diffusionless transformation. We propose that R-CoSi2 lowers interfacial free energy for certain stoichiometries, but that bulk constraints stop the entire layer from transforming.