The properties of a newly discovered pseudomorphic FeSi/Si(111) phase
with the CsCl structure are discussed. Upon annealing the new phase un
dergoes phase transitions to the stable epsilon-FeSi phase, either in
epitaxial or polycrystalline form, depending on film thickness. Instea
d of transforming to epsilon-FeSi, very thin films (d < 15 angstrom) e
xhibit an uptake of Si up to the stoichiometry of FeSi2. The symmetry
of the resulting phase remains unchanged, however, except for prolonge
d annealing close to the transition to beta-FeSi2, where the formation
of fluorite gamma-FeSi2 grains is observed. We emphasize the far reac
hing consequences of the epitaxial stability of the defect-CsCl phase
over a large range of compositions.