Relatively mild annealing sometimes produces unexpectedly large change
s in surface composition of ultra-thin films. We report results of a s
canning tunnelling microscopy study of such annealing in an Fe/Cu(100)
system. Copper appears in the surface region after a short 490 K anne
al. We specifically exclude the possibility of bulk interdiffusion and
conclude that this surface copper comes from the substrate through mi
croscopic pinholes. Our primary finding is that the balance of surface
free energies which strongly prefers Cu/Fe/Cu over Fe/Cu is the main
driving force for pinhole formation and copper segregation. Furthermor
e, we report a significant surface alloying in this otherwise almost i
mmiscible system.