The solid state reaction between copper and silicon has been studied using Rutherford backscattering, glancing-angle x-ray diffraction, scanning electron microscopy, and x-ray photoemission spectroscopy. Schottky-barrier-height measurements on n-type Si (100) have also been performed in the temperature range of 95-295 K with the use of a current-voltage technique. The results show that a metal-rich compound with a composition in the Cu3Si range forms at low temperatures (473 K). The electronic properties of the compound are dominated by the hybridization between the Cu(d) and Si(p) valence states. A direct consequence of this hybridization is the peculiar oxidation behavior of the compound surface; both Cu and Si have been found to oxidize at room temperature. The oxidation of Si in the silicide is enhanced as compared with the oxidation of the elemental single-crystalline Si surface. Upon annealing the oxidized surface, a solid state reaction takes place: Cu2O disappears and a thicker SiO2 layer grows, owing to the large difference in free energies of formation between SiO2 and Cu 2O. The n-type barrier height of 0.79 eV for both the as-deposited metal and the metal-rich silicide phase decreases with increasing temperature with a coefficient close to the temperature coefficient of the indirect energy gap in Si. These results suggest that the Fermi level at the interface is pinned relative to the valence-band edge, independent of temperature.