The structural and electronic properties of the epitaxial Al/Si(111)7×7 interface and their modifications upon thermal annealing were investigated by scanning tunneling microscopy, high‐resolution photoelectron spectroscopy, and low‐energy electron diffraction. Room‐temperature deposition of 40 Å Al on Si(111)7×7 is mainly characterized by epitaxial growth and a decrease of the Fermi‐level position by 0.32 eV. Annealing at temperatures around 500 °C results in the formation of large Al clusters with a thin reacted film in between. Subsequent annealing up to 900 °C results in complete desorption of Al and a recovery of the original 7×7 surface structure, while a potential variation underneath the Si surface, completely different from that of the starting surface, is observed in the Si 2p photoemission spectra. These results strongly indicate the formation of a p+‐Si layer induced by Al diffusion.

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