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Gd2O3 and Gd-doped HfO2 films were deposited on p-type silicon substrates in a reducing atmosphere. Gd 4f photoexcitation peaks at roughly 7 and 5 eV below the valence band maximum have been identified using the resonant photoemission of Gd2O2 and Gd-doped HfO2 films, respectively. In the case of Gd2O3, strong hybridization with the O 2p band is demonstrated, and there is evidence that the Gd 4f weighted band exhibits dispersion in the bulk band structure. The rectifying (diode-like) properties of Gd-doped HfO2–silicon and Gd2O3–silicon heterojunctions are demonstrated.