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Gd-doped HfO2 films were deposited on p-type silicon substrates in a reducing atmosphere. Photoemission measurements indicate the n-type character of Gd-doped HfO2 due to overcompensation with oxygen vacancies. The Gd 4 f photoexcitation peak at 5.5 eV below the valence band maximum is identified using both resonant photoemission and first-principles calculations of the f hole. The rectifying (diode- like) properties of Gd-doped HfO2 to silicon heterojunctions are demonstrated.