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An increase in the density of states between the oxygen 2p bands and the Fermi level is seen with increasing Gd concentrations. In addition, for the Gd-doped HfO2 films, the Gd 4f photoexcitation peak at 5.5 eV below the valence band maximum was identified using resonant photoemission. Electrical measurements show pronounced rectification properties for lightly-doped Gd:HfO2 films on p-Si and for heavily-doped Gd:HfO2 films on n-Si, suggesting a crossover from n-type to p-type behavior with increasing doping level. In addition, there is an increase in the reverse bias current with neutron irradiation.