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ZrO 2 films were grown by atomic layer deposition from ZrCl4 and H2O or a mixture of H2O and H2O2 on Si(100) substrates in the temperature range of 180–600 °C. The films were evaluated in the as-deposited state, in order to follow the effect of deposition temperature on the film quality. The rate of crystal growth increased and the content of residual impurities decreased with increasing temperature. The zirconium-to-oxygen atomic ratio, determined by ion-beam analysis, corresponded to the stoichiometric dioxide regardless of the growth temperature. The effective permittivity of ZrO2 in Al/ZrO2/Si capacitor structures increased from 13–15 in the films grown at 180 °C to 19 in the films grown at 300–600 °C, measured at 100 kHz. The permittivity was relatively high in the crystallized films, compared to the amorphous ones, but rather insensitive to the crystal structure. The permittivity was higher in the films grown using water. The leakage current density tended to be lower and the breakdown field higher in the films grown using hydrogen peroxide.
Kukli et al. (Thu,) studied this question.