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The optical properties, interface structure, and thermal stability of the ZrO2 films grown on Si(100) were investigated in detail. A 2 nm thick interfacial layer (IL) is formed at the ZrO2–Si interface for the as-grown ZrO2. The optical constants of ZrO2 films and IL correspond to amorphous-ZrO2 and amorphous-SiO2, respectively. The oxidation and IL growth at 900 °C, as a function of annealing time, exhibit a two-step behavior with a slow and a fast growth-rate zones. The transition from a zone of slow to fast rate is attributed to structurally modified ZrO2 facilitating the faster oxygen transport to the ZrO2/Si interface. [ABSTRACT FROM AUTHOR]