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Barrier height ( $\phi _{b}$ ), trap state, bandgap ( $E_{g}$ ), and band alignment information of the metal–ZrO2–metal capacitor have been extracted using internal photoemission (IPE) system. By correlating the IPE analysis with I-V and C-V characteristics obtained before and after rapid thermal annealing, origin and transformation of defect states have been successfully investigated. Our analysis revealed that deep-level defects originating from oxygen vacancies near the top electrode are causing of leakage current in MIM capacitor and these defects can be effectively reduced by a proper thermal annealing.