The band alignment of ZrO 2/interfacial layer/Si structure fabricated by simultaneous oxidation and nitridation of sputtered Zr on Si in N 2O at 700°C for different durations has been established by using X-ray photoelectron spectroscopy. Valence band offset of ZrO 2/Si was found to be 4.75 eV, while the highest corresponding conduction offset of ZrO 2/interfacial layer was found to be 3.40 eV; owing to the combination of relatively larger bandgaps, it enhanced electrical breakdown field to 13.6 MV/cm at 10 -6 A/cm 2.