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The effect of a bi-layer structure by varying the Hf composition in Hf-silicate dielectric in improving the electrical performance and reliability of high-κ gate stack n-MOSFETs has been investigated. Introducing Hf-silicate with 19.5% of Hf composition at the bottom layer and 28.5% of Hf on the top of it reduces the leakage current dramatically, while it minimally sacrifices increase in equivalent oxide thickness. Moreover, the structure reduces defect generation rate under gate injection and improves breakdown voltage in comparison to the control samples. Increase in Si-O bonds at the bottom interface, decrease in Coulomb scattering, and increase in dielectric constant in the top layer have been attributed to the overall performance increase of the gate stack.