This study examined the impact of positive bias temperature instability (PBTI) on n-channel metal-oxide-semiconductor field-effect transistor (n- MOSFET) with TiN barrier layer sandwiched between metal gate electrode and HfO2 dielectric. The experimental results clearly demonstrate that the diffusion mechanism of oxygen and nitrogen as a result of the post metallization treatment was the root cause of the PBTI. In this mechanism, the oxygen during the post metallization annealing (PMA) was diffused into TiN layer and replaced the nitrogen in the TiN layer. Subsequently, these replaced nitrogens were diffused into the HfO2, from which these replaced nitrogen atoms were used to passivate the defects in the HfO2. Results show that by increasing the thickness of TiN barrier layer, the driving current and the PBTI of n-MOSFET can be greatly improved. The larger the thickness of the TiN layer is, the better the PBTI reliability becomes.