Ferroelectricity in dopant-free HfO₂ thin films prepared by pulsed laser deposition

As a high-k material, hafnium oxide (HfO₂) has been used in gate dielectrics for decades. Since the discovery of polar phase in Si-doped HfO₂ films, chemical doping has been widely demonstrated as an effective approach to stabilize the ferroelectric phase in HfO₂ based thin films. However, the extra capping layer deposition, post-growth annealing and wake-up effect are usually required to arouse the ferroelectricity in HfO₂ based thin films, resulting in the increase of complexity for sample synthesis and the impediment of device application. In this study, the ferroelectricity is observed in non-capped dopant-free HfO₂ thin films prepared by pulsed laser deposition (PLD) without post-growth annealing. By adjusting the deposited temperature, oxygen pressure and thickness, the maximum polarization up to 14.7 μC/cm² was obtained in 7.4 nm-thick film. The fraction of orthorhombic phase, concentrations of defects and size effects are considered as possible mechanisms for the influences of ferroelectric properties. This study indicates that PLD is an effective technique to fabricate high-quality ferroelectric HfO₂ thin films in the absence of chemical doping, capping layer deposition and post-growth annealing, which may boost the process of nonvolatile memory device application.