Novel hafnium oxide (HfO 2 )-based ferroelectrics reveal full scalability and complementary metal oxide semiconductor integratability compared to perovskite-based ferroelectrics that are currently used in nonvolatile ferroelectric random access memories (FeRAMs). Within the lifetime of the device, two main regimes of wake-up and fatigue can be identified. Up to now, the mechanisms behind these two device stages have not been revealed. Thus, the main scope of this study is an identification of the root cause for the increase of the remnant polarization during the wake-up phase and subsequent polarization degradation with further cycling. Combining the comprehensive ferroelectric switching current experiments, Preisach density analysis, and transmission electron microscopy (TEM) study with compact and Technology Computer Aided Design (TCAD) modeling, it has been found out that during the wake-up of the device no new defects are generated but the existing defects redistribute within the device. Furthermore, vacancy diffusion has been identified as the main cause for the phase transformation and consequent increase of the remnant polarization. Utilizing trap density spectroscopy for examining defect evolution with cycling of the device together with modeling of the degradation results in an understanding of the main mechanisms behind the evolution of the ferroelectric response.

The unexpected ferroelectric properties of nanoscale hafnia-zirconia are considered to be promising for a wealth of applications including ferroelectric memory, field effect transistors, and energy-related applications. However, the reason why the unexpected ferroelectric Pca2 phase can be stabilized has not been clearly understood although numerous extensive theoretical and experimental results have been reported recently. The ferroelectric orthorhombic phase is not a stable phase under processing conditions from the viewpoint of bulk free energy. Although the possibility of stabilization of the ferroelectric phase due to the surface energy effect has been theoretically suggested, such a theoretical model has not been systematically compared with actual experimental results. In this study, the experimental observations on polymorphism in nanoscale HfO-ZrO solid solution thin films of a wide range of film compositions and thicknesses are comprehensively related to the theoretical predictions based on a thermodynamic surface energy model. The theoretical model can semi-quantitatively explain the experimental results on the phase-evolution, but there were non-negligible discrepancies between the two results. To understand these discrepancies, various factors such as the film stress, the role of a TiN capping layer, and the kinetics of crystallization are systematically studied. This work also reports on the evolution of electrical properties of the film, i.e. dielectric, ferroelectric, anti-ferroelectric, and morphotropic phase changes, as a function of the film composition and thickness. The in-depth analyses of the phase change are expected to provide an important guideline for subsequent studies.

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