The ferroelectricity in ultrathin HfO2 offers a viable alternative to ferroelectric memory. A reliable switching behavior is required for commercial applications; however, many intriguing features of this material have not been resolved. Herein, we report an increase in the remnant polarization after electric field cycling, known as the “wake-up” effect, in terms of the change in the polarization-switching dynamics of a Si-doped HfO2 thin film. Compared with a pristine specimen, the Si-doped HfO2 thin film exhibited a partial increase in polarization after a finite number of ferroelectric switching behaviors. The polarization-switching behavior was analyzed using the nucleation-limited switching model characterized by a Lorentzian distribution of logarithmic domain-switching times. The polarization switching was simulated using the Monte Carlo method with respect to the effect of defects. Comparing the experimental results with the simulations revealed that the wake-up effect in the HfO2 thin film is accompanied by the suppression of disorder.

The recent demand for analogue devices for neuromorphic applications requires modulation of multiple nonvolatile states. Ferroelectricity with multiple polarization states enables neuromorphic applications with various architectures. However, deterministic control of ferroelectric polarization states with conventional ferroelectric materials has been met with accessibility issues. Here, we report unprecedented stable accessibility with robust stability of multiple polarization states in ferroelectric HfO 2 . Through the combination of conventional voltage measurements, hysteresis temperature dependence analysis, piezoelectric force microscopy, first-principles calculations, and Monte Carlo simulations, we suggest that the unprecedented stability of intermediate states in ferroelectric HfO 2 is due to the small critical volume size for nucleation and the large activation energy for ferroelectric dipole flipping. This work demonstrates the potential of ferroelectric HfO 2 for analogue device applications enabling neuromorphic computing.

Hafnium oxides‐based ferroelectric materials are promising for applications in nonvolatile memory devices. To control the ferroelectricity of such materials, it is necessary to tune their polymorphism, interfacial features, and defect (oxygen vacancy) distribution. A strategy is described for enhancing the ferroelectric properties of polycrystalline hafnium zirconium oxide (HZO) ultrathin films by modifying the oxygen pressure during the device preparation stage, which involves thermal annealing of TiN electrodes that serve as oxygen reservoirs. Microstructural and chemical characterizations along with theoretical analysis reveal that interfacial layers of TiO2−x (or TiOxNy) can characteristically form between the TiN electrode and the HZO thin film, depending on the oxygen treatment conditions. These interfacial layers directly affect the polymorphic distribution of the as‐deposited HZO. In particular, the engineered interfacial TiO2−x layer facilitates the generation and stabilization of ferroelectric orthorhombic phase HZO by promoting the uniform distribution of oxygen vacancies. Electric field cycling tests further highlight the enhanced ferroelectric polarization and coercive voltage following interfacial engineering. The results presented herein demonstrate successful tuning of the structural and interfacial properties of polycrystalline HZO devices, thus enabling control over their ferroelectric characteristics, which is critical for the fabrication of devices with designed functionality.

Investigations concerning oxygen deficiency will increase our understanding of those factors that govern the overall material properties. Various studies have examined the relationship between oxygen deficiency and the phase transformation from a nonpolar phase to a polar phase in HfO2 thin films. However, there are few reports on the effects of oxygen deficiencies on the switching dynamics of the ferroelectric phase itself. Herein, we report the oxygen- deficiency induced enhancement of ferroelectric switching properties of Si-doped HfO2 thin films. By controlling the annealing conditions, we controlled the oxygen deficiency concentration in the ferroelectric orthorhombic HfO2 phase. Rapid high-temperature (800 °C) annealing of the HfO2 film accelerated the characteristic switching speed compared to low-temperature (600 °C) annealing. Scanning transmission electron microscopy and electron energy-loss spectroscopy (EELS) revealed that thermal annealing increased oxygen deficiencies, and first-principles calculations demonstrated a reduction of the energy barrier of the polarization flip with increased oxygen deficiency. A Monte Carlo simulation for the variation in the energy barrier of the polarization flipping confirmed the increase of characteristic switching speed.

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