The thickness dependences of the crystal structure and electric properties of (111)-oriented epitaxial 0.07YO1.5-0.93HfO2 (YHO7) ferroelectric films were investigated for the film thickness range of 10–115 nm. The YHO7 films were grown by pulsed laser deposition or sputtering at room temperature and subsequent heat treatment. As a substrate for the epitaxial growth of the YHO7 film, (111)-oriented 10 wt. % Sn-doped In2O3(ITO)//(111) yttria-stabilized zirconia was used. X-ray diffraction measurements confirmed that the main crystal phase of these YHO7 films was ferroelectric orthorhombic for up to 115-nm-thick films. Small film-thickness dependences of remanent polarization (Pr) and saturation polarization (Ps) were observed. Thickness dependence of the coercive field (Ec) is also small, and this behavior does not resemble that of conventional ferroelectric films such as Pb(Zr,Ti)O3. Additionally, non-oriented polycrystalline YHO7 films are reported to have similar thickness dependence of Ec and almost the same Ec value to epitaxial YHO7 films. We suggest that the ferroelectric domain is significantly small for both epitaxial and polycrystalline films. Such small domains remain even in thicker films, giving rise to thickness-independent Ec.

Herein, ferroelastic domain switching from the nonpolar b-axis to the polar c-axis oriented domain in 7%-YO1.5-substituted HfO2 (YHO-7) epitaxial ferroelectric films is demonstrated. Scanning transmission electron microscopy (STEM) indicates that the polarization of a pristine film deposited on a Sn-doped In2O3/(001)YSZ substrate by the pulsed laser deposition method tends to be along the in-plane direction to avoid a strong depolarization field with respect to the out-of-plane direction. Applying an electric field aids in ferroelastic domain switching in YHO-7 films. Such films exhibit ferroelectric characteristics with a relatively large saturated polarization around 30 μC/cm2 by polarization reorientation from the in-plane to the out-of-plane directions and an increased dielectric constant. The synchrotron X-ray diffraction measurements with a focused beam for the pristine and poled area indicate ferroelastic 90° domain switching as the odd number reflection disappears, which is only allowed in the nonpolar b-axis orientation. STEM observations also show a significant increase in the c-axis oriented domain. This observation of ferroelastic domain switching strongly supports the conclusion that the ferroelectricity of HfO2 originates from the non-centrosymmetric orthorhombic phase.

Ferroelectricity has been demonstrated in polycrystalline 7%Y-doped HfO2 (YHO7) films with thicknesses ranging from 10 to 930 nm, which were grown on (111)Pt/TiOx/SiO2/(001)Si substrates by pulsed laser deposition at room temperature and subsequent annealing at 1000 °C. The X-ray diffraction pattern suggested that the major crystal phase consists of orthorhombic/tetragonal phases with a small amount of monoclinic phase even for the 930-nm-thick film despite its thickness. Moreover, the hysteresis loops associated with the ferroelectric orthorhombic phase were clearly observed for all samples including even the 930-nm-thick film. The remnant polarization (Pr) and the coercive field (Ec) are 14–17 μC/cm2 and 1300–1600 kV/cm, respectively, at max applied electric fields of ∼4000 kV/cm for all YHO7 films within the present study. These results indicate that the ferroelectric structure and properties of YHO7 films are insensitive to the film thickness.

One of the general features of ferroelectric systems is a complex nature of polarization reversal, which involves domain nucleation and motion of domain walls. Here, time‐resolved nanoscale domain imaging is applied in conjunction with the integral switching current measurements to investigate the mechanism of polarization reversal in yttrium‐doped HfO2 (Y:HfO2)—currently one of the most actively studied ferroelectric systems. More specifically, the effect of film microstructure on the nucleation process is investigated by performing a comparative study of the polarization switching behavior in the epitaxial and polycrystalline Y:HfO2 thin film capacitors. It is found that although the epitaxial Y:HfO2 capacitors tend to switch slower than their polycrystalline counterparts, they exhibit a significantly higher nucleation density and rate, suggesting that this is a rate‐limiting mechanism. In addition, it is observed that under the external fields approaching the activation field value, the switching kinetics can be described equally well by the nucleation limited switching and the Kolmogorov‐Avrami‐Ishibashi models for both types of capacitors. This signifies convergence of two different mechanisms implying that the polarization reversal proceeds via a homogeneous nucleation process unaffected by the film microstructure, which can be considered as approaching the intrinsic switching limit.

Ferroelectricity has been demonstrated in epitaxial 7%Y-doped HfO2 (0.07YO1.5–0.93HfO2, YHO7) films grown by the RF magnetron sputtering method at room temperature without any subsequent annealing. The x-ray diffraction patterns of such films suggested that the decrease in RF power and in the partial oxygen pressure changes the crystal structures of the films from the monoclinic phase to the tetragonal/orthorhombic phase. Clear polarization-electric-field (P–E) hysteresis loops were observed for these epitaxial films with the tetragonal/orthorhombic phase. The obtained remanent polarization (Pr) and coercive field (Ec) values were 14.5 and 12.8 μC/cm2 and 2300 and 2200 kV/cm for the epitaxial films on (111) indium tin oxide (ITO)//(111) yttria-stabilized zirconia (YSZ) and (100)ITO//(100)YSZ substrates, respectively. Moreover, ferroelectricity was also observed in room-temperature-deposited polycrystalline YHO7 films prepared on Pt/TiOx/SiO2/(100)Si, crystallized ITO/soda glass, and amorphous ITO/polyethylene terephthalate substrates, namely, crystalline ferroelectric HfO2-based films were prepared at room temperature on various substrates, including organic flexible substrates, by using the RF magnetron sputtering method. The present results open a path to novel applications of ferroelectric HfO2-based films such as ferroelectric flexible memory.