Ferroelectricity and Curie temperature are demonstrated for epitaxial Y-doped HfO2 film grown on (110) yttrium oxide-stabilized zirconium oxide (YSZ) single crystal using Sn-doped In2O3 (ITO) as bottom electrodes. The XRD measurements for epitaxial film enabled us to investigate its detailed crystal structure including orientations of the film. The ferroelectricity was confirmed by electric displacement filed – electric filed hysteresis measurement, which revealed saturated polarization of 16 μC/cm2. Estimated spontaneous polarization based on the obtained saturation polarization and the crystal structure analysis was 45 μC/cm2. This value is the first experimental estimations of the spontaneous polarization and is in good agreement with the theoretical value from first principle calculation. Curie temperature was also estimated to be about 450 °C. This study strongly suggests that the HfO2-based materials are promising for various ferroelectric applications because of their comparable ferroelectric properties including polarization and Curie temperature to conventional ferroelectric materials together with the reported excellent scalability in thickness and compatibility with practical manufacturing processes.

YO1.5-substituted HfO2 thin films with various substitution amounts were grown on (100) YSZ substrates by the pulsed laser deposition method directly from the vapor phase. The epitaxial growth of film with different YO1.5 amounts was confirmed by the X-ray diffraction method. Wide-area reciprocal lattice mapping measurements were performed to clarify the crystal symmetry of films. The formed phases changed from low-symmetry monoclinic baddeleyite to high-symmetry tetragonal/cubic fluorite phases through an orthorhombic phase as the YO1.5 amount increased from 0 to 0.15. The additional annular bright-field scanning transmission electron microscopy indicates that the orthorhombic phase has polar structure. This means that the direct growth by vapor is of polar orthorhombic HfO2-based film. Moreover, high-temperature X-ray diffraction measurements showed that the film with a YO1.5 amount of 0.07 with orthorhombic structure at room temperature only exhibited a structural phase transition to tetragonal phase above 450 °C. This temperature is much higher than the reported maximum temperature of 200 °C to obtain ferroelectricity as well as the expected temperature for real device application. The growth of epitaxial orthorhombic HfO2-based film helps clarify the nature of ferroelectricity in HfO2-based films (186 words/200 words).

Orientation control of {100}-oriented epitaxial orthorhombic 0.07YO1.5-0.93HfO2 films grown by pulsed laser deposition was investigated. To achieve in-plane lattice matching, indium tin oxide (ITO) and yttria-stabilized zirconia (YSZ) were selected as underlying layers. We obtained (100)- and (001)/(010)-oriented films on ITO and YSZ, respectively. Ferroelastic domain formation was confirmed for both films by X-ray diffraction using the superlattice diffraction that appeared only for the orthorhombic symmetry. The formation of ferroelastic domains is believed to be induced by the tetragonal–orthorhombic phase transition upon cooling the films after deposition. The present results demonstrate that the orientation of HfO2-based ferroelectric films can be controlled in the same manner as that of ferroelectric films composed of conventional perovskite-type material such as Pb(Zr, Ti)O3 and BiFeO3.

In this study, the growth of (111)-oriented epitaxial and textured YO1.5-HfO2 (0.07:0.93 ratio) films using the pulsed laser deposition method is presented. Epitaxial films were prepared on ITO//(111)yttria-stabilized zirconia (YSZ) substrates (ITO: Sn-doped In2O3; YSZ: yttria-stabilized zirconia), while textured films were prepared on (111)Pt/TiOx/SiO2//Si substrates with and without an ITO buffer layer via the grain on grain coherent growth. Inserting an ITO layer increased the volume fraction of the ferroelectric orthorhombic phase. Both the epitaxial and uniaxially textured films exhibited similar ferroelectricity with a remanent polarization of around 10 μC/cm2 and a coercive field of 1.9 to 2.0 MV/cm. These results present us with a way of obtaining stable and uniform ferroelectric properties for each grain and device cells consisting of a small number of grains. This opens the door for ultimately miniaturized ferroelectric devices, such as ferroelectric field effect transistors with small gate length and resistive random access memory using ferroelectric tunnel junctions.

The process of forming the ferroelectric orthorhombic phase was investigated for epitaxial 7% Y-doped (YHO7) films using in situ high-temperature X-ray diffraction. Epitaxial YHO7 films were grown on (111) ITO-coated (111)YSZ substrates by pulsed laser deposition at room temperature and a subsequent heat treatment process. Films deposited at room temperature were crystallized as paraelectric monoclinic phase. The monoclinic phase partially changes to tetragonal phase above 600 °C and perfectly transformed around 950 °C during heating. The change from tetragonal phase to orthorhombic phase was detected at 300 °C, corresponding to the Curie temperature under the cooling process. These results clearly suggest that the tetragonal phase was more stable at 1000 °C for YHO7 films on heating than the other phases, and the formation of this tetragonal phase—the high-temperature paraelectric phase of the ferroelectric orthorhombic phase—is key to the formation of the ferroelectric orthorhombic phase.