Akihiro Akama

Growth of epitaxial orthorhombic YO1.5-substituted HfO2 thin film

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 a...

The demonstration of significant ferroelectricity in epitaxial Y-doped HfO2 film.

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.

Contribution of oxygen vacancies to the ferroelectric behavior of Hf0.5Zr0.5O2 thin films

The ferroelectric properties of the (Hf0.5Zr0.5)O2 films on Pt/Ti/SiO2/Si substrate are investigated. It is found that the films crystallized by annealing in O2 and N2 atmospheres have similar crystal structures as well as remanent polarization and coercive fields. Weak temperature and frequency dependences of the ferroelectric properties indicate that the hysteretic behavior in HfO2-based films originates not from the mobile defects but rather from the lattice ionic displacement, as is the case of the typical ferroelectric materials.

Orientation control and domain structure analysis of {100}-oriented epitaxial ferroelectric orthorhombic HfO2-based thin films

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.

Growth of (111)-oriented epitaxial and textured ferroelectric Y-doped HfO2 films for downscaled devices

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 leng...

Formation of (111) orientation-controlled ferroelectric orthorhombic HfO2 thin films from solid phase via annealing

0.07YO1.5-0.93HfO2 (YHO7) films were prepared on various substrates by pulse laser deposition at room temperature and subsequent heat treatment to enable a solid phase reaction. (111)-oriented 10 wt. % Sn-doped In2O3(ITO)//(111) yttria-stabilized zirconia, (111)Pt/TiOx/SiO2/(001)Si substrates, and (111)ITO/(111)Pt/TiOx/SiO2/(001)Si substrates were employed for film growth. In this study, X-ray diffraction measurements including θ–2θ measurements, reciprocal space mappings, and pole figure measurements were used to study the films. The film on (111)ITO//(111)yttria-stabilized zirconia was an (111)-orientated epitaxial film with ferroelectric orthorhombic phase; the film on (111)ITO/(111)Pt/TiOx/SiO2/(001)Si was an (111)-oriented uniaxial textured film with ferroelectric orthorhombic phase; and no preferred orientation was observed for the film on the (111)Pt/TiOx/SiO2/(001)Si substrate, which does not contain ITO. Polarization–hysteresis measurements confirmed that the films on ITO covered substrates had s...

Crystal structure and magnetism in κ-Al2O3-type AlxFe2-xO3 films on SrTiO3(111)

We prepared κ-Al2O3-type structured AlxFe2-xO3 films in the range of x = 0 – 1.70 deposited on SrTiO3(111) substrates and investigated their crystal structures and magnetic properties. All films could be stabilized in the κ-Al2O3-type orthorhombic phase, and the lattice parameters were found to be monotonically decreased with an increase in the Al content. Neel temperature of AlxFe2-xO3 films was found to decrease with an increase in Al content, until the Al1.70Fe0.30O3 film showed paramagnetic behavior. On the other hand, saturation magnetization showed a maximum 0.79 μB/Fe at 10 K in the Al0.91Fe1.09O3 film, manifesting the preferential occupation of Al in the tetrahedral site. Cross sectional TEM observation has revealed the columnar growth of AlxFe2-xO3 films with an average width of ∼10 nm on the bottom layer that may have a similar cation arrangement with a bixbyite-type structure.