清水 勝

The bulk photovoltaic effect (BPVE) is a mechanism of recent focus for novel solar cells that exceed the power conversion efficiency of p–n junction solar cells because of the quantum mechanical effect to generate photocurrent known as shift current. Ferroelectrics are receiving attention again because of their high voltage generation by the BPVE and converse piezoelectric effect to realize high performance optical actuators. We have investigated the BPVE in ferroelectric BiFeO3 (BFO) single crystal thin films, whereby the photovoltage was enhanced by Mn doping, and 852 V generation was demonstrated at 80 K. The enhancement mechanism was also investigated using soft and hard X-ray photoelectron spectroscopy (SXPES, HAXPES), and soft X-ray absorption spectroscopy with synchrotron radiation. This report reveals a way to new voltage source applications employing the BPVE for high impedance devices with ferroelectrics. Important aspects for designing ferroelectric materials by impurity doping are also discussed.

© 2019 The Japan Society of Applied Physics. This work demonstrated the artificial introduction of charged domain walls (CDWs) into a ferroelectric BiFeO3 (BFO) thin film by domain structure control using a pit-patterned SrTiO3 (STO) (001) surface. The pattern consisted of 1 × 1 μm square holes with sloped sides, fabricated on the STO (001) surface by electron beam lithography and Ar+ ion etching. Scanning electron and atomic force microscopy analyses demonstrated that the pit slopes had angles of 6.1°-7.6°, which were sufficient to limit the in-plane growth direction of the BFO at step edges on the STO surface, and thus control the domain structure. Lateral and vertical piezoresponse scanning force and transmission electron microscopy confirmed the artificial introduction of CDWs in the pit and showed that the sign of the CDWs could be reversed via ferroelectric polarization switching. This domain control technique based on a pit pattern provides a simple approach to the integration of ferroelectric DWs into functional devices.

© 2019 The Japan Society of Applied Physics. We investigated the compositional self-regulation and seeding effects of an Fe2O3 layer during the metalorganic chemical vapor deposition of epitaxial BiFeO3 thin films. The growth of the BiFeO3 films was explained in terms of the prior deposition of Fe2O3 and the subsequent incorporation of Bi2O3 into Fe2O3. The self-regulation of film composition was achieved by supplying excess Bi at high growth temperature. The introduction of an Fe2O3 seed layer as thin as 5 nm promoted homogeneous thin film growth and consequently reduced the leakage and its fluctuation as well as the compositional fluctuation. The seed layer also served to control the interfacial composition between BiFeO3 and SrRuO3.

© 2018 The Japan Society of Applied Physics. Pt/1-μm-thick Bi1.0Fe0.99Mn0.01O3 (BFMO)/Pt coplanar capacitors with an interelectrode distance of 260 μm have been fabricated on vicinal SrTiO3 (STO) (001) substrates by radio frequency magnetron sputtering. The bulk photovoltaic effect of a BFMO thin film has been investigated by measuring the current-voltage (I-V) characteristics of the Pt/BFMO/Pt coplanar capacitors under blue-violet laser illumination (λ = 405 nm). The I-V characteristics show the light-polarization-dependent open-circuit voltage (V OC) with a maximum of -209 V. In addition, the optical strain of a BFMO/STO cantilever with a size of 15 mm × 1.3 mm × 70 μm has been investigated by measuring the displacement of the edge of the cantilever under blue-violet laser illumination. The edge displacement depended on light polarization, indicating that the optical strain is due to the coupling between the bulk photovoltaic effect and the inverse piezoelectric effect.

© 2017 The Japan Society of Applied Physics. Recently, new functionalities of ferroelectric domain walls (DWs) have attracted much attention. To realize novel devices using the functionalities of the DWs, techniques to introduce the DWs at arbitrary positions in the ferroelectric thin films are necessary. In this study, we have demonstrated the introduction of the DWs at arbitrary positions in epitaxial BiFeO3(BFO) thin films using the patterned surface of the SrTiO3(STO) single-crystal substrate. On the slope pattern of the STO surface, the in-plane orientation of BFO has changed because the in-plane orientation of BFO can be controlled by the step propagation direction of the patterned surface. From the piezoresponse scanning force microscopy and X-ray diffraction reciprocal space mapping results, charged 109° DWs have been introduced into the BFO thin film at the bottom and top of the slope pattern of the STO surface. In addition, the conductivity modulation of the positively charged DW has been observed by current-sensitive atomic force microscopy imaging.