Photoelectrochemical Device Designs toward Practical Solar Water Splitting: A Review on the Recent Progress of BiVO4 and BiFeO3 Photoanodes

Solar-driven water splitting technology is considered to be a promising solution for the global energy challenge as it is capable of generating clean chemical fuel from solar energy. Various strategies and catalytic materials have been explored in order to improve the efficiency of the water splitting reaction. Although significant progress has been made, there are many intriguing fundamental phenomena that need to be understood. Herein, we review recent experimental efforts to demonstrate enhancement strategies for efficient solar water splitting, especially for the light absorption, charge carrier separation, and water oxidation kinetics. We also focus on the state of the art of photoelectrochemical (PEC) device designs such as application of facet engineering and the development of a ferroelectric-coupled PEC device. Based on these experimental achievements, future challenges, and directions in solar water splitting technology will be discussed

Anomalous Photocurrent Reversal Due to Hole Traps in AlGaN-Based Deep-Ultraviolet Light-Emitting Diodes

The trap states and defects near the active region in deep-ultraviolet (DUV) light-emitting diodes (LED) were investigated through wavelength-dependent photocurrent spectroscopy. We observed anomalous photocurrent reversal and its temporal recovery in AlGaN-based DUV LEDs as the wavelength of illuminating light varied from DUV to visible. The wavelength-dependent photocurrent measurements were performed on 265 nm-emitting DUV LEDs under zero-bias conditions. Sharp near-band-edge (~265 nm) absorption was observed in addition to broad (300–800 nm) visible-range absorption peaks in the photocurrent spectrum, while the current direction of these two peaks were opposite to each other. In addition, the current direction of the photocurrent in the visible wavelength range was reversed when a certain forward bias was applied. This bias-induced current reversal displayed a slow recovery time (~6 h) when the applied forward voltage was removed. Furthermore, the recovery time showed strong temperature dependency and was faster as the sample temperature increased. This result can be consistently explained by the presence of hole traps at the electron-blocking layer and the band bending caused by piezoelectric polarization fields. The activation energy of the defect state was calculated to be 279 meV using the temperature dependency of the recovery time

Direct In Situ Growth of Centimeter‐Scale Multi‐Heterojunction MoS2/WS2/WSe2 Thin‐Film Catalyst for Photo‐Electrochemical Hydrogen Evolution

To date, the in situ fabrication of the large-scale van der Waals multi-heterojunction transition metal dichalcogenides (multi-TMDs) is significantly challenging using conventional deposition methods. In this study, vertically stacked centimeter-scale multi-TMD (MoS2/WS2/WSe2 and MoS2/WSe2) thin films are successfully fabricated via sequential pulsed laser deposition (PLD), which is an in situ growth process. The fabricated MoS2/WS2/WSe2 thin film on p-type silicon (p-Si) substrate is designed to form multistaggered gaps (type-II band structure) with p-Si, and this film exhibits excellent spatial and thickness uniformity, which is verified by Raman spectroscopy. Among various application fields, MoS2/WS2/WSe2 is applied to the thin-film catalyst of a p-Si photocathode, to effectively transfer the photogenerated electrons from p-Si to the electrolyte in the photo-electrochemical (PEC) hydrogen evolution. From a comparison between the PEC performances of the homostructure TMDs (homo-TMDs)/p-Si and multi-TMDs/p-Si, it is demonstrated that the multistaggered gap of multi-TMDs/p-Si improves the PEC performance significantly more than the homo-TMDs/p-Si and bare p-Si by effective charge transfer. The new in situ growth process for the fabrication of multi-TMD thin films offers a novel and innovative method for the application of multi-TMD thin films to various fields

Bendable BiVO4-Based Photoanodes on a Metal Substrate Realized through Template Engineering for Photoelectrochemical Water Splitting

Unlike planar photoelectrodes, bendable and malleable photoelectrodes extend their application to mechanical flexibility beyond conventional rigid structures, which have garnered new attention in the field of photoelectrochemical water splitting. A bendable metal (Hastelloy), which has both bendability and compatibility with various oxide layers, allows high-temperature processes for crystallization; therefore it is far superior as a substrate than a conventional flexible polymer. In this study, we fabricate bendable BiVO4 crystalline thin films on the metal substrates by employing template layers (SrRuO3/SrTiO3) to reduce the structural misfits between BiVO4 and the substrate. The crystallinities were verified through X-ray diffraction and transmission electron microscopy, and photocatalytic performances were examined. The crystallinity of BiVO4 was significantly improved by utilizing similar lattice constants and affinities between BiVO4 and the oxide template layers. We also formed a type II heterojunction by adding a WO3 layer which complements the charge separation and charge transfer as a photoanode. The photocurrent densities of tensile-bent BiVO4/WO3 thin films with a bending radius of 10 mm are comparable to those of pristine BiVO4/WO3 thin film in various aqueous electrolytes. Moreover, photostability tests showed that the tensile-bent crystalline photoanodes retained 90% of their initial photocurrent density after 24 h, which proved their exceptional durability. Our work demonstrates that the bendable photoelectrodes with crystallinity hold great potential in terms of device structure for solar-driven water splitting.11Nsciescopu

Enhanced ferroelectricity in perovskite oxysulfides

© 2019 American Physical Society.A sulfur element is a promising anion dopant for synthesizing new multifunctional materials and for exploring unusual physical phenomena. However, owing to its volatility, sulfur substitution to oxide materials is challenging, and thus the sulfurization effects on the associated properties have been limitedly studied. Here, a facile method for sulfurization to a perovskite oxide Pb(Zr,Ti)O3 is developed and demonstrated. A thiourea (CH4N2S) solution is used as a precursor for the sulfurization and its doping-level control. By manipulating the sulfur concentration (x), we systematically examine the physical properties of sulfur-doped Pb(Zr,Ti)O3-xSx films. An enhancement in the tetragonality and ferroelectricity by sulfurization is observed with the band-gap reduction, which is consistent with our theoretical predictions. In the sulfurized films, the ferroelectric phonon modes become softened progressively, probably due to the substitution of apical oxygens with sulfur atoms. Our work is of practical interest for designing ferroelectric photovoltaic devices with high performance

Design of ITER divertor VUV spectrometer and prototype test at KSTAR tokamak

Design and development of the ITER divertor VUV spectrometer have been performed from the year 1998, and it is planned to be installed in the year 2027. Currently, the design of the ITER divertor VUV spectrometer is in the phase of detail design. It is optimized for monitoring of chord-integrated VUV signals from divertor plasmas, chosen to contain representative lines emission from the tungsten as the divertor material, and other impurities. Impurity emission from overall divertor plasmas is collimated through the relay optics onto the entrance slit of a VUV spectrometer with working wavelength range of 14.6–32 nm. To validate the design of the ITER divertor VUV spectrometer, two sets of VUV spectrometers have been developed and tested at KSTAR tokamak. One set of spectrometer without the field mirror employs a survey spectrometer with the wavelength ranging from 14.6 nm to 32 nm, and it provides the same optical specification as the spectrometer part of the ITER divertor VUV spectrometer system. The other spectrometer with the wavelength range of 5–25 nm consists of a commercial spectrometer with a concave grating, and the relay mirrors with the same geometry as the relay mirrors of the ITER divertor VUV spectrometer. From test of these prototypes, alignment method using backward laser illumination could be verified. To validate the feasibility of tungsten emission measurement, furthermore, the tungsten powder was injected in KSTAR plasmas, and the preliminary result could be obtained successfully with regard to the evaluation of photon throughpu

Design of ITER divertor VUV spectrometer and prototype test at KSTAR tokamak

Design and development of the ITER divertor VUV spectrometer have been performed from the year 1998, and it is planned to be installed in the year 2027. Currently, the design of the ITER divertor VUV spectrometer is in the phase of detail design. It is optimized for monitoring of chord-integrated VUV signals from divertor plasmas, chosen to contain representative lines emission from the tungsten as the divertor material, and other impurities. Impurity emission from overall divertor plasmas is collimated through the relay optics onto the entrance slit of a VUV spectrometer with working wavelength range of 14.6–32 nm. To validate the design of the ITER divertor VUV spectrometer, two sets of VUV spectrometers have been developed and tested at KSTAR tokamak. One set of spectrometer without the field mirror employs a survey spectrometer with the wavelength ranging from 14.6 nm to 32 nm, and it provides the same optical specification as the spectrometer part of the ITER divertor VUV spectrometer system. The other spectrometer with the wavelength range of 5–25 nm consists of a commercial spectrometer with a concave grating, and the relay mirrors with the same geometry as the relay mirrors of the ITER divertor VUV spectrometer. From test of these prototypes, alignment method using backward laser illumination could be verified. To validate the feasibility of tungsten emission measurement, furthermore, the tungsten powder was injected in KSTAR plasmas, and the preliminary result could be obtained successfully with regard to the evaluation of photon throughpu

Tailoring Crystallographic Orientations to Substantially Enhance Charge Separation Efficiency in Anisotropic BiVO4 Photoanodes

In photoelectrochemical (PEC) water splitting, BiVO4 is considered the most promising photoanode material among metal oxide semiconductors because of its relatively narrow optical bandgap and suitable band structure for water oxidation. Nevertheless, until now, the solar-to-hydrogen conversion efficiency of BiVO4 has shown significant limitations for commercialization because of its poor charge transport. Various strategies, including the formation of a heterojunction and doping of electron donors, have been implemented to enhance the charge transport efficiency; however, fundamental approaches are required for further enhancement. In this regard, we report the fundamental approach for BiVO4 thin film photoanodes by fabricating epitaxial oxide thin films with different crystallographic orientations for PEC water splitting. The crystalline anisotropy generally reveals distinct physical phenomena along different crystallographic orientations. In the same vein, in terms of the anisotropic properties of BiVO4, the electrical conductivity of BiVO4 is greater along the ab-plane than along the c-axis. Consequently, as the crystallographic orientation of the BiVO4 thin film changes from (001) to (010), the charge transport properties in the epitaxial BiVO4 thin film are significantly enhanced. Thus, at 1.23 V-RHE, the photocurrent density of the epitaxial BiVO4 (010) thin film (2.29 mA cm(-2)) is much higher than that of the epitaxial BiVO4 (001) thin film (0.74 mA cm(-2)) because of significant enhancement in charge transport properties even for undoped BiVO4. These results strongly suggest that the growth of epitaxial BiVO4 thin films with specific crystallographic orientations has great potential to considerably improve the charge transport efficiency of photoanodes for solar water splitting.112Nsciescopu

Enhanced Photocatalytic Performance Depending on Morphology of Bismuth Vanadate Thin Film Synthesized by Pulsed Laser Deposition

We have fabricated high quality bismuth vanadate (BiVO₄) polycrystalline thin films as photoanodes by pulsed laser deposition (PLD) without a postannealing process. The structure of the grown films is the photocatalytically active phase of scheelite-monoclinic BiVO₄ which was obtained by X-ray diffraction (XRD) analysis. The change of surface morphology for the BIVO₄ thin films depending on growth temperature during synthesis has been observed by scanning electron microscopy (SEM), and its influence on water splitting performance was investigated. The current density of the BiVO₄ film grown on a glass substrate covered with fluorine-doped tin oxide (FTO) at 230 °C was as high as 3.0 mA/cm² at 1.23 V versus the potential of the reversible hydrogen electrode (<i>V</i>_RHE) under AM 1.5G illumination, which is the highest value so far in previously reported BiVO₄ films grown by physical vapor deposition (PVD) methods. We expect that doping of transition metal or decoration of oxygen evolution catalyst (OEC) in our BiVO₄ film might further enhance the performance