• Journal of Electrochemical Science and Technology
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• v.13 no.4
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• pp.504-504
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• 2022

• Journal of Surface Science and Engineering
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• v.55 no.2
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• pp.63-69
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• 2022

Preparing various types of thin films of oxide semiconductors is a promising approach to fabricate efficient photoanodes and photocathodes for hydrogen production via photoelectrochemical (PEC) water splitting. In this work, we investigate the feasibility of an efficient photocathode for PEC water reduction of a p-type oxide semiconductor cupric oxide (CuO) thin film prepared via a facile method combined with sputtering Cu metallic film on fluorine-doped thin oxide (FTO) coated glass substrate and subsequent thermal oxidation of the sputtered Cu metallic film in dry air. Characterization of the structural, optical, and PEC properties of the CuO thin film prepared at various Cu sputtering powers reveals that we can obtain an optimum CuO thin film as an efficient PEC photocathode at a Cu sputtering power of 60 W. The photocurrent density and the optimal photocurrent conversion efficiency for the optimum CuO thin film photocathode are found to be -0.3 mA/cm² and 0.09% at 0.35 V vs. RHE, respectively. These results provide a promising route to fabricating earth-abundant copper-oxide-based photoelectrode for sunlight-driven hydrogen generation using a facile method.

• Korean Journal of Materials Research
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• v.26 no.11
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• pp.604-610
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• 2016

We report on the fabrication and characterization of a novel $Cu_2O/CuO$ heterojunction structure with CuO nanorods embedded in $Cu_2O$ thin film as an efficient photocathode for photoelectrochemical (PEC) solar water splitting. A CuO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method; then, a $Cu_2O$ thin film was electrodeposited onto the CuO nanorod array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy, as well as Raman scattering. The PEC properties of the fabricated $Cu_2O/CuO$ heterojunction photocathode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the $Cu_2O/CuO$ photocathode was found to exhibit negligible dark current and high photocurrent density, e.g. $-1.05mA/cm^2$ at -0.6 V vs. $Hg/HgCl_2$ in $1mM\;Na_2SO_4$ electrolyte, revealing the effective operation of the oxide heterostructure. The photocurrent conversion efficiency of the $Cu_2O/CuO$ photocathode was estimated to be 1.27% at -0.6 V vs. $Hg/HgCl_2$. Moreover, the PEC current density versus time (J-T) profile measured at -0.5 V vs. $Hg/HgCl_2$ on the $Cu_2O/CuO$ photocathode indicated a 3-fold increase in the photocurrent density compared to that of a simple $Cu_2O$ thin film photocathode. The improved PEC performance was attributed to a certain synergistic effect of the bilayer heterostructure on the light absorption and electron-hole recombination processes.

• Journal of Hydrogen and New Energy
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• v.16 no.2
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• pp.130-135
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• 2005

Cadmium selenide is one of the group IIb-VI compounds, which is the promising semiconductor material due to its wide range of technological applications in optoelectronic devices such as photoelectrochemical cells, solid state solar cells, thin film photoconductors etc. CdSe has optical band gap of 1.7-1.8eV and proper conduction band edge for water splitting. CdSe films are coated with small thickness(20-50nm) nanocrystalline $TiO_2$ film by electrodeposition or chemical bath deposition methods and PEC properties of CdSe and CdSe/$TiO_2$ sandwich structure are studied. The photoactivity of CdSe and CdSe/$TiO_2$ films deposited on titanium substrate is studied in aqueous electrolyte of 1M NaOH solution. Photocurrent and photovoltage obtained were of the order of 2-4 mA/$cm^2$ and 0.5V, respectively, under the intensity of illumination of 100 mW/$cm^2$.

• Journal of the Microelectronics and Packaging Society
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• v.27 no.2
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• pp.33-38
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• 2020

In the photoelectrochemical (PEC) water splitting, GaN is one of the most promising photoanode materials due to high stability in electrolytes and adjustable energy band position. However, the application of GaN is limited because of low efficiency. To improve solar to hydrogen conversion efficiency, we introduce a Cobalt Phosphate (Co-pi) catalyst by photo-electrodeposition. The Co-pi deposition GaN were characterized by SEM, EDS, and XPS, respectively, which illustrated that Co-pi was successfully decorated on the surface of GaN. PEC measurement showed that photocurrent density of GaN was 0.5 mA/㎠ and that of Co-pi deposited GaN was 0.75 mA/㎠. Impedance and Mott-Schottky measurements were performed, and as a result of the measurement, polarization resistance (R_p) and increased donor concentration (N_D) values decreased from 50.35 Ω to 34.16 Ω were confirmed. As a result of analyzing the surface components before and after the water decomposition, it was confirmed that the Co-pi catalyst is stable because Co-pi remains even after the water decomposition. Through this, it was confirmed that Co-pi is effective as a catalyst for improving GaN efficiency, and when applied as a catalyst to other photoelectrodes, it is considered that the efficiency of the PEC system can be improved.

• Electronic Materials Letters
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• v.18
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• pp.391-399
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• 2022

Photoelectrochemical (PEC) water splitting is one of the critical energy conversion techniques to prepare for future energy demands. Among the various trials to construct effective water splitting semiconductor photoelectrodes, In₂O₃/In₂S₃ heterostructures can be promising candidates for their advantageous properties in solar water oxidation. Herein, we synthesized In₂O₃ nanorods on FTO substrate through a direct glancing angle deposition method. Subsequently, the In₂S₃ layer was conformally coated on In₂O₃ nanorods through facile chemical bath deposition. As synthesized photoanodes of In₂O₃/In₂S₃ form type II junction, leading to considerable cathodic onset potential shift with the increased photocurrent density compared to pristine samples. To further enhance PEC properties, the interficial engineering strategies of the Co ion doping and the deposition of ultra-thin Al₂O₃ film were carried out. Co ion could facilitate the charge transfer in photoanodes through the increased surface area, and the 2 nm Al₂O₃ layer coated above the photoanode effectively worked as the passivation layer to stabilize the photoanodes in alkaline electrolytes environments. This work would contribute to developing efficient photoanodes through various nanoscale engineering strategies.

• Journal of Surface Science and Engineering
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• v.52 no.5
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• pp.258-264
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• 2019

Assembling heterostructures by combining dissimilar oxide semiconductors is a promising approach to enhance charge separation and transfer in photoelectrochemical (PEC) water splitting. In this work, the CuO nanorods array/$Cu_2O$ thin film bilayered heterostructure was successfully fabricated by a facile method that involved a direct electrodeposition of the $Cu_2O$ thin film onto the vertically oriented CuO nanorods array to serve as the photoelectrode for the PEC water oxidation. The resulting copper-oxide-based heterostructure photoelectrode exhibited an enhanced PEC performance compared to common copper-oxide-based photoelectrodes, indicating good charge separation and transfer efficiency due to the band structure realignment at the interface. The photocurrent density and the optimal photocurrent conversion efficiency obtained on the CuO nanorods/$Cu_2O$ thin film heterostructure were $0.59mA/cm^2$ and 1.10% at 1.06 V vs. RHE, respectively. These results provide a promising route to fabricating earth-abundant copper-oxide-based photoelectrode for visible-light-driven hydrogen generation using a facile, low-cost, and scalable approach of combining electrodeposition and hydrothermal synthesis.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2067-2072
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• 2013

Hydrogen ($H_2$) treatment using a two-step $TiO_2$ nanotube (TONT) film was performed under various annealing temperatures from $350^{\circ}C$ to $550^{\circ}C$ and significantly influenced the extent of hydrogen treatment in the film. Compared with pure TONT films, the hydrogen-treated TONT (H:TONT) film showed substantial improvement of material features from structural, optical and electronic aspects. In particular, the extent of enhancement was remarkable with increasing annealing temperature. Light absorption by the H:TONT film extended toward the visible region, which was attributable to the formation of sub-band-gap states between the conduction and valence bands, resulting from oxygen vacancies due to the $H_2$ treatment. This increased donor concentration about 1.5 times higher and improved electrical conductivity of the TONT films. Based on these analyses and results, photoelectrochemical (PEC) performance was evaluated and showed that the H:TONT film prepared at $550^{\circ}C$ exhibited optimal PEC performance. Approximately twice higher photocurrent density of 0.967 $mA/cm^2$ at 0.32 V vs. NHE was achieved for the H:TONT film ($550^{\circ}C$) versus 0.43 $mA/cm^2$ for the pure TONT film. Moreover, the solar-to-hydrogen efficiency (STH, ${\eta}$) of the H:TONT film was 0.95%, whereas a 0.52% STH efficiency was acquired for the TONT film. These results demonstrate that hydrogen treatment of TONT film is a simple and effective tool to enhance PEC performance with modifying the properties of the original material.

• Korean Journal of Materials Research
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• v.31 no.2
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• pp.92-96
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• 2021

We report the growth and enhanced photoelectrochemcial (PEC) water-splitting reactivity of few-layer MoS2 nanosheets on TiO2 nanowires. TiO2 nanowires with lengths of ~1.5 ~ 2.0 ㎛ and widths of ~50~300 nm are synthesized on fluorine-doped tin oxide substrates at 180 ℃ using hydrothermal methods with Ti(C4H9O)4. Few-layer MoS2 nanosheets with heights of ~250 ~ 300 nm are vertically grown on TiO2 nanowires at a moderate growth temperature of 300 ℃ using metalorganic chemical vapor deposition. The MoS2 nanosheets on TiO2 nanowires exhibit typical Raman and ultraviolet-visible light absorption spectra corresponding to few-layer thick MoS2. The PEC performance of the MoS2 nanosheet/TiO2 nanowire heterostructure is superior to that of bare TiO2 nanowires. MoS2/TiO2 heterostructure shows three times higher photocurrent than that of bare TiO2 nanowires at 0.6 V. The enhanced PEC photocurrent is attributed to improved light absorption of MoS2 nanosheets and efficient charge separation through the heterojunction. The photoelectrode of the MoS2/TiO2 heterostructure is stably sustained during on-off switching PEC cycle.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2015.05a
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• pp.101-101
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• 2015

Photoelectrochemical water splitting is considered as a promising method of transforming solar energy into chemical energy stored in the type of hydrogen. An n-type $WO_3$ semiconductor is one of the most promising photoanodes for hydrogen production from water splitting. Films annealed at lower temperatures consisted of amorphous, whereas films annealed above $500^{\circ}C$ comprised solely of monoclinic $WO_3$. In this study, we observed photoactivity of $WO_3$ as increasing thickness of $WO_3$. And it shows good photoacivity as thickness increases. Also we tried to improve photoactivity through surface modification and bulk modification by using hydrogen treatment and conducting polymer. The photocurrent was measured in potentiostatic method with the three electrode system. A Pt wire and Ag / AgCl electrode were used as the counter electrode and the reference electrode, respectively. photocurrent-time (I-T) curve was measured at a bias potential of 0.79 V.