• Electronic Materials Letters
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• v.14 no.6
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• pp.733-738
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• 2018

Undoped and Mn-doped $In_2O_3$ films were prepared by radiofrequency magnetron sputtering technique. The effects of Mn doping on the structural and optical properties of as-prepared films were investigated using X-ray diffraction, X-ray photoelectron spectroscopy and ultraviolet-visible spectroscopy. Mn doping can enhance the intensity of (222) peak in Mn-doped $In_2O_3$ thin film, indicating Mn dopant promotes preferred orientation of crystal growth along (222) plane. XPS analyses revealed that the doped Mn ions exist at + 2 oxidation states, substituting for the $In^{3+}$ sites in the $In_2O_3$ lattice. UV-Vis measurements show that the optical band gap $E_g$ decreases from 3.33 to 2.87 eV with Mn doping in $In_2O_3$, implying an increasing sp-d exchange interaction in the film. Our work demonstrates a practical means to manipulate the band gap energy of $In_2O_3$ thin film via Mn impurity doping, and significantly improves the photoelectrochemical activity.

• 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.

• Journal of the Korean institute of surface engineering
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• v.55 no.4
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• pp.215-221
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• 2022

In the present work, copper oxide thin films were formed by heat-treatment method with different temperatures and atmosphere, e.g., at 200 ~ 400 ℃; in air and Ar atmosphere. The morphological, electrical and optical properties of the thermally fabricated Cu oxide films were analyzed by SEM, XRD, and UV-VIS spectrometer. Thereafter, photoelectrochemical properties of the thermal copper oxide films were analyzed under solar light (AM 1.5, 100 mW/cm²). Conclusively, the highest photocurrent was obtained with Cu₂O formed under the optimum annealing condition at 300 ℃ in air atmosphere. In addition, EIS results of Cu oxide formed in air atmosphere showed relatively low resistance and long electron life-time compared with Cu Oxide fabricated in Ar atmosphere at the same temperature. This is because heat-treatment in Ar atmosphere could not form Cu₂O due to lack of oxygen, and thermally formed CuO at high temperature suppressed stability and conductivity of the Cu oxide.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.99-102
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• 2009

$TiO_2$ nanotube arraysdecorated with ${\alpha}-Fe_2O_3$ were prepared by forming a nanotube-like $TiO_2$ film on a Ti sheet using an anodization process, followed by electrochemical deposition treatment to decorate hematite (${\alpha}-Fe_2O_3$) nanoparticles on the $TiO_2$ nanotube arrays. The SEM and XRD results revealed that the ${\alpha}-Fe_2O_3$ nanoparticles were homogeneously embedded on the surface of the $TiO_2$ nanotube arrays. The activity of hydrogen production by photocatalytic water decomposition for the ${\alpha}-Fe_2O_3/TiO_2$ nanotube array composite was examined under visible light irradiation.

• Korean Journal of Materials Research
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• v.34 no.4
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• pp.202-207
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• 2024

In this study, we undertook detailed experiments to increase hydrogen production efficiency by optimizing the thickness of titanium dioxide (TiO₂) thin films. TiO₂ films were deposited on p-type silicon (Si) wafers using atomic layer deposition (ALD) technology. The main goal was to identify the optimal thickness of TiO₂ film that would maximize hydrogen production efficiency while maintaining stable operating conditions. The photoelectrochemical (PEC) properties of the TiO₂ films of different thicknesses were evaluated using open circuit potential (OCP) and linear sweep voltammetry (LSV) analysis. These techniques play a pivotal role in evaluating the electrochemical behavior and photoactivity of semiconductor materials in PEC systems. Our results showed photovoltage tended to improve with increasing thickness of TiO₂ deposition. However, this improvement was observed to plateau and eventually decline when the thickness exceeded 1.5 nm, showing a correlation between charge transfer efficiency and tunneling. On the other hand, LSV analysis showed bare Si had the greatest efficiency, and that the deposition of TiO₂ caused a positive change in the formation of photovoltage, but was not optimal. We show that oxide tunneling-capable TiO₂ film thicknesses of 1~2 nm have the potential to improve the efficiency of PEC hydrogen production systems. This study not only reveals the complex relationship between film thickness and PEC performance, but also enabled greater efficiency and set a benchmark for future research aimed at developing sustainable hydrogen production technologies.

• Journal of Electrochemical Science and Technology
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• v.2 no.4
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• pp.187-192
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• 2011

Photoelectrochemical performances of ZnO electrodes are enhanced by coupling with cobalt-based catalyst (CoPi) in phosphate electrolyte (pH 7). For this study, hexagonal pillar-shaped ZnO nanorods are grown on ZnO electrodes through a chemical bath deposition, onto which CoPi is deposited with different photodeposition times (10-30 min). A scanning electron microscopic study indicates that CoPi deposition does not induce any change of ZnO morphology and an energy-dispersive X-ray spectroscopic analysis shows that inorganic phosphate ions (Pi) exist on ZnO surface. Bare ZnO electrodes generate the current of ca. $0.36mA/cm^2$ at a bias potential of 0.5 V vs. SCE, whereas ZnO/CoPi (deposited for 10 min) has ca. 50%-enhanced current ($0.54mW/cm^2$) under irradiation of AM 1.5G-light ($400mW/cm^2$). The excess loading of CoPi on ZnO results in decrease of photocurrents as compared to bare ZnO likely due to limited electrolyte access to ZnO and/or CoPi-mediated recombination of photogenerated charge carriers. The primary role of CoPi is speculated to trap the photogenerated holes and thereby oxidize water into molecular oxygen via an intervalency cycle among Co(II), Co(III), and Co(IV).

• 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.

• Applied Chemistry for Engineering
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• v.26 no.3
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• pp.306-310
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• 2015

In this research, hematite nanoparticles were synthesized by DC thermal plasma process to increase the overall surface area. The effect of binders on hematite electrodes was investigated by changing the type and composition of binders when preparing electrodes. Nitrogen gas was also added to the DC thermal plasma process in order to dope the hematite with N for enhancing photoelectrochemical properties of hematite nanoparticles. The efficiency of water splitting reaction was measured by linear sweep voltammetry (LSV) under solar simulator. In LSV measurements, the onset potential and maximum current density at a fixed voltage were measured. The durability of electrodes was checked by repeating LSV measurements. CMC (carboxymethyl cellulose) binder with 50 : 1 composition exhibits the highest current density of $12mA/cm^2$ and CMC binder with 20 : 1 composition, showing the initial current density of $3mA/cm^2$, endures 20 times of repetitive LSV measurements. Effects of nitrogen doping on hematite nanoparticles were proven to be insignificant.

• Journal of Electrochemical Science and Technology
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• v.9 no.4
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• pp.282-291
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• 2018

The pristine fluorine-doped $SnO_2$ (abbreviated as FTO) inverse opal (IO) was developed using a 410 nm polystyrene bead template. The nanolayered copper tungsten oxide ($CuWO_4$) was decorated on the FTO IO film using a facile electrochemical deposition, subsequently followed by annealing at $500^{\circ}C$ for 90 min. The morphologies, crystalline structure, optical properties and photoelectrochemical characteristics of the FTO and $CuWO_4$-decorated FTO (briefly denoted as $FTO/CuWO_4$) IO film were investigated by field emission scanning electron microscopy, X-ray diffraction, UV-vis spectroscopy and electrochemical impedance spectroscopy, showing FTO IO in the hexagonally closed-pack arrangement with a pore diameter and wall thickness of about 300 nm and 20 nm, respectively. Above this film, the $CuWO_4$ was electrodeposited by controlling the cycling number in cyclic voltammetry, suggesting that the $CuWO_4$ formed during 4 cycles (abbreviated as $CuWO_4$(4 cycles)) on FTO IO film exhibited partial distribution of $CuWO_4$ nanoparticles. Additional distribution of $CuWO_4$ nanoparticles was observed in the case of $FTO/CuWO_4$(8 cycles) IO film. The $CuWO_4$ layer exhibits triclinic structure with an indirect band gap of approximately 2.5 eV and shows the enhanced visible light absorption. The photoelectrochemical (PEC) behavior was evaluated in the 0.5 M $Na_2SO_4$ solution under solar illumination, suggesting that the $FTO/CuWO_4$(4 cycles) IO films exhibit a photocurrent density ($J_{sc}$) of $0.42mA/cm^2$ at 1.23 V vs. reversible hydrogen electrode (RHE, denoted as $V_{RHE}$), while the FTO IO and $FTO/CuWO_4$(8 cycles) IO films exhibited a $J_{sc}$ of 0.14 and $0.24mA/cm^2$ at $1.23V_{RHE}$, respectively. This difference can be explained by the increased visible light absorption by the $CuWO_4$ layer and the favorable charge separation/transfer event in the cascading band alignment between FTO and $CuWO_4$ layer, enhancing the overall PEC performance.

• Transactions of the Korean hydrogen and new energy society
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• v.34 no.5
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• pp.413-420
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• 2023

Holmium-doped TiO₂ nanotubes (Ho-TNTs) were manufactured through anodization treatment and electrochemical deposition, and optimization experiments were conducted using various Holmium doping concentrations and time as variables. Surface as well as electrochemical characteristics were analyzed to study the prepared photocatalysts. Ho-TNTs were found to exist only in anatase phase through X-ray diffraction analysis. Ho-TNTs with 0.01 wt% 100 seconds shows a photocurrent density of 3.788 mA/cm² and an effective photo-conversion efficiency (PCE) of 4.30%, which is more efficient than pure TiO₂ nanotubes (pure-TNTs) (at bias potential 1.5 V vs. Hg/HgO). The photocatalytic activity of the aforementioned Ho-TNTs for hydrogen production was evaluated with the result of -29.20 µmol/h·cm².