• Journal of Electrochemical Science and Technology
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• v.14 no.4
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• pp.388-396
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• 2023

Photoelectrochemical (PEC) water splitting is a vital source of clean and sustainable hydrogen energy. Moreover, the large-scale H₂ production is currently necessary, while long-term stability and high PEC activity still remain important issues. In this study, a GaN-based photoelectrode was modified by an additional NH₃ treatment (900℃ for 10 min) and its PEC behavior was monitored. The bare GaN exhibited a highly crystalline wurtzite structure with the (002) plane and the optical bandgap was approximately 3.2 eV. In comparison, the NH₃-treated GaN film exhibited slightly reduced crystallinity and a small improvement in light absorption, resulting from the lattice stress or cracks induced by the excessive N supply. The minor surface nanotexturing created more surface area, providing electroactive reacting sites. From the surface XPS analysis, the formation of an N-Ga-O phase on the surface region of the GaN film was confirmed, which suppressed the charge recombination process and the positive shift of E_FB. Therefore, these effects boosted the PEC activity of the NH₃-treated GaN film, with J values of approximately 0.35 and 0.78 mA·cm^-2 at 0.0 and 1.23 V_RHE, respectively, and an onset potential (V_on) of -0.24 V_RHE. In addition, there was an approximate 50% improvement in the J value within the highly applied potential region with a positive shift of V_on. This result could be explained by the increased nanotexturing on the surface structure, the newly formed defect/trap states correlated to the positive V_on shift, and the formation of a GaO_xN_1-x phase, which partially blocked the charge recombination reaction.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.87-87
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• 2010

Photoelectrochemical (PEC) systems are promising methods of producing H2 gas using solar energy in an aqueous solution. The photoelectrochemical properties of numerous metal oxides have been studied. Among them, the PEC systems based on TiO2 have been extensively studied. However, the drawback of a PEC system with TiO2 is that only ultraviolet (UV) light can be absorbed because of its large band gap (3.2 - 3.4 eV). Two approaches have been introduced in order to use PEC cells in the visible light region. The first method includes doping impurities, such as nitrogen, into TiO2, and this technique has been extensively studied in an attempt to narrow the band gap. In comparison, research on the second method, which includes visible light water splitting in molecular photosystems, has been slow. Mallouk et al. recently developed electrochemical water-splitting cells using the Ru(II) complex as the visible light photosensitizer. the dye-sensitized PEC cell consisted of a dye-sensitized TiO2 layer, a Pt counter electrode, and an aqueous solution between them. Under a visible light (< 3 eV) illumination, only the dye molecule absorbed the light and became excited because TiO2 had the wide band gap. The light absorption of the dye was followed by the transfer of an electron from the excited state (S*) of the dye to the conduction band (CB) of TiO2 and its subsequent transfer to the transparent conducting oxide (TCO). The electrons moved through the wire to the Pt, where the water reduction (or H2 evolution) occurred. The oxidized dye molecules caused the water oxidation because their HOMO level was below the H2O/O2 level. Organic dyes have been developed as metal-free alternatives to the Ru(II) complexes because of their tunable optical and electronic properties and low-cost manufacturing. Recently, organic dye molecules containing multi-branched, multi-anchoring groups have received a great deal of interest. In this work, tri-branched tri-anchoring organic dyes (Dye 2) were designed and applied to visible light water-splitting cells based on dye-sensitized TiO2 electrodes. Dye 2 had a molecular structure containing one donor (D) and three acceptor (A) groups, and each ended with an anchoring functionality. In comparison, mono-anchoring dyes (Dye 1) were also synthesized. The PEC response of the Dye 2-sensitized TiO2 film was much better than the Dye 1-sensitized or unsensitized TiO2 films.

• Journal of the Microelectronics and Packaging Society
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• v.28 no.1
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• pp.13-20
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• 2021

GaN has shown good potential owing to its better chemical stability than other materials and tunable bandgap with materials such as InN and AlN. Tunable bandgap allows GaN to make the maximum utilization of the solar spectrum, thus improves the solar-to-hydrogen (STH) efficiency. In addition, GaN band gap contains the oxidation and reduction level of water, so it can split water without external voltage. However, STH efficiency using GaN itself is low and has been actively studied recently to improve it. In this thesis, we have summarized the studies related to the use of GaN as a photoelectrode for photoelectrochemical water splitting.

• Journal of the Korean Ceramic Society
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• v.53 no.4
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• pp.400-405
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• 2016

Ferric oxide (${\alpha}-Fe_2O_3$, hematite) is an n-type semiconductor; due to its narrow band gap ($E_g=2.1eV$), it is a highly attractive and desirable material for use in solar hydrogenation by water oxidation. However, the actual conversion efficiency achieved with $Fe_2O_3$ is considerably lower than the theoretical values because the considerably short diffusion length (2-4 nm) of holes in $Fe_2O_3$ induces excessive charge recombination and low absorption. This is a significant hurdle that must be overcome in order to obtain high solar-to-hydrogen conversion efficiency. In consideration of this, it is thought that elemental doping, which may make it possible to enhance the charge transfer at the interface, will have a marked effect in terms of improving the photoactivities of ${\alpha}-Fe_2O_3$ photoanodes. Herein, we report on the synthesis by pulsed electrodeposition of ${\alpha}-Fe_2O_3$-based anodes; we also report on the resulting photoelectrochemical (PEC) properties. We attempted Ti-doping to enhance the PEC properties of ${\alpha}-Fe_2O_3$ anodes. It is revealed that the photocurrent density of a bare ${\alpha}-Fe_2O_3$ anode can be dramatically changed by controlling the condition of the electrodeposition and the concentration of $TiCl_3$. Under optimum conditions, a modified ${\alpha}-Fe_2O_3$ anode exhibits a maximum photocurrent density of $0.4mA/cm^2$ at 1.23 V vs. reversible hydrogen electrode (RHE) under 1.5 G simulated sunlight illumination; this photocurrent density value is about 3 times greater than that of unmodified ${\alpha}-Fe_2O_3$ anodes.

• Journal of the Korean Electrochemical Society
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• v.23 no.2
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• pp.25-38
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• 2020

Photoelectrochemical water splitting has been considered as the most promising technology for generating hydrogen energy. Transition metal dichalcogenide (TMD) compounds have currently attracted tremendous attention due to their outstanding ability towards the catalytic water-splitting hydrogen evolution reaction (HER). Herein, we report the synthesis method of various transition metal dichalcogenide including MoS₂, MoSe₂, WS₂, and WSe₂ nanosheets as excellent catalysts for solar-driven photoelectrochemical (PEC) hydrogen evolution. Photocathodes were fabricated by growing the nanosheets directly onto Si nanowire (NW) arrays, with a thickness of 20 nm. The metal ion layers were formed by soaking the metal chloride ethanol solution and subsequent sulfurization or selenization produced the transition metal chalcogenide. They all exhibit excellent PEC performance in 0.5 M H₂SO₄; the photocurrent reaches to 20 mA cm^-2 (at 0 V vs. RHE) and the onset potential is 0.2 V under AM1.5 condition. The quantum efficiency of hydrogen generation is avg. 90%. The stability of MoS₂ and MoSe₂ is 90% for 3h, which is higher than that (80%) of WS₂ and WSe₂. Detailed structure analysis using X-ray photoelectron spectroscopy for before/after HER reveals that the Si-WS₂ and Si-WSe₂ experience more oxidation of Si NWs than Si-MoS₂ and Si-MoSe₂. This can be explained by the less protection of Si NW surface by their flake shape morphology. The high catalytic activity of TMDs should be the main cause of this enhanced PEC performance, promising efficient water-splitting Si-based PEC cells.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.157.1-157.1
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• 2016

In this work, we experimentally investigated the solar absorption performance of Cu-based scalable nanostructured surfaces and compared their performance with the conventional TiNOX. We fabricated Cu-based nanostructured surfaces with a controlled chemical oxidation process applicable to a large area or complex geometry. We optimized the process parameters including the chemical compounds, dipping time and process temperature. We conducted both lab-scale and outdoor experiments to characterize the conversion efficiency of each absorber surfaces with single and double glazing setup. Lab-scale experiment was conducted with $50mm{\times}50mm$ absorber sample with 1-sun condition (1kW/m2) using a solar simulator (PEC-L01) with measuring the temperature at the absorber plate, cover glass, air gap and ambient. From the lab-scale experiment, we obtained ${\sim}91^{\circ}C$ and $94^{\circ}C$ for CuO and TiNOX surfaces after 1 hr of solar illumination at single glazing, respectively. To measure the absorber performance at actual operating condition, outdoor experiment was also conducted using $110mm{\times}110mm$ absorber sample. We measured the solar flux with thermopile detector (919P-040-50). From outdoor experiment, we observed ${\sim}123^{\circ}C$ and $131^{\circ}C$ for CuO and TiNOX with 0.6 kW/m2 insolation at double glazing, respectively. We showed that the suggested nanostructured CuO solar absorber has near-equivalent collection efficiency compared with the state-of-the-art TiNOX surfaces even with much simpler manufacturing process that does not require an expensive equipment.

• Journal of Electrochemical Science and Technology
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• v.10 no.4
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• pp.424-432
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• 2019

Planar BiVO₄ and 3 wt% Mo-doped BiVO₄ (abbreviated as Mo:BiVO₄) film were prepared by the facile spin-coating method on fluorine doped SnO₂(FTO) substrate in the same precursor solution including the Mo precursor in Mo:BiVO₄ film. After annealing at a high temperature of 450℃ for 30 min to improve crystallinity, the films exhibited the monoclinic crystalline phase and nanoporous architecture. Both films showed no remarkably discrepancy in crystalline or morphological properties. To investigate the effect of surface passivation exploring the Al₂O₃ layer, the ultra-thin Al₂O₃ layer with a thickness of approximately 2 nm was deposited on BiVO₄ film using the atomic layer deposition (ALD) method. No distinct morphological modification was observed for all prepared BiVO₄ and Mo:BiVO₄ films. Only slightly reduced nanopores were observed. Although both samples showed some reduction of light absorption in the visible wavelength after coating of Al₂O₃ layer, the Al₂O₃ coated BiVO₄ (Al₂O₃/BiVO₄) film exhibited enhanced photoelectrochemical performance in 0.5 M Na₂SO₄ solution (pH 6.5), having higher photocurrent density (0.91 mA/㎠ at 1.23 V vs. reversible hydrogen electrode (RHE), briefly abbreviated as V_RHE) than BiVO₄ film (0.12 mA/㎠ at 1.23 V_RHE). Moreover, Al₂O₃ coating on the Mo:BiVO₄ film exhibited more enhanced photocurrent density (1.5 mA/㎠ at 1.23 V_RHE) than the Mo:BiVO₄ film (0.86 mA/㎠ at 1.23 V_RHE). To examine the reasons, capacitance measurement and Mott-Schottky analysis were conducted, revealing that the significant degradation of capacitance value was observed in both BiVO₄ film and Al₂O₃/Mo:BiVO₄ film, probably due to degraded capacitance by surface passivation. Furthermore, the flat-band potential (V_FB) was negatively shifted to about 200 mV while the electronic conductivities were enhanced by Al₂O₃ coating in both samples, contributing to the advancement of PEC performance by ultra-thin Al₂O₃ layer.