• Journal of the Microelectronics and Packaging Society
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• v.23 no.4
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• pp.113-117
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• 2016

Recently, hydrogen is regarded as important energy in the future, because it is clean and renewable. The photoelectrochemical (PEC) system, which produce hydrogen using water splitting by solar energy, is one of the most promising energy systems because it has abundant energy sources and good theoretical efficiency. GaN has recently been regarded as suitable photoelectrode that could be used to split water to generate hydrogen without extra bias because its band edge position include water redox potential ($V_{redox}=1.23$ vs. SHE). GaN also shows considerable corrosion resistance in aqueous solutions and it is possible to control its properties, such as structure, band gap, and catalyst characteristics, in order to improve solar energy conversion efficiency. But, even if the band edge position of GaN make PEC reaction facilitate without bias, the overpotential of oxygen evolution reaction could reduce the efficiency of system. One of the ways to decrease overpotential is introduction of co-catalyst on photoelectrode. In this paper, we will investigate the effect of manganese dioxide ($MnO_2$) as a co-catalyst. $MnO_2$ particles were dispersed on GaN photoelectrode by spincoater and analyzed properties of the PEC system using potentiostat (PARSTAT4000). After coating $MnO_2$, the flat-band potential ($V_{fb}$) and the onset voltage ($V_{onset}$) were moved negatively by 0.195 V and 0.116 V, respectively. The photocurrent density increased on $MnO_2$ coated sample and time dependence was also improved. These results showed $MnO_2$ has an effect as a co-catalyst and it would enhance the efficiency of overall PEC system.

• Korean Journal of Materials Research
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• v.27 no.11
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• pp.631-635
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• 2017

We report facile solution processing of mesoporous hematite (${\alpha}-Fe_2O_3$) thin films for high efficiency solar-driven water splitting. $Fe_2O_3$ thin films were prepared on fluorine doped tin oxide(FTO) conducting substrates by spin coating of a precursor solution followed by annealing at $550^{\circ}C$ for 30 min. in air ambient. Specifically, the precursor solution was prepared by dissolving non-toxic $FeCl_3$ as an Fe source in highly versatile dimethyl sulfoxide(DMSO) as a solvent. The as-deposited and annealed thin films were characterized for their morphological, structural and optical properties using field-emission scanning electron microscopy(FE-SEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and UV-Vis absorption spectroscopy. The photoelectrochemical performance of the precursor (${\alpha}-FeOOH$) and annealed (${\alpha}-Fe_2O_3$) films were characterized and it was found that the ${\alpha}-Fe_2O_3$ film exhibited an increased photocurrent density of ${\sim}0.78mA/cm^2$ at 1.23 V vs. RHE, which is about 3.4 times higher than that of the ${\alpha}-FeOOH$ films ($0.23mA/cm^2$ at 1.23 V vs. RHE). The improved performance can be attributed to the improved crystallinity and porosity of ${\alpha}-Fe_2O_3$ thin films after annealing treatment at higher temperatures. Detailed electrical characterization was further carried out to elucidate the enhanced PEC performance of ${\alpha}-Fe_2O_3$ thin films.

• Prospectives of Industrial Chemistry
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• v.24 no.1
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• pp.14-24
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• 2021

최근 전 세계적으로 이산화탄소를 포함한 대기 오염원의 배출을 줄이고 화석연료를 대체할 수 있는 차세대 청정에너지원으로 '수소'를 주목하고 있다. 하지만 현재까지 사회에 유통되는 대부분의 수소는 화석연료 개질을 기반으로 생산되기 때문에 2차 환경오염의 위험을 가지고 있다. 이에 이산화탄소 배출이 없이 태양에너지로부터 물을 분해해 수소를 생산하는 광전기화학 수소 생산 기술이 주목받고 있다. 단 광전기화학 물분해 수소생산을 실현하기 위해서는 수소를 충분히 생산시킬 수 있는 충분한 전류밀도, 과전압을 최소화하는 높은 개시전위, 및 그 생산비용을 최소화 할 수 있는 저렴한 공정 등을 동시에 만족시킬 수 있는 광전극 소재 개발이 필요하다. 최근 광소자용 소재로 각광을 받는 유기금속 할라이드 페로브스카이트 소재가 상기의 조건들을 상당히 만족할 것으로 기대되고 있어 광전기화학 물분해 셀로 적용되는 연구들이 수행되고 있다. 본 기고문에서는 유기금속 할라이드 페로브스카이트 소재기반 광전기화학 물분해 관련 최신 연구동향과 전망을 다루고자 한다.

• Proceedings of the Materials Research Society of Korea Conference
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• 2010.05a
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• pp.3.1-3.1
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• 2010

Water splitting reaction using photocatalysts is of great interest in the utilization of solar energy [1]. In the present work, visible light-responsive $TiO_2$ thin films (Vis-$TiO_2$) were prepared by a radio frequency magnetron sputtering (RF-MS) deposition method and applied for the separate evolution of $H_2$ and $O_2$ from water as well as the photofuel cell. Special attentions will be focused on the effect of HF treatment of Vis-$TiO_2$ thin films on their photocatalytic activities. Vis-$TiO_2$ thin films were prepared by an RF-MS method using a calcined $TiO_2$ plate and Ar as the sputtering gas. The Vis-$TiO_2$ thin films were then deposited on the Ti foil substrate with the substrate temperature at 873 K (Vis-$TiO_2$/Ti). Vis-$TiO_2$/Ti thin films were immersed in a 0.045 vol% HF solution at room temperature. The effect of HF treatments on the activity of Vis-$TiO_2$/Ti thin films for the photocatalytic water splitting reaction have been investigated. Vis-$TiO_2$/Ti thin films treated with HF solution (HF-Vis-$TiO_2$/Ti) exhibited remarkable enhancement in the photocatalytic activity for $H_2$ evolution from a methanol aqueous solution as well as in the photoelectrochemical performance under visible light irradiation as compared with the untreated Vis-$TiO_2$/Ti thin films. Moreover, Pt-loaded HF-Vis-$TiO_2$/Ti thin films act as efficient and stable photocatalysts for the separate evolution of $H_2$ and $O_2$ from water under visible light irradiation in the presence of chemical bias. Thus, HF treatment was found to be an effective way to improve the photocatalytic activity of Vis-$TiO_2$/Ti thin films. Furthermore, unique separate type photofuel cell was fabricated using a Vis-$TiO_2$ thin film as an electrode, which can generate electrical power under solar light irradiation by using various kinds of biomass derivatives as fuel. It was found that the introduction of an iodine ($I^-/{I_3}^-$) redox solution at the cathode side enables the development of a highly efficient photofuel cell which can utilize a cost-efficient carbon electrode as an alternative to the Pt cathode.

• 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.

• 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 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.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.3
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• pp.244-249
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• 2007

The present work considers the concept of enzymatic photoelectrochemical generation of hydrogen through water splitting using a Xe lamp as a source of light. A solar cell was applied to the system in order to shift the level of electrochemical energy of the system, resulting in the rate of hydrogen production at $43\;{\mu}mol/(cm^2{\times}hr)$ in cathodic compartment with an anodized tubular $TiO_2$ electrode(ATTE, $5^{\circ}C$/1hr in 0.5 wt% HF-$650^{\circ}C$/5hr). The trend of the rate of hydrogen production, for the ATTEs with different annealing temperature from $350^{\circ}C$ to $850^{\circ}C$, fairly well coincided with the photoelectrical properties measured by potentiostat. The actual chemical bias through imposition of two electrolytes of different pHs between anode(13.68) and cathode(7.5) was 0.24eV.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.99.2-99.2
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• 2011

Transparent conducting oxides (TCOs) supported on glass are widely used as substrates in PEC studies for photovoltaic hydrogen generation applications However, high sheet resistane ($10{\sim}15{\Omega}/cm^2$) and fragileness of glass-supported TCO substrates are the obstacles to produce the large area PEC cells. Such internal sheet resistance is detrimental to efficient collection of photogenerated majority charge carriers at the photoactive material and electrolyte interface. Moreover, these TCO substrates are very expensive and consume about 40~60% cost of the devices. Hence, a low sheet resistance of the substrate is a key point in improving the performance of PEC devices. Metallic substrates coated with a photoactive material would be a good choice for efficient charge collection. Such metal substrates based photanodes are best candidate for large-scale phtoelectrochemical water splitting for hydrogen generation. In this study, we report the enhanced PEC performance of $WO_3$ film on metal(chemical etched, bare) substrate. It is proposed that interface between $WO_3$ and the metal substrate is responsible for efficient charge transfer and demonstrated significant improvement in the photoelectrochmical performance. X-ray diffration and FESEM suduies reveled that $WO_3$ films are monoclinic, porous, polycrystalline with average grain size of ~50nm. Photocurrent of $WO_3$ prepared on metal substrates was measured in 0.5M $H_2SO_4$ electroyte under simulated $100mW/cm^2$ illumination.