• 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 the Microelectronics and Packaging Society
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• v.25 no.3
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• pp.1-5
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• 2018

In this study, the effects of indium (In) doping in InGaN/GaN multi quantum well (MQW) on photoelectrochemical (PEC) properties were investigated. Each quantum well (QW) layer with controlled In content were grown on sapphire substrate. Before growth of MQW, GaN growth consisted of various stages in the following order: buffer GaN growth, undoped GaN growth, and Si-doped n-type GaN growth. Absorbance of InGaN/GaN MQW having different In composition was higher than that of the InGaN/GaN MQW having a constant In composition. It indicates that InGaN layer having different In composition absorbs light having a broad spectrum energy. These results are in agreement with those in photoluminescence (PL). After evaluation of PEC properties, it demonstrated that InGaN/GaN MQW having different In composition was improved InGaN/GaN MQW having constant In composition in PEC water splitting ability.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.183-183
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• 2012

최근 환경오염과 천연자원의 고갈로 태양광을 이용한 수소와 산소를 제조하는 광전기화학적 물분해 반응이 많은 관심을 받고 있다. 본 연구에서는 란타늄 알루미네이트 단결정 기판 위에 니오븀을 도핑한 이산화 티타늄을 증착 시킨 후 two-step sol-gel법을 이용하여 아나타제 이산화티탄늄 나노막대를 성장시켰다. 성장시킨 아나타제 티타늄산화 막대는 구조적인 특징과 모양, 크기를 전구체 용액의 수소이온화지수(pH)를 조절함으로써 변화 시킬 수 있다. 니오븀을 도핑한 이산화 티타늄 기판 위에 높은 수소이온화지수(pH 10 이상)을 이용하여 우선 배향된 아나타제 나노 막대를 성장 시킬 수 있으며, 주사전자현고해상도 투과전자현미경, x선 회절 분석기를 통해 구조적 특성을 평가하였다. 또한 수소이온화지수를 조절(pH 9)하여 만든 다결정질 아나타제 나노구형과 우선배향된 나노막대의 전하이동특성을 분석하기 위하여 기체 색층분석법(GC), 광전기화학법(PEC), 임피던스를 측정하였다.

• 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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• 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.

• 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 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.

• 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.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2271-2275
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• 2013

We report on the photoelectrochemical properties of partially reduced mesoporous titania thin films. The fabrication is achieved by synthesizing mesoporous titania thin films through the self-assembly of a titania precursor and a block copolymer, followed by aging and calcination, and heat-treatment under a $H_2$ (1 torr) environment. Depending on the temperature used for the reaction with $H_2$, the degree of the reduction (generation of oxygen vacancies) of the titania is controlled. The oxygen vacancies induce visible light absorption, and decrease of resistance while the mesoporosity is practically unaltered. The photoelectrochemical activity data on these films, by measuring their photocurrent-potential behavior in 1 M NaOH electrolyte under AM 1.5G 100 mW $cm^{-2}$ illumination, show that the three effects of the oxygen vacancies contribute to the enhancement of the photoelectrochemical properties of the mesoporous titania thin films. The results show that these oxygen deficient $TiO_2$ mesoporous thin films hold great promise for a solar hydrogen generation. Suggestions for the materials design for improved photoelectrochemical properties are made.