• Journal of Electrochemical Science and Technology
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• v.7 no.1
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• pp.1-12
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• 2016

The production of oxygen and hydrogen from solar water splitting has been considered to be an ultimate solution for energy and environmental issues, and over the past few years, nano-sized semiconducting metal oxides alone and with graphene have been shown to have great promise for use in photocatalytic water splitting. It is challenging to find ideal materials for photoelectrochemical water splitting, and these have limited commercial applicability due to critical factors, including their physico-chemical properties, the rate of charge-carrier recombination and limited light absorption. This review article discusses these main features, and recent research progress and major factors affect the performance of the water splitting reaction. The mechanism behind these interactions in transition metal oxides and graphene based nano-structured semiconductors upon illumination has been discussed in detail, and such characteristics are relevant to the design of materials with a superior photocatalytic response towards UV and visible light.

• Journal of the Korean Ceramic Society
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• v.32 no.11
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• pp.1262-1268
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• 1995

Photoelectrochemical properties of p-GaAs electrode have been investigated. I-V characteristic shows that the cathodic photocurrent is observed at -0.7 V vs. SCE. The photoresponse at near 870~880nm wavelength indicates that the photogenerated carriers contibuted to the observed current. The maximum converson efficiency of 35% is obtained for a Xe lamp light source at 400nm. In C-V relation, capacitance peaks appeared at the frequencies of 100Hz and 300Hz due to the activation of the interfacial states which exist at the energy level corresponding to the one-third of the GaAs band gap. The difference of about 1.1V between flatband potential (Vfb) from the Mott-Schottky method and onset voltage from I-V curve is observed due to the trap of carriers at the interfacial states in the boundary between GaAs and electrolyte. In case of WO3 deposited p-GaAs electrode, higher positive onset current and photocurent density are obtained. This can be explained by the fact that carriers are generated by light penetrated into the WO3 thin flm as well as p-GaAs substrate and then move into the electrolyte effectively.

• 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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• 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.

• Korean Journal of Materials Research
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• v.30 no.11
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• pp.601-608
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• 2020

In this work, Ag₃PO₄/In₂S₃ nanocomposites with low loading of In₂S₃ (5-15 wt %) are fabricated by two step chemical precipitation approach. The microstructure, composition and improved photoelectrochemical properties of the as-prepared composites are studied by X-ray diffraction pattern (XRD), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photocurrent density, EIS and amperometric i-t curve analysis. It is found that most of In₂S₃ nanoparticles are deposited on the surfaces of Ag₃PO₄. The as-prepared Ag₃PO₄/In₂S₃ composite (10 wt%) is selected and investigated by SEM and TEM, which exhibits special morphology consisting of lager size substrate (Ag₃PO₄), particles and some nanosheets (In₂S₃). The introduction of In₂S₃ is effective at improving the charge separation and transfer efficiency of Ag₃PO₄/In₂S₃, resulting in an enhancement of photoelectric behavior. The origin of the enhanced photoelectrochemical activity of the In₂S₃-modified Ag₃PO₄ may be due to the improved charge separation, photocurrent stability and oriented electrons transport pathways in environment and energy applications.

• 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.

• Transactions of the Korean hydrogen and new energy society
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• v.13 no.1
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• pp.34-41
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• 2002

CdS and $TiO_2$ nanoparticles were made by the precipitation method and sol-gel method, respectively, and they were mixed mechanically and then treated with the hydrothermal processing. CdS-$TiO_2$ composite particulate films were thus prepared by casting CdS-$TiO_2$ mixed sol onto $SnO_2$ conducting glass and a subsequent heat-treatment at $400^{\circ}C$. Again, the physico-chemical and photoelectrochemical properties of these films were controlled by the surface treatment with $TiCl_4$ aqueous solution. The photocurrents and the hydrogen production rates measured under the present experimental conditions varied in the range of $3.5{\sim}4.5mA/cm^2$ and $0.3{\sim}1.8cc/cm^2$-hr, respectively, and showed the maximum values at the $CdS/[CdS+TiO_2]$ mole ratio of 0.2. Also, the surface treatment with $TiCl_4$ aqueous solution caused a considerable improvement in the photocatalytic activity, Probably as a result of close contacts between the primary particles by the etching effect of $TiCl_4$ It was found that the photoelectrochemical performance of these particulate films could be effectively enhanced by this approach.

• Korean Journal of Materials Research
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• v.29 no.3
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• pp.196-203
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• 2019

We report on the fabrication and characterization of an oxide photoanode with a zinc oxide (ZnO) nanorod array embedded in cuprous oxide ($Cu_2O$) thin film, namely a $ZnO/Cu_2O$ oxide p-n heterostructure photoanode, for enhanced efficiency of visible light driven photoelectrochemical (PEC) water splitting. A vertically oriented n-type ZnO nanorod array is first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type $Cu_2O$ thin film is directly electrodeposited onto the vertically oriented ZnO nanorod array to form an oxide p-n heterostructure. The introduction of $Cu_2O$ layer produces a noticeable enhancement in the visible light absorption. From the observed PEC current density versus voltage (J-V) behavior under visible light illumination, the photoconversion efficiency of this $ZnO/Cu_2O$ p-n heterostructure photoanode is found to reach 0.39 %, which is seven times that of a pristine ZnO nanorod photoanode. In particular, a significant PEC performance is observed even at an applied bias of 0 V vs $Hg/Hg_2Cl_2$, which makes the device self-powered. The observed improvement in the PEC performance is attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential including the light absorption and separation processes of photoinduced charge carriers, which provides a new avenue for preparing efficient photoanodes for PEC water splitting.

• Korean Journal of Materials Research
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• v.28 no.4
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• pp.214-220
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• 2018

We report on the fabrication and photoelectrochemical(PEC) properties of a $Cu_2O$ thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in $Cu_2O$ thin film as an efficient photoelectrode for solar-driven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type $Cu_2O$ thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated $Cu_2O/ZnO$ p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the $Cu_2O/ZnO$ photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., $0.77mA/cm^2$ at 0.5 V vs $Hg/HgCl_2$ in a $1mM\;Na_2SO_4$ electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs $Hg/HgCl_2$, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.

• Journal of the Microelectronics and Packaging Society
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• v.24 no.4
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• pp.59-63
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• 2017

The n-type GaN semiconductor has excellent properties as a photoelectrode, but it has disadvantage that its reliability is deteriorated due to the photocorrosion because the oxygen reaction occurs on the surface. For this reason, there are fundamental attempts to avoid photocorrosion reaction of GaN surfaces by using the p-type GaN as a photoelectrode where hydrogen generation reaction occurs on the surface. However, p-type GaN has a problem of low efficiency because of its high resistivity and low hole mobility. In this study, we try to improve the photocurrent efficiency by activation process for the p-type GaN. The p-type GaN was annealed for 1 min. at $500^{\circ}C$ in $N_2$ atmosphere. Hall effect measurement system was used for the electrical properties and potentiostat (PARSTAT4000) was used to measure the photoelectrochemical (PEC) characteristics. Consequently, the photocurrent density was improved more than 1.5 times by improving the activation process for the p-type GaN. Also, its reliability was maintained for 3 hours.