• Journal of Hydrogen and New Energy
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• v.33 no.1
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• pp.113-120
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• 2022

Quantum dots (QDs) are attractive photosensitizer candidates for application not only in solar cells but also in solar hydrogen generation. For the prepartion of highly efficient QD-sensitized photoelectrodes, it is important to reduce electron recombination at the photoanode/electrolyte interface. Here, we study on the coating condition of ZnS passivation layers on the photoanodes in QD-sensitized solar cells (QDSCs). The ZnS passivation layers are coated by successive ionic layer adsorption and reaction method, and as the cation precursor, zinc acetate and zinc nitrate are empolyed. Due to the higher pH of cation precursor solution, the ZnS loading is improved when the zinc acetate is used, compared to the zinc nitrate. This improved loading of ZnS leads to the reduced electron recombination at the surface of photoanodes and the enhaced conversion efficiency of QDSCs from 6.07% to 7.45%.

• Journal of Hydrogen and New Energy
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• v.18 no.4
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• pp.452-457
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• 2007

Titanium foil and mesh(anodized tubular $TiO_2$ electrode, ATTE) were anodized in a bath at $5^{\circ}C$ with 20V external bias applied, then annealed at different temperatures($450^{\circ}C{\sim}850^{\circ}C$) to obtain tubular $TiO_2$ on the Ti substrate. The prepared sample was used to investigate rate of hydrogen production as well as Cr(VI) reduction. The ATTEs annealed at relatively lower temperatures showed higher activity than those at relatively higher temperatures. In particular, the Cr(VI) reduction was pH-dependent. To improve photocatalytic Cr(VI) reduction with the ATTEs, two configurations, fixing foil type and rotating mesh type, were also compared. As a result, the rotating mesh type was much more effective for Cr(VI) reaction than the former due to the more efficient use of the light. In the rotating type reactor, as the rotating speed increased, the rate of the Cr(VI) reduction was getting faster.

• Journal of Hydrogen and New Energy
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• v.22 no.4
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• pp.432-442
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• 2011

Anodized tubular $TiO_2$ electrodes (ATTEs) with three noticeably different lengths are prepared to determine their optimum length for the photo-driven activity in the reaction of Cr(VI) reduction and hydrogen evolution. The ATTEs with ethylene glycol have longer $TiO_2$ tubes (7-15.6 ${\mu}m$) than those with hydrfluoric acid (0.6-0.8 ${\mu}m$). These samples, which differ only in the length of the tubes, with a wall thickness of ca. 20 nm, consist mainly of an anatase crystalline phase after heat treatment at $650^{\circ}C$, since the anatase crystallites at the tube walls do not undergo transformation into rutile phase, due to the constraints imposed by the wall thickness. Among them, the medium size (ca. 8 ${\mu}m$) tubes provide the optimum conditions, irrespective of the light intensity, which is explained in terms of the correlation between the amount of photons and the adsorbed electron acceptors and their location. Photocatalytic Cr(VI) reduction leads to ca. 60% reduction of Cr(VI) even under 1 sun irradiation with the medium-sized anodized $TiO_2$ tubes, but only ca. 20% with the short- and long-sized tubes. For hydrogen evolution, tubes longer than 8 ${\mu}m$ do not exhibit better performance with any light intensity.

• 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.28 no.5
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• pp.261-267
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• 2018

Hydrothermal synthesis of highly crystalline $TiO_2$ nanorods is a well-developed technique and the nanorods have been widely used as the template for growth of various core-shell nanorod structures. Magneli/CdS core-shell nanorod structures are fabricated for the photoelectrochemical cell (PEC) electrode to achieve enhanced carrier transport along the metallic magneli phase nanorod template. However, the long and thin $TiO_2$ nanorods may form a high resistance path to the electrons transferred from the CdS layer. $TiO_2$ nanorods synthesized are reduced to magneli phases, $TixO_{2x-1}$, by heat treatment in a hydrogen environment. Two types of magneli phase nanorods of $Ti_4O_7$ and $Ti_3O_5$ are synthesized. Structural morphology and X-ray diffraction analyses are carried out. CdS nano-films are deposited on the magneli nanorods for the main light absorption layer to form a photoanode, and the PEC performance is measured under simulated sunlight irradiation and compared with the conventional $TiO_2/CdS$ core-shell nanorod electrode. A higher photocurrent is observed from the stand-alone $Ti_3O_5/CdS$ core-shell nanorod structure in which the nanorods are grown on both sides of the seed layer.

• Solar Energy
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• v.11 no.2
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• pp.70-76
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• 1991

Electrochemical reaction utilizing the semiconducting photoanodes can be applied to the photoelectrolysis of water to produce hydrogen. In this preliminary experiment, $TiO_2$ photoanodes were prepared by sintering anatase-$TiO_2$ powder at $1,250^{\circ}C$ and thermal oxidizing titanium plate at $850^{\circ}C$ in air and oxygen, respectively. Their surface structures were observed by XRD and optical microscope. I-E characteristics of thermally oxidized $TiO_2$ photoanode were also investigated under illuminated and dark conditions using 1 N and 0.1 N NaOH electrolyte solutions.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.75.2-75.2
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• 2013

Atomic layer deposition (ALD), utilizing self-limiting surface reactions, could offer promising perspectives for future efficient energy conversion devices. The capabilities of ALD for surface/interface modification and construction of novel architectures with sub-nanometer precision and exceptional conformality over high aspect ratio make it more valuable than any other deposition methods in nanoscale science and technology. In the context, a variety of researches on fabrication of active materials for energy conversion applications by ALD are emerging. Among those materials, one-dimensional nanotubular titanium dioxide, providing not only high specific surface area but also efficient carrier transport pathway, is a class of the most intensively explored materials for energy conversion systems, such as photovoltaic cells and photo/electrochemical devices. The monodisperse, stoichiometric, anatase, TiO2 nanotubes with smooth surface morphology and controlled wall thickness were fabricated via low-temperature template-directed ALD followed by subsequent annealing. The ALD-grown, anatase, TiO2 nanotubes in alumina template show unusual crystal growth behavior which allows to form remarkably large grains along axial direction over certain wall thickness. We also fabricated dye-sensitized solar cells (DSCs) introducing our anatase TiO2 nanotubes as photoanodes, and studied the effect of blocking layer, TiO2 thin films formed by ALD, on overall device efficiency. The photon convertsion efficiency ~7% were measured for our TiO2 nanotubebased DSCs with blocking layers, which is ~1% higher than ones without blocking layer. We also performed open circuit voltage decay measurement to estimate recombination rate in our cells, which is 3 times longer than conventional nanoparticulate photoanodes. The high efficiency of our ALD-grown, anatase, TiO2 nanotube-based DSCs may be attributed to both enhanced charge transport property of our TiO2 nanotubes photoanode and the suppression of recombination at the interface between transparent conducting electrode and iodine electrolytes by blocking layer.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.417-417
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• 2016

Global environmental deterioration has become more serious year by year and thus scientific interests in the renewable energy as environmental technology and replacement of fossil fuels have grown exponentially. Photoelectrochemical (PEC) cell consisting of semiconductor photoelectrodes that can harvest light and use this energy directly to split water, also known as photoelectrolysis or solar water splitting, is a promising renewable energy technology to produce hydrogen for uses in the future hydrogen economy. A major advantage of PEC systems is that they involve relatively simple processes steps as compared to many other H2 production systems. Until now, a number of materials including TiO2, WO3, Fe2O3, and BiVO4 were exploited as the photoelectrode. However, the PEC performance of these single absorber materials is limited due to their large charge recombinations in bulk, interface and surface, leading low charge separation/transport efficiencies. Recently, coupling of two materials, e.g., BiVO4/WO3, Fe2O3/WO3 and CuWO4/WO3, to form a type II heterojunction has been demonstrated to be a viable means to improve the PEC performance by enhancing the charge separation and transport efficiencies. In this study, we have prepared a triple-layer heterojunction BiVO4/WO3/SnO2 photoelectrode that shows a comparable PEC performance with previously reported best-performing nanostructured BiVO4/WO3 heterojunction photoelectrode via a facile solution method. Interestingly, we found that the incorporation of SnO2 nanoparticles layer in between WO3 and FTO largely promotes electron transport and thus minimizes interfacial recombination. The impact of the SnO2 interfacial layer was investigated in detail by TEM, hall measurement and electrochemical impedance spectroscopy (EIS) techniques. In addition, our planar-structured triple-layer photoelectrode shows a relatively high transmittance due to its low thickness (~300 nm), which benefits to couple with a solar cell to form a tandem PEC device. The overall PEC performance, especially the photocurrent onset potential (Vonset), were further improved by a reactive-ion etching (RIE) surface etching and electrocatalyst (CoOx) deposition.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.06a
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• pp.441-441
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• 2009

Dye-sensitized solar cells (DSSCs) have been widely investigated as a next-generation solar cell because of their simple fabrication process and low coats. The cells use a porous nanocrystalline TiO2 matrix coated with a sensitizer dye that acts as the light-harvesting element. The photo-exited dye injects electrons into the $TiO_2$ particles, and the oxide dye reacts with I- in the electrolyte in regenerative cycle that is completed by the reduction of $I_3^-$ at a platinum-coated counter electrode. Since $TiO_2$ porous film plays a key role in the enhancement of photoelectric conversion efficiency of DSSC, many scientists focus their researches on it. Especially, a high light-to-electricity conversion efficiency results from particle size and crystallographic phase, film porosity, surface structure, charge and surface area to volume ratio of porous $TiO_2$ electrodes, on which the dye can be sufficiently adsorbed. Effective treatment of the photoanode is important to improve DSSC performance. In this paper, to obtain properties of surface and dispersion as nitric acid treated $TiO_2$ photoelectrode was investigate. The photovoltaic characteristics of DSSCs based the electrode fabricated by nitric acid pre-treatment $TiO_2$ materials gave better performances on both of short circuit current density and open circuit voltage. We compare dispersion of $TiO_2$ nanoparticles before and after nitric acid treatment and measured Ti oxidized state from XPS. Low charge transfer resistance was obtained in nitric acid treated sample than that of untreated sample. The dye-sensitized solar cell based on the nitric acid treatment had open-circuit voltage of 0.71 V, a short-circuit current of 15.2 mAcm-2 and an energy conversion efficiency of 6.6 % under light intensity of $100\;mWcm^{-2}$. About 14 % increases in efficiency obtained when the $TiO_2$ electrode was treated by nitric acid.

• Macromolecular Research
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• v.17 no.12
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• pp.963-968
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• 2009

Liquid crystal (LC; E7 and/or ML-0249)-embedded, poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP)-based, polymer electrolytes were prepared for use in dye-sensitized solar cells (DSSCs). The electrolytes contained 1-methyl-3-propylimidazolium iodide (PMII), tetrabutylammonium iodide (TBAI), and iodine ($I_2$), which participate in the $I_3^-/I^-$ redox couple. The incorporation of photochemically stable PVdF-co-HFP in the DSSCs created a stable polymer electrolyte that resisted leakage and volatilization. DSSCs, with liquid crystal(LC)-embedded PVdF-co-HFP-based polymer electrolytes between the amphiphilic ruthenium dye N719 absorbed to the nanocrystalline $TiO_2$ photoanode and the Pt counter electrode, were fabricated. These DSSCs displayed enhanced redox couple reduction and reduced charge recombination in comparison to that fabricated from the conventional PVdF-co-HFP-based polymer electrolyte. The behavior of the polymer electrolyte was improved by the addition of optimized amounts of plasticizers, such as ethylene carbonate (EC) and propylene carbonate (PC). The significantly increased short-circuit current density ($J_{sc}$, $14.60\;mA/cm^2$) and open-circuit voltage ($V_{oc}$, 0.68 V) of these DSSCs led to a high power conversion efficiency (PCE) of 6.42% and a fill factor of 0.65 under a standard light intensity of $100\;mW/cm^2$ irradiation of AM 1.5 sunlight. A DSSC fabricated by using E7-embedded PVdF-co-HFP-based polymer electrolyte exhibited a maximum incident photon-to-current conversion efficiency (IPCE) of 50%.