• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.117.2-117.2
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• 2011

Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline TiO2 electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline TiO2. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1081-1088
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• 2013

Two new metal-free organic dyes bridged by anthracene-mediated ${\pi}$-conjugated moieties were successfully synthesized for use in a dye-sensitized solar cell (DSSC). A N,N-diphenylthiophen-2-amine unit in these dyes acts as an electron donor, while a (E)-2-cyano-3-(thiophen-2-yl)acrylic acid group acts as an electron acceptor and an anchoring group to the $TiO_2$ electrode. The photovoltaic properties of (E)-2-cyano-3-(5-((10-(5-(diphenylamino)thiophen-2-yl)anthracen-9-yl)ethynyl)thiophen-2-yl)acrylic acid (DPATAT) and (E)-2-cyano-3-(5'-((10-(5-(diphenylamino)thiophen-2-yl)anthracen-9-yl)ethynyl)-2,2'-bithiophen-5-yl)acrylic acid (DPATABT) were investigated to identify the effect of conjugation length between electron donor and acceptor on the DSSC performance. By introducing an anthracene moiety into the dye structure, together with a triple bond and thiophene moieties for fine-tuning of molecular configurations and for broadening the absorption spectra, the short-circuit photocurrent densities ($J_{sc}$), and open-circuit photovoltages ($V_{oc}$) of DSSCs were improved. The improvement of $J_{sc}$ in DSSC made of DPATABT might be attributed to much broader absorption spectrum and higher molecular extinction coefficient (${\varepsilon}$) in the visible wavelength range. The DPATABT-based DSSC showed the highest power conversion efficiency (PCE) of 3.34% (${\eta}_{max}$ = 3.70%) under AM 1.5 illumination ($100mWcm^{-2}$) in a photoactive area of $0.41cm^2$, with the $J_{sc}$ of $7.89mAcm^{-2}$, the $V_{oc}$ of 0.59 V, and the fill factor (FF) of 72%. In brief, the solar cell performance with DPATABT was found to be better than that of DPATAT-based DSSC.

• Korean Journal of Materials Research
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• v.19 no.1
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• pp.50-53
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• 2009

Multi-walled carbon nanotubes (MWNTs) were synthesized on different substrates (bare Si and $SiO_2$/Si substrate) to investigate dye-sensitized solar cell (DSSC) applications as counter electrode materials. The synthesis of MWNTs samples used identical conditions of a Fe catalyst created by thermal chemical vapor deposition at $900^{\circ}C$. It was found that the diameter of the MWNTs on the Si substrate sample is approximately $5{\sim}10nm$ larger than that of a $SiO_2$/Si substrate sample. Moreover, MWNTs on a Si substrate sample were well-crystallized in terms of their Raman spectrum. In addition, the MWNTs on Si substrate sample show an enhanced redox reaction, as observed through a smaller interface resistance and faster reaction rates in the EIS spectrum. The results show that DSSCs with a MWNT counter electrode on a bare Si substrate sample demonstrate energy conversion efficiency in excess of 1.4 %.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.64.1-64.1
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• 2010

The morphology of mesoporous $TiO_2$ films plays an important role in the operation of a DSSC. For example, the energy conversion efficiency of DSSCs with well-organized mesoporous $TiO_2$ films is much higher than those with traditional films possessing a random morphology. In previous research, well-organized mesoporous $TiO_2$ films have mainly been synthesized using an amphiphilic block copolymer, e.g., a poly(ethylene oxide) (PEO)-based template. A graft copolymer is more attractive than a block copolymer due to its low cost and the ease with which it can be synthesized. In this work, we provide the first report on the successful synthesis of well-organized mesoporous $TiO_2$ films templated by an organized graft copolymer as a structure directing agent. Well-organized mesoporous $TiO_2$ films with excellent channel connectivities were developed via the sol gel processusing an organized PVC-g-POEM graft copolymer synthesized by one-pot ATRP. The careful adjustment of copolymer composition and solvent affinity using a THF/$H_2O$/HCl mixture was used to systematically vary the material structure. The influence of the material structure on solar cell performance was then investigated. A solid-state DSSC employing both the graft copolymer templated organized 700 nm-thick $TiO_2$ films and graft copolymer electrolytes exhibited a solar conversion efficiency of 2.2% at 100 $mW/cm^2$. This value was approximately two-fold higher than that attained from a DSSC employing a random mesoporous $TiO_2$ film. The solar cell performance was maximized at 4.6% when the film thickness was increased to $2.5{\mu}m$. We believe that this graft copolymer-directed approach introduces a new and simple route toward the synthesis of well-organized metal oxide films as an alternative to a conventional block copolymer-based template.

• Korean Chemical Engineering Research
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• v.48 no.4
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• pp.506-510
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• 2010

Electron recombinations in electrolyte solution reduce light-to-energy conversion efficiency at the nanoporous electrode surface of dye sensitized solar cells. In this study, we improved the conversion efficiency using an energy barrier at the nanoporous electrode surface to control the recombination process. The energy barrier was formed by coating nanoporous $TiO_2$ electrode with $Nb_2O_5$ material. We investigated the influence of energy barrier on the cell efficiency depending on the coating thickness. Nanoporous $TiO_2$ electrode was coated about 5 nm thickness by 12 times coatings, and so the coating layer was grown about 0.417 nm for every time. Enhancement of conversion efficiency from 2.55% to 4.25% was achieved at 0.834 nm coating thickness, and it was believed as the optimum thickness for minimizing the electron recombination process in our experimental system.

• Applied Chemistry for Engineering
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• v.21 no.4
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• pp.405-410
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• 2010

The photovoltaic performance of DSSCs fabricated with different electrode thickness and different annealing temperature with the P25 $TiO_2$ and the Dyesol $TiO_2$ was measured. Thickness change of $TiO_2$ electrodes was measured using cross-sectional FE-SEM before and after annealing. Photovoltaic efficiencies of DSSCs were also measured by changing annealing temperature of platinum (Pt) paste on the counter electrode. Photovoltaic performances of DSSCs made with one layer of P25 (${\sim}20.4\;{\mu}m$) and one layer of Dyesol $TiO_2$ (${\sim}9.1\;{\mu}m$) annealed at $500^{\circ}C$ for 30 min. showed highest efficiencies of 3.8% and 5.8%, respectively.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.396-396
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• 2012

$TiO_2$ anatase nanotube arrays (NTAs) were grown by electrochemical anodization and followed annealing of Ti foil. Ethylene glycol/$NH_4F$-based organic electrolyte was used for electrolyte solution and using second anodization process to obtain free-standing NTAs. After obtaining NTAs, ITO film was deposited by sputtering process on bottom of NTAs. UV-curable NOA was used for attach free-standing NTAs on flexible plastic substrate (PEN). Solid state electrolyte (spiro-OMeTAD) was coated via spin-coating method on top of attached NTAs. Ag was deposited as a counter electrode. Under AM 1.5 simulated sunlight, optical characteristics of devices were investigated. In order to use flexible polymer substrate, processes have to be conducted at low temperature. In case of $TiO_2$ nano particles (NPs), however, crystallization of NPs at high temperature above $450^{\circ}C$ is required. Because NTAs were conducted high temperature annealing process before NTAs transfer to PEN, it is favorable for using PEN as flexible substrate. Fabricated flexible solid-state DSSCs make possible the preventing of liquid electrolyte corrosion and leakage, various application.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.18 no.4
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• pp.1-7
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• 2017

Cobalt silicide was used as a counter electrode in order to confirm its reliability in dye-sensitized solar cell (DSSC) devices. 100 nm-Co/300 nm-Si/quartz was formed by an evaporator and cobalt silicide was formed by vacuum heat treatment at $700^{\circ}C$ for 60 min to form approximately 350 nm-CoSi. This process was followed by etching in $80^{\circ}C$-30% $H_2SO_4$ to remove the cobalt residue on the cobalt silicide surface. Also, for the comparison against Pt, we prepared a 100 nm-Pt/glass counter electrode. Cobalt silicide was used for the counter electrode in order to confirm its reliability in DSSC devices and maintained for 0, 168, 336, 504, 672, and 840 hours at $80^{\circ}C$. The photovoltaic properties of the DSSCs employing cobalt silicide were confirmed by using a simulator and potentiostat. Cyclic-voltammetry, field emission scanning electron microscopy, focused ion beam scanning electron microscopy, and energy dispersive spectrometry analyses were used to confirm the catalytic activity, microstructure, and composition, respectively. The energy conversion efficiency (ECE) as a function of time and ECE of the DSSC with Pt and CoSi counter electrodes were maintained for 504 hours. However, after 672 hours, the ECEs decreased to a half of their initial values. The results of the catalytic activity analysis showed that the catalytic activities of the Pt and CoSi counter electrodes decreased to 64% and 57% of their initial values, respectively(after 840 hours). The microstructure analysis showed that the CoSi layer improved the durability in the electrolyte, but because the stress concentrates on the contact surface between the lower quartz substrate and the CoSi layer, cracks are formed locally and flaking occurs. Thus, deterioration occurs due to the residual stress built up during the silicidation of the CoSi counter electrode, so it is necessary to take measures against these residual stresses, in order to ensure the reliability of the electrode.

• Applied Chemistry for Engineering
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• v.22 no.1
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• pp.98-103
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• 2011

We prepared a counter electrode by electroplating Ni as underlayer and Pt as plating layer on the FTO glass to increase the efficiency of dye-sensitized solar cell (DSSC). We found an excellent adhesion between Ni underlayer and FTO glass when Ni underlayer was electroplated at $10mA/cm^2$ for 2 min on FTO glass. We observed Ni and Pt metal diffraction peaks by XRD analysis when Ni underlayer was electroplated at $10mA/cm^2$ for 2 min, and Pt layer was electroplated at $5mA/cm^2$ for 1 min on the Ni underlayer. Photovoltaic performance and impedance analysis of DSSCs fabricated with this counter electrode shows the highest efficiency of 5.6% and the lowest resistance of 75 ohm.

• Clean Technology
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• v.20 no.3
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• pp.306-313
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• 2014

Nanoporous $TiO_2$ films are commonly used as working electrodes in dye-sensitized solar cells (DSSCs). So far, there have been attempts to synthesize films with various $TiO_2$ nanostructures to increase the power-conversion efficiency. In this work, vertically aligned rutile $TiO_2$ nanorods were grown on fluorinated tin oxide (FTO) glass by hydrothermal synthesis, followed by deposition of an anatase $TiO_2$ film. This new method of anatase $TiO_2$ growth avoided the use of a seed layer that is usually required in hydrothermal synthesis of $TiO_2$ electrodes. The dense anatase $TiO_2$ layer was designed to behave as the electron-generating layer, while the less dense rutile nanorods acted as electron-transfer pathwaysto the FTO glass. In order to facilitate the electron transfer, the rutile phase nanorods were treated with a $TiCl_4$ solution so that the nanorods were coated with the anatase $TiO_2$ film after heat treatment. Compared to the electrode consisting of only rutile $TiO_2$, the power-conversion efficiency of the rutile-anatase hybrid $TiO_2$ electrode was found to be much higher. The total thickness of the rutile-anatase hybrid $TiO_2$ structures were around $4.5-5.0{\mu}m$, and the highest power efficiency of the cell assembled with the structured $TiO_2$ electrode was around 3.94%.