• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.100-101
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• 2012

The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.68.2-68.2
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• 2010

Dye-sensitized solar cells (DSSC) show great promise as an inexpensive alternative to conventional p-n junction solar cells. Investigations into the various factors influencing the photovoltaic efficiency have recently been intensified. The conventional absorber electrode in DSSC is composed of compacted or sintered $TiO_2$ nanopowder that carries an anchored organic dye. The absorbance of incident light in the DSC is realized by specifically engineered dye molecules placed on the semiconductor electrode surface ($TiO_2$). The dye absorbs light at wavelengths up to about 920nm, the energy of the exited state of the molecule should be about 1.35eV above the electronic ground state corresponding to the ideal band gap of a single band gap solar cell. The dye molecules ar adhered onto the nanostrutured $TiO_2$ electrode by immersing the sintered electrode into a dye solution, typically 3mM in alcohol, for a long enough period to fully impregnate the electrode. However, the concentrations of the dye is slightly changed due to the evaporation of the alcohol. The dye is more expensive than other materials in DSSC and related to the efficiency of DSSC. Therefore, the concentrations of the dye should be carefully measured. In this study, we investigated to the dye loading on fired $TiO_2$ powder as a function of temperature by the TG-DTA and the dye solution by UV-visible spectroscopy after the impregnation process. The dye loading is related to the porosity of the nanostructured $TiO_2$ electrode.

• Applied Chemistry for Engineering
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• v.31 no.5
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• pp.467-474
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• 2020

Polymer solar cells have attracted extensive attention over the past decade due to their benefits, such as good solution-process-ability, light weight, low-cost, mechanically flexibility, and high efficiency. Conjugated (CPE) and non-conjugated (NPE) polyelectrolyte materials have been employed to avoid the typical weaknesses associated with conventional metal oxide interlayers. However, the application of CPEs is more complicated than that of NPEs because the synthesis procedures are complicated. NPEs containing charged ion groups can provide numerous benefits for renewable energy applications. Especially when implemented in polymer solar cells.

• Resources Recycling
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• v.20 no.2
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• pp.45-53
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• 2011

We devised a procedure for the recovery of silicon and tempered glass from waste photovoltaic (PV) modules using optimized conditions. The tempered glass was recovered without any damage using organic solvents. The surface material is removed by applying an acid solution on the surface of the PV cell. Through our proposed method, we offer a much more efficient approach for recycling solar cells with a surfactant than the conventional method. This process, we obtained pure silicon with a yield of 90% by chemical treatment with the surfactant at room temperature for 18 min. The silicon yield was characterized using an inductively coupled plasma-atomic emission spectrometer.

• Polymer(Korea)
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• v.37 no.6
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• pp.694-701
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• 2013

A new copolymer named T-TI24T (poly((5,5-(2-butyl-5,6-bisdecyloxy-4,7-di-thiophen-2-yl-isoindole-1,3-dione))- alt-(2,5-thiophene))) based on phthalimide derivative and thiophene is synthesized by the Stille-coupling reaction. The polymer shows relatively high number average molecular weight of 86500 g/mol with good solubility in common organic solvents such as chloroform, 1,2-dichlorobenzene, and toluene and is thermally stable up to $380^{\circ}C$. Besides, it possesses a relatively low highest occupied molecular orbital (HOMO) energy level of -5.33 eV, promising the high open circuit voltage ($V_{oc}$) for photovoltaic applications. Active layer solution of polymer T-TI24T-as a donor and (6)-1-(3-(methoxycarbonyl)- {5}-1-phenyl[5,6]-fullerene (PCBM)-as an acceptor in different weight ratios is applied to fabricate the polymer solar cell devices. The ratio of polymer/PCBM affects the solar cell efficiency and the best performance exhibits in the device with polymer/PCBM = 1:3 (w/w), which shows a power conversion efficiency (PCE) of 0.199% and a $V_{oc}$ of 0.99 V, respectively. Even though the device shows the very low PCE, the $V_{oc}$ is higher than that of well known bulk heterojunction type solar cell based on P3HT:PC61BM (c.a. 0.5 V).

• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.417-423
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• 2011

A series of new quinoxaline-based thiophene copolymers (PQx2T, PQx4T, and PQx6T) was synthesized via Yamamoto and Stille coupling reactions. The $M_ws$ of PQx2T, PQx4T, and PQx6T were found to be 20,000, 12,000, and 29,000, with polydispersity indices of 2.0, 1.2, and 1.1, respectively. The UV-visible absorption spectra of the polymers showed two distinct absorption peaks in the ranges 350 - 460 nm and 560 - 600 nm, which arose from the ${\pi}-{\pi}^*$ transition of oligothiophene units and intramolecular charge transfer (ICT) between a quinoxaline acceptor and thiophene donor. The HOMO levels of the polymer ranged from -5.37 to -5.17 eV and the LUMO levels ranged from -3.67 to -3.45 eV. The electrochemical bandgaps of PQx2T, PQx4T, and PQx6T were 1.70, 1.71, and 1.72 eV, respectively, thus yielding low bandgap behavior. PQx2T, PQx4T, and PQx6T had open circuit voltages of 0.58, 0.42, and 0.47 V, and short circuit current densities of 2.9, 5.29 and 9.05 mA/$cm^2$, respectively, when $PC_{71}BM$ was used as an acceptor. For the solar cells with PQx2T-PQx6T:$PC_{71}BM$ (1:3) blends, an increase in performance was observed in going from PQx2T to PQx6T. The power conversion efficiencies of PQx2T, PQx4T, and PQx6T devices were found to be 0.69%, 0.73%, and 1.80% under AM 1.5 G (100 mW/$cm^2$) illumination.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.8.1-8.1
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• 2011

Nanocrystalline titanium dioxide ($TiO_2$) materials have been widely used as an electron collector in DSSC. This is required to have an extremely high porosity and surface area such that the dye can be sufficiently adsorbed and be electronically interconnected, resulting in the generation of a high photocurrent within cells. In particular, their geometrical structures and crystalline phase have been extensively investigated as important issues in improving its photovoltaic efficiency. In this study, we present a new strategy to fabricate a photoelectrode having a periodic structured $TiO_2$ film templated from 1D or 3D polystyrene (PS) microspheres array. Monodisperse PS spheres of various radiuses were used for colloidal array on FTO glasses and two types of photoelectrode structures with different $TiO_2$ materials were investigated respectively. One is the igloo-shaped electrode prepared by $TiO_2$ deposition by RF-sputtering onto 2D microsphere-templated substrates. At the interface between the film and substrate, there are voids formed by the decomposition of PS microspheres during the calcination step. These holes might be expected to play the predominant roles as scattering spherical voids to promote a light harvesting effect, a spacious structure for electrolytes with higher viscosity and effective paths for electron transfer. Additionally the nanocrystalline $TiO_2$ phase prepared by the RF-sputtering method was previously reported to improve the electron drift mobility within $TiO_2$ electrodes. This yields solar cells with a cell efficiency of 2.45% or more at AM 1.5 illumination, which is a very remarkable result, considering its $TiO_2$ electrode thickness (<2 ${\mu}m$). This study can be expanded to obtain higher cell efficiency by higher dye loading through the increase of surface area or multi-layered stacking. The other is the inverse opal photonic crystal electrode prepared by titania particles infusion within 3D colloidal arrays. To obtain the enlargement of ordered area and high quality of crystallinity, the synthesis of titania particles coated with a organic thin layer were applied instead of sol-gel process using the $TiO_2$ precursors. They were dispersed so well in most solvents without aggregates and infused successfully within colloidal array structures. This ordered mesoporous structure provides the large surface area leading to the enough adsorption of dye molecules and have an light harvesting effect due to the photonic band gap properties (back-and-forth reflection effects within structures). A major advantage of this colloidal array template method is that the pore size and its distribution within $TiO_2$ photoelectrodes are determined by those of latex beads, which can be controlled easily. These materials may have promising potentials for future applications of membrane, sensor and so on as well as solar cells.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.65-65
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• 2012

Copper zinc tin sulfide ($Cu_2ZnSnS_4$, CZTS) is a very promising material as a low cost absorber alternative to other chalcopyrite-type semiconductors based on Ga or In because of the abundant and economical elements. In addition, CZTS has a band-gap energy of 1.4~1.5eV and large absorption coefficient over ${\sim}10^4cm^{-1}$, which is similar to those of $Cu(In,Ga)Se_2$(CIGS) regarded as one of the most successful absorber materials for high efficient solar cell. Most previous works on the fabrication of CZTS thin films were based on the vacuum deposition such as thermal evaporation and RF magnetron sputtering. Although the vacuum deposition has been widely adopted, it is quite expensive and complicated. In this regard, the solution processes such as sol-gel method, nanocrystal dispersion and hybrid slurry method have been developed for easy and cost-effective fabrication of CZTS film. Among these methods, the hybrid slurry method is favorable to make high crystalline and dense absorber layer. However, this method has the demerit using the toxic and explosive hydrazine solvent, which has severe limitation for common use. With these considerations, it is highly desirable to develop a robust, easily scalable and relatively safe solution-based process for the fabrication of a high quality CZTS absorber layer. Here, we demonstrate the fabrication of a high quality CZTS absorber layer with a thickness of 1.5~2.0 ${\mu}m$ and micrometer-scaled grains using two different non-vacuum approaches. The first solution-processing approach includes air-stable non-toxic solvent-based inks in which the commercially available precursor nanoparticles are dispersed in ethanol. Our readily achievable air-stable precursor ink, without the involvement of complex particle synthesis, high toxic solvents, or organic additives, facilitates a convenient method to fabricate a high quality CZTS absorber layer with uniform surface composition and across the film depth when annealed at $530^{\circ}C$. The conversion efficiency and fill factor for the non-toxic ink based solar cells are 5.14% and 52.8%, respectively. The other method is based on the nanocrystal dispersions that are a key ingredient in the deposition of thermally annealed absorber layers. We report a facile synthetic method to produce phase-pure CZTS nanocrystals capped with less toxic and more easily removable ligands. The resulting CZTS nanoparticle dispersion enables us to fabricate uniform, crack-free absorber layer onto Mo-coated soda-lime glass at $500^{\circ}C$, which exhibits a robust and reproducible photovoltaic response. Our simple and less-toxic approach for the fabrication of CZTS layer, reported here, will be the first step in realizing the low-cost solution-processed CZTS solar cell with high efficiency.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.19 no.6
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• pp.646-651
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• 2018

This paper reports that the electronic properties at a $P3HT/TiO_2$ interface associated with exciton dissociation and transport can be tailored by the insertion of a graphene quantum dot (GQD) layer. For donor/acceptor interface modification in an $ITO/TiO_2/P3HT/Al$ photovoltaic (PV) device, a continuous GQD film was prepared by a sonication treatment in solution that simplifies the conventional processes, including laser fragmentation and hydrothermal treatment, which limits a variety of component layers and involves low cost processing. The high conductivity and favorable energy alignment for exciton dissociation of the GQD layer increased the fill factor and short circuit current. The origin of the improved parameters is discussed in terms of the broad light absorption and enhanced interfacial carrier transport.