• Korean Chemical Engineering Research
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• v.54 no.3
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• pp.299-304
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• 2016

Characteristics of self-propagating reaction for the preparation of ZnO powder from precursors composed of nitrate and citrate compounds were examined. The ratio of C/N was maintained in range of 0.7~0.8 to initiate the self-propagating reaction between the reducing citrate and oxidizing nitrate groups. The samples were decomposed thermally by using TGA. The sudden decomposition occurred in the range of X > 0.5 in a very short time with a very sharp decrease of mass, indicating that the self-propagating reaction would occur. Friedman, Ozawa-Flynn-Wall and Vyazovkin methods were employed to predict the activation energy, reaction order and frequency factor of the reaction rate in the rate determining step of X < 0.5 range. The activation energy increased with increasing fractional conversion in the range of 46~130 (kJ/min). The reaction order decreased in the range of 2.9~0.9, while the frequency factor increased in the range of 85~278 ($min^{-1}$), respectively, with increasing the rate of temperature increase.

• Journal of the Korean Applied Science and Technology
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• v.33 no.4
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• pp.734-740
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• 2016

The micron-sized indium zinc tin oxide (IZTO) particles were prepared by spray pyrolysis from aqueous precursor solution for indium, zinc, and tin and organic additives such as citric acid (CA) and ethylene glycol (EG) were added to aqueous precursor solution for indium, zinc, and tin. The obtained IZTO particles prepared by spray pyrolysis from the aqueous solution without organic additives had spherical and filled morphologies, whereas the IZTO particles obtained with organic additives had more hollow and porous morphologies. The micron-sized IZTO particles with organic additives were changed fully to nano-sized IZTO particles, whereas the micron-sized IZTO particles without organic additives were not changed fully to nano-sized IZTO particle after post-treatment at $700^{\circ}C$ for 2 hours and wet-ball milling for 24 hours. Surface resistances of micron-sized IZTO's before post-heat treatment and wet-ball milling were much higher than those of nano-sized IZTO's after post-heat treatment and wet-ball milling. From IZTO with composition of 80 wt. % $In_2O_3$, 10 wt. % ZnO, and 10 wt. % $SnO_2$ which showed a smallest surface resistance IZTO after post-heat treatment and wet-ball milling, thin films were deposited on glass substrates by pulsed DC magnetron sputtering, and the electrical and optical properties were investigated.

• Journal of Powder Materials
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• v.25 no.6
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• pp.487-493
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• 2018

The impact of different mixing methods and sintering temperatures on the microstructure and piezoelectric properties of PZNN-PZT ceramics is investigated. To improve the sinterability and piezoelectric properties of these ceramics, the composition of $0.13Pb((Zn_{0.8}Ni_{0.2})_{1/3}Nb_{2/3})O_3-0.87Pb(Zr_{0.5}Ti_{0.5})O_3$ (PZNN-PZT) containing a Pb-based relaxor component is selected. Two methods are used to create the powder for the PZNN-PZT ceramics. The first involves blending all source powders at once, followed by calcination. The second involves the preferential creation of columbite as a precursor, by reacting NiO with $Nb_2O_5$ powder. Subsequently, PZNN-PZT powder can be prepared by mixing the columbite powder, PbO, and other components, followed by an additional calcination step. All the PZNN-PZT powder samples in this study show a nearly-pure perovskite phase. High-density PZNN-PZT ceramics can be fabricated using powders prepared by a two-step calcination process, with the addition of 0.3 wt% MnO2 at even relatively low sintering temperatures from $800^{\circ}C$ to $1000^{\circ}C$. The grain size of the ceramics at sintering temperatures above $900^{\circ}C$ is increased to approximately $3{\mu}m$. The optimized PZNN-PZT piezoelectric ceramics show a piezoelectric constant ($d_{33}$) of 360 pC/N, an electromechanical coupling factor ($k_p$) of 0.61, and a quality factor ($Q_m$) of 275.

• 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.

• Korean Journal of Food Science and Technology
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• v.27 no.4
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• pp.564-570
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• 1995

N-Benzoyl-L-aspartyl-L-phenylalanine methyl ester(BzAPM), a novel aspartame precursor, was investigated for its enzymatic synthesis by immobilized thermolysin using a water-miscible organic solvent system. The substrate used were N-benzoyl-L-aspartic acid(BzAsp) and L-phenylalanine methyl ester (PheOMe). Synthetic conditions such as substrates concentration, temperature, pH, and some metallic ions were varied to study their effects on BzAPM synthesis. The synthetic reaction rate increased linearly as the PheOMe concentration increased at a constant concentration of BzAsp(100 mM), and the maximum reaction rate was obtained at BzAsp concentration of 200 mM when 300 mM PheOMe was used. The optimum pH and temperature were found to be 6.1 and $40^{\circ}C$, respectively. The metallic ions such as $Zn^{2+},\;Mg^{2+},\;Mn^{2+},\;Fe^{2+},\;Pb^{2+}\;and\;Cu^{2+}$ at 5 mM level showed inhibitory effect on BzAPM synthesis, while $Co^{2+}$ and $Ca^{2+}$ ion increased synthesis. $Co^{2+}$ ion was also found to have synergistic effect with $Ca^{2+}$ ion. Benzoic acid, L-phenylalanin and NaCl showed inhibitory effect.

• Korean Journal of Materials Research
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• v.12 no.9
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• pp.761-766
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• 2002

Fine $LaPO_4$:Tb phosphor particles with spherical shape were prepared by spray pyrolysis. The influence of the precursor type of phosphorous such as ($NH_4$)$_2$$HPO_4$, $NH_4$$H_2$$PO_4$, ($NH_4$)$_3$$PO_4$ and $H_3$$PO_4$ on the morphology and brightness of particles was investigated. As-prepared particles by spray pyrolysis had spherical shape when ($NH_4$)$_2$ $HPO_4$ and $NH_4$$H_2$$PO_4$ were used as the precursor of phosphorous. The precursor type of phosphorous affected the photoluminescence intensity of $LaPO_4$:Tb phosphor particles, but not significant. With changing the content of activator(Tb) and excess of phosphorous, the optimal composition giving the highest photoluminescence intensity was found. The spherical morphology of prepared $LaPO_4$:Tb particles was completely maintained even after the posttreatment up to $1050^{\circ}C$. When the posttreatment temperature was over $1100^{\circ}C$, the particles did not have the spherical shape anymore. However, the highest photoluminescence intensity of prepared $LaPO_4$:Tb particles was obtained at $1050^{\circ}C$. The photoluminescence characteristics of prepared $_LaPO4$:Tb under the vacuum ultraviolet(VUV) illumination was comparable with that of the commercial $Zn_2$$V_4$:Mn and (La,Ce)PO$_4$:Tb phosphor particles. At the optimal condition, the decay time of prepared spherical $LaPO_4$:Tb phosphor particles was about 6.8ms.

• Proceedings of the Materials Research Society of Korea Conference
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• 2010.05a
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• pp.29.2-29.2
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• 2010

최근 박막형 LED 및 박막형 태양전지등의 기존 마이크로 소자들의 효율향상을 위한 개선으로 나노구조를 이용한 나노소자 제작이 관심을 받고 있다. 이는 가능성으로만 여겨져왔던 나노기술이 기존 박막형 소자에서 포화된 효율상향 접근방식의 한계에 따른 것으로 생각되며, 나아가 나노기술로 제작된 나노소자가 우리 생활을 채우게 될 날이 얼마남지 않은 것을 의미한다. 특히, 디스플레이 소자에서의 나노기술은 더욱 더 중요시 되고 있다. 그로 인해 투명성과 우수한 광전기적 특성을 지닌 산화물 반도체와 그 나노구조 대한 관심이 날로 높아지고 있으며, 그 가운데 산화아연계(ZnO, MgZnO등) 나노구조를 이용한 나노소자 제작이 많이 연구되고 있다. 산화아연은 c축으로 우선 배향성을 가지는 우르짜이트 구조로써, 나노선 성장이 다른 산화물에 비해 용이하고 그 물리적, 화학적 특성이 안정 우수하다. 이러한 산화아연 나노선 제작법 가운데, 유기금속화학기상증착법은 다른 성장법에 비해 결정학적 광학적 특성이 우수하고 성장속도가 빨라 고품질 나노선 성장에 용이한 장비로 각광받고 있다. 하지만 bottom-up 공정을 기반으로 한 나노소자제작에서 몇 가지 문제점을 가지고 있다. 1) 수직형 대면적 성장, 2) 나노선 밀도 조절의 어려움, 3) 기판과의 계면층에 자발적으로 생성되는 계면층의 제거, 4) 고온성장시 precursor의 증발 문제 등이 그것이다. 이러한 문제점을 해결하기 위해 산화아연 나노구조 성장 시, 마그네슘(Mg)을 도입하여, 각 원소의 조성 차이에 따라 기판 표면에 30nm 두께 미만의 상분리층(단결정+비정질층)을 자발적으로 형성시켰다. 성장이 진행됨에 따라, 아연이 rich한 단결정 층에서는 나노선이 선택적으로 성장하게 하였고, 마그네슘이 rich한 비정질 층에서는 성장이 이루어지지 않게 하였다. 따라서 산화아연이 증발되는 온도영역에서 10nm 이하 직경을 가지는 나노선을 자발적으로 계면층 없이 수직 성장하였다. 또한, 표면의 단결정, 비정질의 사이즈를 Mg 유량으로 적절히 조절한 결과, 산화아연계 나노월 구조성장이 가능하였다.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.480-480
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• 2010

In the present work, we studied effect of the deposition parameters on the structure and properties of ZnO films deposited by DC arc plasmatron. The varied parameters were gas flow rates, precursor composition, substrate temperature and post-deposition annealing temperature. Vapor of Zinc acetylacetone was used as source materials, oxygen was used as working gas and argon was used as the cathode protective gas and a transport gas for the vapor. The plasmatron power was varied in the range of 700-1,500 watts. Flow rate of the gases and substrate temperature rate were varied in the wide range to optimize the properties of the deposited coatings. After deposition films were annealed in the hydrogen atmosphere in the wide range of temperatures. Structure of coatings was investigated using XRD and SEM. Chemical composition was analyzed using x-ray photo-electron spectroscopy. Sheet conductivity was measured by 4-point probe method. Optical properties of the transparent ZnO-based coatings were studied by the spectroscopy. It was shown that deposition by a DC Arc plasmatron can be used for low-cost production of zinc oxide films with good optical and electrical properties. Sheet resistance of 4 Ohms cm was achieved after the deposition and 30 min annealing in the hydrogen at $350^{\circ}C$. Elevation of the substrate temperature during the deposition process up to $350^{\circ}C$ leads to decreasing of the film's resistance due to rearrangement of the crystalline structure.

• Korean Chemical Engineering Research
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• v.45 no.6
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• pp.566-572
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• 2007

Two hybrid catalysts for the direct synthesis of DME were prepared and the catalytic activity of these catalysts were investigated. The hybrid catalyst for the direct synthesis of DME was composed as the catalytic active components of methanol synthesis and dehydration. The methanol synthesis catalyst was formed from the precursor contained Cu and Zn, the methanol dehydration catalyst was used ${\gamma}-Al_2O_3$. As PM-CZ+D and CP-CZA/D, Two hybrid catalysts were prepared by physical mixing method (PM-CZ+D) and precipitation method (CP-CZA/D), respectively. PM-CZ+D was prepared by physically mixing methanol synthesis catalyst and methanol dehydration catalyst, CP-CZA/D was prepared by depositing Cu-Zn or Cu-Zn-Al components on ${\gamma}-Al_2O_3$. The crystallinity and the surface morphology of synthesized catalyst were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to investigate the physical property of prepared catalyst. And BET surface area by $N_2$ adsorption and the surface area of Cu by $N_2O$ chemisorption were investigated about the hybrid catalysts. In addition, catalytic activity of these hybrid catalysts was examined with varying reaction conditions. At that time, the reaction temperature of $250{\sim}290^{\circ}C$, the reaction pressure of 50~70 atm, the $[H_2]/[CO]$ mole ratio of 0.5~2.0 and the space velocity of $1,500{\sim}6,000h^{-1}$ were investigated the catalytic activity. From these results, it was confirmed that the reactivity of CP-CZA/D was higher than that of PM-CZ+D. When the conditions of reaction temperature, pressure, $[H_2]/[CO]$ ratio and space velocity were $260^{\circ}C$, 50 atm and 1.0, $3,000h^{-1}$ respectively, CO conversion using CP-CZA/D hybrid catalyst was 72% and the CO conversion of CP-CZA/D was more than 20% compared with the CO conversion of PM-CZ+D. It was known that Cu surface area of CP-CZA/D hybrid catalyst was higher than that of hybrid PM-CZ+D catalyst using $N_2O$ chemisorption. It was assumed that the catalytic activity was improved because Cu particle of hybrid catalyst prepared by precipitation method was well dispersed.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.101.1-101.1
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• 2010

$Cu(InGa)Se_2$ (CIGS) 태양전지는 박막형 태양전지 중 가장 높은 에너지 변환 효율이 보고 되고 있다. CIGS 태양전지를 제조하는 방법은 3 단계 동시 증착법, 금속 전구체의 셀렌화 공정법, 전기 증착법 등이 있다. 이 중 금속 전구체의 셀렌화 공정법은 다른 제조 방법에 비해 대면적 생산에 유리하고, 비교적 공정 과정이 간단하다는 장점이 있다. 하지만 금속 전구체의 미세구조 및 제조 방법, 셀렌화 공정의 최적화에 대한 연구가 부족하다. 본 실험에서는 후면전극으로 사용되는 Mo 층이 증착된 소다회 유리(soda-lime glass)를 기판으로 사용하였다. Cu-In(4:6), Cu-Ga(6:4) 타겟을 DC 스퍼터링 시스템을 이용하여 금속 전구체를 증착하였다. 이 후 미국 Delawere 대학교의 IEC 연구소와 한국전자통신연구원 (ETRI)에서 금속 전구체의 셀렌화 공정을 진행하였다. 셀렌화 공정 전후의 금속 전구체의 결정 크기와 미세구조의 변화를 관찰하기 위하여 주사전자현미경 (SEM)과 X선 회절 분석기 (XRD)를 사용하였다. 센렌화 공정이 진행된 금속 전구체 위에 버퍼층으로 사용되는 CdS와 전면전극으로 사영되는 ZnO, ITO 층을 합성한 후 에너지 변환 효율을 측정하였다. 최고 효율은 9.7%로 관찰되었다.