• 한국진공학회지
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• 제2권4호
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• pp.486-490
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• 1993

Cd4SnSea6 & Cd4SnSe6 : Co2+ single crystals were grown by the chemical transport reaction (CTR) method. The grown single crystlas crrystallize in the monoclinic structrue and have the direct band gaps. The energy gaps of them are 1.68eV for Cd4SnSea6 & Cd4SnSe6 : Co2+ at 293K. The impurity opticla absorption peaks due to cobalt dped with impurity appear at 4879cm-1, 5392cm-1 and 6247 com-1, and are attributed to the electron transitions between the split energy levels of Co2+ ion sited at Td symmetry of Cd4SnSe6 single crystal.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2005년도 하계학술대회 논문집 Vol.6
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• pp.607-608
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• 2005

In this paper, author describe the undoped and $Co^{2+}$(0.5mole%) doped $Cd_4SnSe_6$ single crystals were grown by the chemical transport reaction(CTR) method. The grown single crystals crystallize in the monoclinic structure of space group Cc and have the direct band gap structure. The energy gaps of them are 1.68 eV for $Cd_4SnSe_6$ and 1.50 eV for $Cd_4SnSe_6:Co^{2+}$ at 300K respectively.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2002년도 제4회 영호남학술대회 논문집
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• pp.25-30
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• 2002

The ternary semiconducting compounds of the $A_{4}BX_{6}$(A=Cd, Zn, Hg; B=Si, Sn, Ge; X=S, Se, Te) type exhibit strong fluorescence and high photosensitivity in the visible and near infrared ranges, so these are supposed to be materials applicable to photoelectrical devices. These materials were synthesized and single crystals were first grown by Nitsche, who identified the crystal structure of the single crystals. In this paper. author describe the undoped and $Co^{2+}$-doped $Zn_{4}SnSe_{6}$ single crystals were grown by the chemical transport reaction(CTR) method using iodine of $6mg/cm^{3}$ as a transport agent. For the crystal. growth, the temperature gradient of the CTR furnace was kep at $700^{\circ}C$ for the source aone and at $820^{\circ}C$ for the growth zone for 7-days. It was found from the analysis of x-ray diffraction that undoped and $Co^{2+}$-doped $Zn_{4}SnSe_{6}$ compounds have a monoclinic structure. The optical absorption spectra obtained near the fundamental absorption edge showed that these compounds have a direct energy gaps. These temperature dependence of the optical energy gap were closely investigated over the temperature range 10[K]~300[K]

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.472.1-472.1
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• 2014

현재 Cu(In,Ga)Se2나 Cu2ZnSn(S,Se)4 (CZTSSe)계 박막태양전지의 버퍼층으로 가장 많이 사용되는 물질은 CdS이다. 하지만 Cd의 독성 문제로 인해 사용에 제약이 있고, CdS의 작은 밴드갭(~2.4 eV)으로 인해 단 파장 영역에서 광활성층의 빛 흡수를 저해하는 문제 때문에 새로운 대체 물질을 찾으려는 연구가 많이 이루어지고 있다. 이러한 관점에서, ZnS계 물질은 독성 원소인 Cd을 사용하지 않고, 3.6 eV 정도의 큰 밴드갭을 가지기 때문에, CdS 버퍼층을 대체하기 위한 물질로 관심을 받고 있다. ZnS계 버퍼층을 증착하는 위해 chemical bath deposition (CBD), molecular beam epitaxy (MBE), thermal evaporation, spray pyrolysis, sputtering, elecrtrodepostion 등의 다양한 공정이 사용될 수 있다. 본 연구에서는 상기의 다양한 공정 가운데, 공정 단가가 낮고, 대면적 공정에 용이한 CBD 공정을 이용하여 ZnS계 버퍼층을 증착하는 연구를 수행하였다. 용액의 조성, 농도, 공정 온도, 시간 등을 비롯한 다양한 공정 변수가 ZnS계 박막의 morphology, 조성, 결정성, 광학적 특성 등 다양한 특성에 미치는 영향이 체계적으로 연구되었다. 또한, 상기 ZnS계 버퍼층을 CZTSSe 박막태양전지에 적용하여 CdS를 성공적으로 대체할 수 있음을 확인하였다. 본 연구를 통하여 ZnS계 버퍼층이 향후 친환경적인 박막태양전지 제조에 활용될 수 있는 가능성을 확인할 수 있었다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2015년도 제49회 하계 정기학술대회 초록집
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• pp.86.2-86.2
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• 2015

Cu2ZnSn(S,Se)4 thin film solar cells have been fabricated using sputtered Cu/Sn/Zn metallic precursors on Mo coated sodalime glass substrate without using a toxic H2Se and H2S atmosphere. Cu/Sn/Zn metallic precursors with various thicknesses were prepared using DC magnetron sputtering process at room temperature. As-deposited metallic precursors were sulfo-selenized inside a graphite box containing S and Se pellets using rapid thermal processing furnace at various sulfur to selenium (S/Se) compositional ratio. Thin film solar cells were fabricated after sulfo-selenization process using a 65 nm CdS buffer, a 40 nm intrinsic ZnO, a 400 nm Al doped ZnO, and Al/Ni top metal contact. Effects of sulfur to selenium (S/Se) compositional ratio on the microstructure, crystallinity, electrical properties, and cell efficiencies have been studied using X-ray diffraction, Raman spectroscopy, field emission scanning electron microscope, I-V measurement system, solar simulator, quantum efficiency measurement system, and time resolved photoluminescence spectrometer. Our fabricated Cu2ZnSn(S,Se)4 thin film solar cell shows the best conversion efficiency of 9.24 % (Voc : 454.6 mV, Jsc : 32.14 mA/cm2, FF : 63.29 %, and active area : 0.433 cm2), which is the highest efficiency among Cu2ZnSn(S,Se)4 thin film solar cells prepared using sputter deposited metallic precursors and without using a toxic H2Se gas. Details about other experimental results will be discussed during the presentation.

• 한국재료학회지
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• 제32권11호
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• pp.481-488
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• 2022

The Cu₂ZnSn(S_xSe_1-x)₄ (CZTSSe) absorbers are promising thin film solar cells (TFSCs) materials, to replace existing Cu(In,Ga)Se₂ (CIGS) and CdTe photovoltaic technology. However, the best reported efficiency for a CZTSSe device, of 13.6 %, is still too low for commercial use. Recently, partially replacing the Zn²⁺ element with a Cd²⁺element has attracting attention as one of the promising strategies for improving the photovoltaic characteristics of the CZTSSe TFSCs. Cd²⁺ elements are known to improve the grain size of the CZTSSe absorber thin films and improve optoelectronic properties by suppressing potential defects, causing short-circuit current (J_sc) loss. In this study, the structural, compositional, and morphological characteristics of CZTSSe and CZCTSSe thin films were investigated using X-ray diffraction (XRD), X-ray fluorescence spectrometer (XRF), and Field-emission scanning electron microscopy (FE-SEM), respectively. The FE-SEM images revealed that the grain size improved with increasing Cd²⁺ alloying in the CZTSSe thin films. Moreover, there was a slight decrease in small grain distribution as well as voids near the CZTSSe/Mo interface after Cd²⁺ alloying. The solar cells prepared using the most promising CZTSSe absorber thin films with Cd²⁺ alloying (8 min. 30 sec.) exhibited a power conversion efficiency (PCE) of 9.33 %, J_sc of 34.0 mA/cm², and fill factor (FF) of 62.7 %, respectively.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 추계학술발표대회
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• pp.35.1-35.1
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• 2011

New photovoltaic (PV) materials and manufacturing approaches are needed for meeting the demand for lower-cost solar cells. The prototypal thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4~1.6 ev and a large absorption coefficient of ${\sim}10^4\;cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative method for large area deposition of CZTS thin films that is potentially high throughput and inexpensive when used to produce monolithically integrated solar panel modules. Specifically, we have developed an aqueous chemical approach based on chemical bath deposition (CBD) with a subsequent sulfurization heat treatment. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and good optical properties. A preliminary solar cell device was fabricated to demonstrate rectifying and photovoltaic behavior.

• 한국산업보건학회지
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• 제6권2호
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• pp.249-264
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• 1996

This study was conducted for the purpose of obtaining the fundamental data on improvement of working environment and contributing to health improvement of workers who dealed with metal by assessing the metal concentration in air of industries located in Chang-Won Industrial Complex. Authors measured the concentration of metals(Al, Cd, Cr, Cu, Mn, Ni, Pb, Sn and Zn) is the air to 25 working processes of 73 industries by flame atomic absorption spectrometry from February to December 1994. Personal air sampler was used for air sampling with mixed cellulose-ester membrane filter. The results were as follows : 1. The geometric means(range) of metal concentration; 1) Al: $0.1505mg/m^3$ ($0.0147-18.6100mg/m^3$) 2) Cd: $0.0077mg/m^3$ ($0.0003-7.0710mg/m^3$) 3) Cr: $0.0163mg/m^3$ ($0.0013-1.1510mg/m^3$) 4) Cu: $0.0097mg/m^3$ ($0.0009-0.4950mg/m^3$) 5) Mn: $0.0412mg/m^3$ ($0.0006-4.7877mg/m^3$) 6) Ni: $0.0088mg/m^3$ ($0.0001-1.0170mg/m^3$) 7) Pb: $0.0152mg/m^3$ ($0.0015-0.4499mg/m^3$) 8) Sn: $0.0486mg/m^3$ ($0.0037-0.1500mg/m^3$) 9) Zn: $0.1911mg/m^3$ ($0.0122-8.2920mg/m^3$) 2. The geometric mean of lead exceeded TWA in assembling process of other general purpose machinery not elsewhere classified products manufacturing industries.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.99.1-99.1
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• 2012

The thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4 - 1.6 eV and a large absorption coefficient of ~104 $cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative aqueous chemical approach based on chemical bath deposition (CBD) method for large area deposition of CZTS thin films. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and some factors like triethanolamine, ammonia, temperature which strongly affect on the morphology of CZTS film.

• 한국산림과학회지
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• 제88권4호
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• pp.510-522
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• 1999

대기 오염물질인 $SO_2$, $SO{_4}^{-2}$, $NO{_3}^-$, $Cl^-$가 분진(粉塵)이나 강우와 함께 지표에 이르러 토양에 흡수 축적되고 중금속은 생활하수 및 음식 쓰레기, 공장 폐기물, 비료, 살충제 및 살균제, 채광활동 등에서 여러 가지 경로인 물질의 순환과정을 통해서 수권(水圈)이나 토양에 축적된다. 대기오염물질인 $SO{_4}^{-2}$, $NO{_3}^-$, $Cl^-$와 중금속은 식물 필수영양소(Co, Cu, Mo, Mn, Ni, V, Zn)와 인체나 동물에 유독성을 갖는 중금속(Cd, As, Pb, Hg, Cr, Se, Mo, Co) 중에서 Se, Mo, Zn, Cd, Pb, Mn, Cr, Co, V, As, Cu, Ni을 분석대상으로 하였고 이들의 도시에서 오염상태를 알기 위하여 도시지역인 광주 시내에 식재되어 있는 가로수 및 녹지대조성 수종과 대조구로서 광주에서 23km 떨어져 있는 나주시 산포면 산제리 소재 전라남도 산림환경연구소 구내에 생육하고 있는 수종을 대상으로 분석하였다. 분석대상 수종은 은행나무, 상수리나무, 개잎갈나무, 양버즘나무, 아까시나무, 오리나무, 메타세쿼이아, 느티나무, 벗나무, 소나무를 대상으로 하여 뿌리 및 잎 그리고 이들이 생육하고 있는 토양에 함유되어 있는 대기오염물질과 중금속의 함량을 분석 측정한 결과 다음과 같았다. 1. $SO{_4}^{-2}$, $NO{_3}^-$, $Cl^-$가 도시지역의 토양이 시외지역 토양보다 높은 함량을 보이고 있으며 $SO{_4}^{-2}$, $NO{_3}^-$이온은 뿌리보다 잎의 함량이 더 높았다. 2. $SO{_4}^{-2}$, $NO{_3}^-$이온의 흡수량이 은행나무, 아까시나무, 느티나무, 상수리나무, 양버즘나무가 많아 도시 가로수나 녹지대 조성수종으로 적합하다고 생각된다. 3. 토양에 중금속의 함유량은 도시지역이나 시외지역에서 Mn > Zn > V > Cr > Pb > Ni > Cu > Mo> Cd 순이고, Mn, Zn, Pb, V, Cu는 도시토양이 시외지역 토양보다 많은 양이 검출되었는데 이는 각종 오염원으로부터 오염된 결과로 생각된다. 뿌리와 잎에 함유된 중금속의 함유량도 Mn>Zn>Cr>Cu>V>Ni 순으로서 V의 순위가 다를 뿐 토양의 함유량의 크기순서와 같았다. 4. Mn과 Zn은 식물체에 흡수를 서로 방해하는 Antagonism 관계에 있는 것으로 알려져 있으나 본 연구에서는 Antagonism을 인정 할 수 없었다. 5. Sn, Mo, Cd, Pb는 도시지역이나 시외지역 토양에 축적되어 있으나 수목에 흡수되지 않아 뿌리나 잎에서 검출되지 않았다. 또 Se, Co와 As는 토양, 잎, 뿌리에서 검출되지 않았다. 6. 도시지역이나 시외지역에서 조사된 10개 수종 중 중금속의 흡수력이 특별히 월등하다고 인정할만한 수종이 없었다.