• Journal of the Korean Vacuum Society
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• v.2 no.4
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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.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.07a
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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.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.08a
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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]

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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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.

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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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.

• Korean Journal of Materials Research
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• v.32 no.11
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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.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.10a
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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.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.6 no.2
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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.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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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.

• Journal of Korean Society of Forest Science
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• v.88 no.4
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• pp.510-522
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• 1999

The air pollutants ; $SO_2$, $SO{_4}^{-2}$, $NO{_3}^-$, $Cl^-$ are absorbed into soils through falling with dusts and rain from the atmosphere. The sources of heavy metal contaminants in the environments are agricultural and horticultural materials, sewage sludges, fossil fuel combustion, metallurgical industries, electronics and waste disposal etc.. The soils and hydrosphere can be polluted on the way of the circulation of these heavy metals. Studied pollutant anions are $SO{_4}^{-2}$, $NO{_3}^-$ and $Cl^-$ and heavy metals are Se, Mo, Zn, Cd, Pb, Mn, Cr, Co, V, As, Cu and Ni which are the elements to be concerned with the essentials for plants, with animal and human health. This study is with the aim of selecting the species of roadside trees and green space trees which have excellent absorption of air pollutants and heavy metals from the atmosphere and the soils in the urban area. Two areas are designated to carry out this study : urban area ; Kwangju city and rural area ; the yard of Forest Environment Institute of Chollanam-do, at Sanje-ri, Sampo-myum, Naju city, Chollanam-do (23km away from Kwangju). This study is carried out to understand the movement of anions and heavy metals from the soils to the trees in both areas, the absorption of anions and heavy metals from atmosphere into leaves and the amounts of anions and heavy metals in leaves and fine roots(< 1mm dia.) of roadside trees and green space trees in Kwangju and trees in the yard of Forest Environment Institute of Chollanam-do. The tree species selected for this study in both areas are Ginkgo biloba, Quercus acutissima, Cedrus deodara, Platanus occidentalis, Robinia pseudoacacia, Alnus japonica. Metasequoia glyptostroboides. Zekova serrata. Prunus serrulata var. spontanea, and Pinus densiflora. The results of the study are as follows : 1. $SO{_4}^{-2}$, $NO{_3}^-$ and $Cl^-$ concentrations are higher in the soils of the urban area than in those of the rural area, and $NO{_3}^-$ and $SO{_4}^{-2}$ are higher in the leaves than in the roots due to the absorption of the these pollutants through the stomata. 2. Ginkgo biloba, Robinia pseudoacacia. Zekova serrata, Quercus acutissima, and Platanus occidentalis can be adequated to the roadside trees and the environmental trees due to their good absorption of $NO{_3}^-$ and $SO{_4}^{-2}$. 3. Heavy metals in the soils of both areas are in the order of Mn > Zn > V > Cr > Pb > Ni > Cu > Mo> Cd, and in the leaves and roots of the trees in the both areas are in the order of Mn>Zn>Cr>Cu>V>Ni. Both orders are similar ones except V. There are more in the urban soils than in the rural soils in amount of Mn, Zn, Pb, V, Cu. 4. It is supposed that there is no antagonism between Mn and Zn in this study. 5. Se, Co and As are not detected in the soils, the leaves and the roots in both areas. Sn, Mo, Cd and Pb are also not detected in the leaves and roots in spite of considerable amount in the soils of both areas.