• Economic and Environmental Geology
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• v.34 no.1
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• pp.39-53
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• 2001

Environmental pollution of the Tohyun mine creek area was investigated on the basis of geology, mineralogy and geochemistry. In soils and sediments of the mine area, ${Al_2}{O_3}/{Na_2O}$ and ${K_2}O/{Na_2}O$ ratios are partly negative correlation against ${SiO_2}/{Al_2}{O_3}$, respectively. Geochemical characteristics of some trace and rare earth elements such as V/Ni, Ni/Co, La/Ce, Th/Yb, Th/U, La/Th, ${La_N}/{Yb_N}$, La/Sc and Sc/Th are revealed a narrow range and homogeneous compositions may be explained by simple source lithology. These results suggest that sediments source of the host shale around the mine area could be originated by basic to intermediate igneous rocks. Mineral compositions of soil and sediment near the mine area were partly variable mineralogy, which are composed of quartz, mica, feldspar, chlorite, clay minerals and some pyrite. Soils and sediments with highly concentrated heavy minerals, gravity separated mineralogy, are composed of some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, goethite and various kinds of hydroxide minerals on the polished sections. As normalized by bed rock composition, average enrichment indices of major elements in sediments, precipitates, farmland soils and paddy soils are 1.0, 1.7, 0.9 and 0.8, respectively. Maximum concentration of environmental toxic elements in the mine creek are detected with Ag = 186 ppm, As = 17,100 ppm, Bi = ]27 ppm, Cd = 77 ppm, Cu = 12,299 ppm, Pb = 8,897 ppm, Sb = 1,350 ppm, W = 599 ppm and Zn = 12,250 ppm, which are increasing with total FeO increasing, and extremely high concentrations of surface sediments and precipitates near the waste rock dump. These toxic elements (As, Bi, Cd, Cu, Pb, Sb, W and Zn) of the samples, normalizing by host rock concentration, revealed that average enrichment index is 106.0 for sediments, 279.6 for precipitates, 3.5 for farmland soils and 1.6 for paddy soils. However, on the basis of EPA values, enrichment indices of all the samples are 40.7, 121.4, 1.3 and 0.6, respectively.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.191.2-191.2
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• 2014

Cu/ZnO/$Al_2O_3$ is widely used methanol synthesis catalyst at elevated pressures P (50 to 100 bar) and temperatures T (473 to 573 K) using $CO_2$, CO, $H_2$ syngas mixture. Although Cu step and planar defects have been regarded as active sites in this catalyst, detailed $CO_2$ hydrogenation procedure has been still unknown and debated as well as initial intermediate. In this study, we investigated the mechanism of $CO_2$ hydrogenation on Cu(111) model surface at P (1 bar) and T (298 to 450 K) using reflection absorption infrared spectroscopy (RAIRS). Two distinct formates by hydrogenation of $CO_2$, on step and on terrace, show different behavior with elevating temperature. The peak intensity of on step formate was continuously decreased above 360 K up to 450K in contrast to the increase of on terrace formate. These phenomena are strong possibilities that the formate is initial intermediate and is desorbed by hydrogenation reaction because thermal desorption temperature of formate (~470 K) is much higher than desorption of on step formate. And the formate production peak of on step site was weakly correlated with CO formation.

• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3281-3289
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• 2011

The materials composed of the 3d series transition metals are introduced into the hydrocarbon steam-reforming reaction in order to enhance the $H_2$ production and abruptly depress the catalytic deactivation resulting from the strong sintering between the Ni component and the ${\gamma}-Al_2O_3$ support. The conventional impregnation method is used to synthesize the Ni/3d series metal/${\gamma}-Al_2O_3$ materials through the sequentially loading Ni source and the 3d series metal (Ti, V, Cr, Mn, Fe, Co, Cu, and Zn) sources onto the ${\gamma}-Al_2O_3$ support. The Mnloaded material exhibits a significantly higher reforming reactivity than the conventional Ni/${\gamma}-Al_2O_3$ and the other Ni/3d series metal/${\gamma}-Al_2O_3$ materials. Particularly the addition of Mn selectively improves the $H_2$ product selectivity by eliminating the formation of $CH_4$ and CO. The $H_2$ production is maximized at a value of 95% over Ni(0.3)/Mn(0.3)/${\gamma}-Al_2O_4$(1.0) with a butane conversion of 100% above $750^{\circ}C$ for up to 55 h.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.393-393
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• 2016

Cu(In,Ga)Se2 (CIGS) 박막 태양전지는 높은 효율과 낮은 제조비용, 높은 신뢰성으로 인해 박막 태양전지 중 가장 각광받고 있다. 특히 유리기판 대신 가볍고 유연한 철강소재나 플라스틱 소재를 이용하여 발전분야 외에 건물일체형, 수송용, 휴대용등 다양한 분야에 적용이 가능하다. 이러한 유연 기판을 이용한 CIGS 태양전지의 개발을 위해서는 기판의 특성에 따른 다양한 공정개발이 선행되어야 한다. Stainless steel과 같은 철강기판의 경우 Fe, Ni, Cr등의 불순물이 확산되어 흡수층의 특성을 저하시켜 효율을 감소시킨다. 따라서 이러한 철강 기판의 경우 불순물의 확산을 방지하는 확산방지막이 필수적이다. 이러한 유연기판의 특성을 고려하여 본 연구에서는 기존의 두껍고 추가 장비가 요구되는 SiOx나 Al2O3 대신 200nm 이하의 ZnO 박막을 이용하여 확산방지막을 제조하였다. 유연기판으로 STS 430 stainless steel을 이용하였다. 먼저 stainless steel 기판을 이용하여 기판에 의한 흡수층의 특성을 분석하였으며 ZnO 확산 방지막의 유무 및 두께에 따른 흡수층 및 소자의 특성을 분석하였다. 이때 확산 방지막은 기존 TCO 공정에서 사용되는 i-ZnO를 사용하였으며 RF sputter를 이용하여 50~200nm로 두께를 달리하며 특성 비교를 실시하였다. 효율은 확산방지막을 적용하지 않았을 때 약 5.9%에서 확산 방지막 적용시 약 10.7%로 증가하였다. 그 후 기판으로부터 확산되는 불순물의 유입에 의한 결함을 분석하기 위해 DLTS를 이용하여 소자 특성을 분석하였다. 온도는 80~300K으로 가변하며 측정을 실시하였으며 그 후 계산을 통해 activation energy와 capture cross section 값을 구하였다. DLTS 분석 결과 Ni이 CIGS 흡수층으로 확산되어 NiCu anti-site를 형성하여 태양전지의 효율을 감소시키는 것을 확인하였다. 모든 흡수층은 Co-Evaporation 방법을 이용하여 제조하였으며 제조된 흡수층은 SEM, XRF, XRD, GD-OES, PL, Raman등을 이용하여 분석하였으며 그 외 일반적인 방법을 이용하여 Mo, CdS, TCO, Al grid를 제조하였다. AR 코팅은 제외 하였으며 제조된 소자는 솔라 시뮬레이터를 이용하여 효율 특성 분석을 실시하였으며 Q.E. 분석을 실시하였다.

• Economic and Environmental Geology
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• v.31 no.4
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• pp.297-310
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• 1998

Geochemical characteristics of environmental toxic elements at the Narim mine area were investigated on the basis of major, minor, rare earth element geochemistry and mineralogy. Ratios of $Al_2O_3/Na_2O$ and $K_2O/Na_2O$ in soils and sediments range from 11.57 to 22.21 and from 1.86 to 3.93, and are partly negative and positive correlation against $SiO_2/Al_2O_3$ (3.41 to 4.78), respectively. These suggested that sediment source of host granitic gneiss could be due to rocks of high grade metamorphism originated by sedimentary rocks. Characteristics of some trace and rare earth elements of V/Ni (0.33 to 1.95), Ni/Co (2.00 to 6.50), Zr/Hf (11.27 to 53.10), La/Ce (0.44 to 0.55), Th/Yb (4.07 to 7.14), La/Th (2.35 to 3.93), $La_N/Yb_N$ (6.58 to 13.67), Co/Th (0.63 to 2.68), La/Sc (3.29 to 5.94) and Sc/Th (0.49 to 1.00) are revealed a narrow range and homogeneous compositions may be explained by simple source lithology. Major elements in all samples are enriched $Al_2O_3$, MgO, $TiO_2$ and LOI, especially $Fe_2O_3$ (mean=7.36 wt.%) in sediments than the composition of host granitic gneiss. The average enrichment indices of major and rare earth elements from the mining drainage are 2.05 and 2.91 of the sediments and are 2.02 and 2.60 of the soils, normalizing by composition of host granitic gneiss, respectively. Average composition (ppm) of minor and/or environmental toxic elements in sediments and soils are Ag=14 and 1, As=199 and 14, Cd=22 and 1, Cu=215 and 42, Pb=1770 and 65, Sb=18 and 3, Zn=3333 and 170, respectively, and extremely high concentrations are found in the subsurface sediments near the ore dump. Environmental toxic elements were strongly enriched in all samples, especially As, Cd, Cu, Pb, Sb and Zn. The level of enrichment was very severe in mining drainage sediments, while it was not so great in the soils. Based on the EPA value, enrichment index of toxic elements is 8.63 of mining drainage sediments and 0.54 of soils on the mining drainage. Mineral composition of soils and sediments near the mining area were partly variable being composed of quartz, mica, feldspar, amphibole, chlorite and clay minerals. From the gravity separated mineralogy, soils and sediments are composed of some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, goethite and various hydroxide minerals.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.298-299
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• 2010

Cu(In, Ga)Se2 (CIGS) 박막 태양전지는 Soda lime glass/Mo/CIGS/CdS/ZnO/ITO/Al 의 구조를 가지고 있다. CIGS 화합물은 direct bandgap 구조를 하고 있으며, 광흡수율이 다른 어떤 물질들 보다 뛰어나 박막으로도 충분히 태양광을 흡수할 수 있다. 또한 Ga의 도핑 농도에 따른 밴드갭 조절도 가능하다. 이러한 성질들로 인해 현재 박막태양전지로서 20.1%의 최고효율을 가지고 있다.[1] CIGS 박막 태양전지에서 p-CIGS layer와 스퍼터링으로 증착되는 n-ZnO layer사이의 buffer 층으로 chemical bath deposition (CBD)-CdS 박막을 주로 사용한다. CBD-CdS 박막은 n-ZnO 스퍼터로 증착 시킬 때, CIGS 층의 손상을 최소화하고, 이 두 층 사이에서의 격자상수와 밴드갭의 차이를 줄여주어 CIGS 박막태양전지의 효율을 증가 시키는 역할을 한다. 하지만, Cd (카드뮴)의 심각한 독성과 낮은 밴드갭(2.4eV)으로 인해 CIGS 층에서의 광흡수율을 줄여, CdS를 대체할 새로운 buffer 층의 필요성이 대두되었다.[2] 그 대안으로 ZnS, Zn(O, S, OH), (Zn, Mg)O, In2S3 같은 물질이 연구되고 있다. 현재 CBD-ZnS를 buffer 층으로 사용한 CIGS 박막태양전지의 효율은 최고 18.6%로 CBD-CdS의 최고효율보다는 약 1.5% 낮지만, ZnS가 높은 밴드갭(3.7~3.8eV)과 Cd-free 물질이라는 점에서 CdS를 대체할 물질로 각광받고 있다. 본 연구에서는 기존의 CdS 박막을 제조하는 방법과 같은 방법인 CBD를 이용하여 ZnS 박막을 제조하였다. ZnS 박막을 제조하기 위해서는 Zinc sulfate, Thiourea, 암모니아가 사용된다. 암모니아의 mol 농도에 따른 CBD-ZnS/CIGS 박막태양전지의 효율 변화를 관찰하기 위해 암모니아의 mol 농도는 1 mol, 2 mol, 3 mol, 4 mol, 5 mol, 6 mol, 그 이상의 과량을 사용하여 실험하였다. 실험 결과, 암모니아농도 5 mol에서 효율 13.82%를 확인할 수 있었다. 최고효율을 보인 조건인 암모니아 농도가 5 mol 일 때, Voc는 0.602V, Jsc는 33.109mA/cm2, FF는 69.4%를 나타내었다.

• Economic and Environmental Geology
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• v.31 no.2
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• pp.111-125
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• 1998

Dispersion, migration and enrichment of environmental toxic elements from the Samkwang Au-Ag mine area were investigated based upon major, minor and rare earth element geochemistry. The Samkwang mine area composed mainly of Precambrian granitic gneiss. The mine had been mined for gold and silver, but closed in 1996. According to the X-ray powder diffraction, mineral composition of stream sediments and soils were partly variable mineralogy, which are composed of quartz, orthoclase, plagioclase, amphibole, muscovite, biotite and chlorite, respectively. Major element variations of the host granitic gneiss, stream sediments and soils of mining and non-mining drainage, indicate that those compositions are decrese $Al_2O_3$, $Fe_2O_3$, MgO, $TiO_2$, $P_2O_5$ and LOI with increasing $SiO_2$ respectively. Average compositional ranges (ppm) of minor and/or environmental toxic elements within those samples are revealed as As=<2-4500, Cd=<1-24, Cu=6-117, Sb=1-29, Pb=17-1377 and Zn=32-938, which are extremely high concentrations of sediments from the mining drainage (As=2006, Cd=l1, Cu=71, Pb=587 and Zn=481 ppm, respectively) than concentrations of the other samples and host granitic gneiss. Major elements (average enrichment index=6.53) in all samples are mostly enriched, excepting $SiO_2$, $Na_2O$ and $K_2O$, normalized by composition of host granitic gneiss. Rare earth element (average enrichment index=2.34) are enriched with the sediments from the mining drainage. Minor and/or environmental toxic elements within all samples on the basis of host rock were strongly enriched of all elements (especially As, Br, Cu, Pb and Zn), excepting Ba, Cr, Rb and Sr. Average enrichment index of trace elements in all samples is 15.55 (sediments of mining drainage=37.33). Potentially toxic elements (As, Cd, Cr, Cu, Ni, Pb, and Zn) of the samples revealed that average enrichment index is 46.10 (sediments of mining drainage=80.20, sediments of nonmining drainage=5.35, sediments of confluent drainage=20.22, subsurface soils of mining drainage=7.97 and subsurface soils of non-mining drainage=4.15). Sediments and soils of highly concentrated toxic elements are contained some pyrite, arsenopyrite, sphalerite, galena and goethite.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.486-486
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• 2014

CIGS 박막태양 전지는 I-III-VI2 Chalcopyrite 결정구조를 가진 화합물 반도체 태양전지로 인위적인 밴드갭 조작이 용이하여 효율 향상에 높은 가능성을 보이고 있다. 4원소 화합물인 CIGS 광흡수층의 대표적인 제조 방법으로는 co-evaporation 공정법이 있다. 동시 증발법은 CIGS 결정을 최적화하기 위하여 박막이 증착되는 동안 기판의 온도를 3단계로 변화시켜주는 3-stage 공정을 통하여 제작된다. 일반적으로 CIGS 박막태양전지는 전면전극으로 투명전도막이 사용되며 높은 광투과성과 전기전도성을 가져야 한다. 투명전도막의 광학적, 전기적 특성은 CIGS 박막태양전지의 효율에 영향을 미치기 때문에 최적화된 조건이 요구된다. 본 연구에서는 CIGS 광흡수층은 Ga/(In+Ga)=0.31, Cu/(In+Ga)=0.86으로 최적화 시켰으며, 투명전도막은 Al이 도핑된 ZnO 박막을 RF 마그네트론 스퍼터링법을 이용하여 증착하였다. ZnO:Al 박막의 두께를 가변하여 증착하였으며 박막의 특성을 평가하고, CIGS 광흡수층에 이를 적용함으로써 태양전지 변환효율 특성을 연구하였다. CIGS 박막 태양전지의 투명전극인 ZnO:Al 박막의 두께가 500 nm 일 때, Jsc=29.521 mA/cm2, Voc=564 mV, FF factor=71.116%, Efficiency=12.375%의 광 변환효율을 얻을 수 있었으며, 이에 따른 투명 전도막의 전기적, 광학적 특성을 통해 CIGS 박막태양전지에 미치는 영향에 대해 조사하였다.

• Proceedings of the Materials Research Society of Korea Conference
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• 2006.05a
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• pp.38.1-38.1
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• 2006

• Economic and Environmental Geology
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• v.25 no.1
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• pp.27-39
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• 1992

Several pyrophyllite deposits occur around the Milyang area where Cretaceous andesitic rocks and spatially related granitic rocks are widely distributed. Pyrophyllite ores consist mainly of pyrophyllite, and quartz with small amount of sericite, pyrite, dumortierite, and diaspore. The andesitic rocks and spatially related granitic rocks in this area suggest that they could be formed from the same series of a calc-alkaline magma series. The contents of $SiO_2$, $Al_2O_3$, LOI(loss on ignition) are enriched, and $K_2O$, $Na_2O$, CaO, MgO, $Fe_2O_3$ are depleted in altered andesitic rocks and ores. Enrichment of As, Cr, Sr, V, Sb and depletion of Ba, Cs, Ni, Rb, U, Y, Co, Sc, Zn are characteristic during mineralization. The pyrophyllite ores can be discriminated from the altered-and unaltered wall-rocks by an increasing of $(La/Lu)_{cn}$ from 4.18~22.13 to 8.98~55.05. In R-mode cluster analysis, Yb-Lu-Y, La-Ce-Hf-Th-U-Zr, $TiO_2-V-Al_2O_3$, Sm-Eu, $CaO-Na_2O-MnO$, Cu-Zn-Ag, $K_2O-Rb$ are closely correlated. In the discriminant analysis of multi-element data, $P_2O_5$, As, Cr and $Fe_2O_3$, Sr are helpful to identify the ores from the unaltered-and altered wall-rocks. In the factor analysis, the factors of alteration of andesitic rocks and ore mineralization were extracted. In the change of ions per unit volume, $SiO_2$, $Al^{3+}$ and LOI are enriched and $Na^+$, $K^+$, $Ca^{2+}$, $Mg^{2+}$, $Mn^{2+}$ and $Fe^{3+}$ are depleted during the alteration processes. The Milyang and the Sungjin pyrophyllite deposits could be mineralized by hydrothermal alteration in a geochemical condition of low activity ratio of alkaline ions to hydrogen ion with reference to spatially related granitic rocks.