• Economic and Environmental Geology
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• v.24 no.2
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• pp.131-150
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• 1991

The Weolseong diatreme was temporally and spatially related to the intrusion of the Gadaeri granite, and was -mineralized by meteoric aqueous fluids. In the Nokdong As-Zn deposit, pyrite, aresenopyrite and sphalerite are the most abundant sulfide minerals. They are associated with minor amount of magnetite, pyrrhotite, chalcopyrite and cassiterite, and trace amounts of Pb-Sb-Bi-Ag sulphosalts. The AsZn ore probably occurred at about $350^{\circ}C$ according to fluid inclusion and compositional data estimated from the arsenic content of arsenopyrite and iron content of sphalerite intergrown with pyrrhotite + chalcopyrite + cubanite. Heating studies of fluid inclusions in quartz indicate a temperature range between 180 and $360^{\circ}C$, and freezing data indicate a salinity range from 0.8 to 4.1 eq.wt % NaCl. The coexisting assemblage pyrite + pyrrhotite + arsenopyrite suggests that $H_2S$ was the dominate reduced sulfur species, and defines fluid parameter thus: $10^{-34.5}$ < ${\alpha}_{S_2}$ < $10^{-33}$, $10^{-11}$ < $f_{S_2}$ < $10^{-8}$, -2.4 < ${\alpha}_{S_2}$ < -1.6 atm and pH= 5.2 (sericte stable) at $300^{\circ}C$. The sulfur isotope values ranged from 1.8 to 5.5% and indicate that the sulfur in the sulfides is of magmatic in origin. The carbon isotope values range from -7.8 to -11.6%, and the oxygen isotope values from the carbonates in mineralized wall rock range from 2 to 11.4%. The oxygen isotope compositions of water coexisting with calcite require an input of meteoric water. The geochemical data indicate that the ore-forming fluid probably was generated by a variety of mechanisms, including deep circulation of meteoric water driven by magmatic heat, with possible input of magniatic water and ore component.

• Economic and Environmental Geology
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• v.35 no.1
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• pp.1-12
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• 2002

Manus Basin, located in the equatorial western Pacific, is a back arc basin formed by collision between the IndoAustralian and the Pacific Plates. The basin is host to numerous hydrothermal vent fields and ore deposits. The basement rocks of the Manus Basin consist primarily of dacite and basaltic andesite. Some of the minerals that form the hydrothermal chimneys that were dredged on the Manus basin include pyrite, chalcopyrite, marcasite, sphalerite and galena. The chimneys can be classified into chalcopyrite dominant Cu-rich type and sphalerite dominant Zn-rich type. The concentration of Zn shows good positive correlation with that of Sb, Cd and Ag. The content of Cu, on the other hand, positively correlates with that of Mo, Mn and Co. For samples that were taken from Zn-rich chimney, a strong positive correlation is found between Au and Zn contents. The chimney also shows enrichments of Cd, Mn and Sb. On the other hand, the samples from Cu-rich chimney exhibit strong correlation among Au, Zn and Pb, and are enriched in Mo and Co concentration. Average contents of Au in Cu-rich and Znrich chimneys were 15.9 ppm and 29.0 ppm, respectively. Because of high concentration of Au with Ag and Cu, the ore deposit have high economic potential. Homogenization temperatures and salinities of fluid inclusions in anhydrite and amorphous silica from Zn-rich chimney are estimated to be l74-220$^{\circ}$C and 2.7-3.6 equiv. wt. % NaCI, respectively. These value suggest that ore forming processes were occurred at around 200$^{\circ}$C and that the oxygen fugacity changed from 2: 10$^{-39.5}$bar to -s: 10$^{-40.8}$bar and the sulfur fugacity from -s: 10$^{-14.7}$bar to 10$^{-13.4}$bar during the process. It appears that the temperature at which the ores formed on Cu-rich chimney was higher than that on Zn-rich chimney.

• Economic and Environmental Geology
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• v.50 no.5
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• pp.325-340
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• 2017

The Seongdo Pb-Zn deposit, located in the northwestern part of the Ogcheon Metamorphic Belt, consists of skarn ore replacing limestone within the Hwajeonri Formation of Ogcheon Group and hydrothermal vein ore filling the fracture of host rock. Skarn minerals comprise mostly hedenbergitic pyroxene, garnet displaying oscillatory zonal texture composed of grossular and andradite, and a small amount of wollastonite, tremolite, and epidote, indicating reducing condition of formation. Ore minerals of skarn ore include sphalerite and galena with a small amount of pyrite, pyrrhotite, and chalcopyrite. In hydrothermal vein ore, arsenopyrite, sphalerite, chalcopyrite, and pyrite occur with a small amount of galena, native Bi, and stannite. Chemical compositions of sphalerite vary from 17.4 mole% FeS in average for dark grey sphalerite, 3.6 mole% for reddish brown sphalerite in skarn ore, and to 10.3 mole% FeS in hydrothermal vein ore. In comparison with representative metallic deposits in South Korea on the FeS-MnS-CdS diagram, skarn and hydrothermal vein ore plot close to the field of Pb-Zn deposits and Au-Ag deposits, respectively. Arsenic contents of arsenopyrite in hydrothermal vein ore decrease from 31.93~33.00 at.% in early stage to 29.58~30.21 at.% in middle stage, and their corresponding mineralizing temperature and sulfur fugacity are $441{\sim}490^{\circ}C$, $10^{-6}{\sim}10^{-4.5}atm$. and $330{\sim}364^{\circ}C$, <$10^{-8}atm$. respectively. Phase equilibrium temperatures calculated from Fe and Zn contents for coexisting sphalerite and stannite in hydrothermal vein are $236{\sim}254^{\circ}C$. Sulfur isotope compositions are 5.4~7.2‰ for skarn ore and 5.4~8.4‰ for hydrothermal vein ore, being similar or slightly higher to magmatic sulfur, suggesting that ore sulfur was mostly of magmatic origin with partial derivation from host rocks. However, much higher sulfur isotope equilibrium temperatures of $549^{\circ}C$와 $487^{\circ}C$, respectively for skarn ore and hydrothermal ore, than those estimated from phase equilibria imply that isotopic equilibrium has not been fully established.

• Economic and Environmental Geology
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• v.35 no.3
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• pp.179-189
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• 2002

The Geology of the Shizhuyuan W-Sn-Bi-Mo deposits, situated 16 Ian southeast of Chengzhou City, Hunan Province, China, consist of Proterozoic metasedimentary rocks, Devonian carbonate rocks, Jurassic granitic rocks, Cretaceous granite porphyry and ultramafic dykes. The Shizhuyuan polymetallic deposits were associated with medium- to coarse-grained biotite granite of stage I. According to occurrences of ore body, ore minerals and assemblages, they might be classified into three stages such as skarn, greisen and hydrothernlal stages. The skarn is mainly calcic skarn, which develops around the Qianlishan granite, and consists of garnet, pyroxene, vesuvianite, wollastonite, amphibolite, fluorite, epidote, calcite, scheelite, wolframite, bismuthinite, molybdenite, cassiterite, native bismuth, unidetified Bi- Te-S system mineral, magnetite, and hematite. The greisen was related to residual fluid of medium- to coarse-grained biotite granite, and is classified into planar and vein types. It is composed of quartz, feldspar, muscovite, chlorite, tourmaline, topaz, apatite, beryl, scheelite, wolframite, bismuthinite, molybdenite, cassiterite, native bismuth, unknown uranium mineral, unknown REE mineral, pyrite, magnetite, and chalcopyrite with minor hematite. The hydrothermal stage was related to Cretaceous porphyry, and consist of quartz, pyrite and chalcopyrite. Scheelite shows a zonal texture, and higher MoO) content as 9.17% in central part. Wolframite is WO); 71.20 to 77.37 wt.%, FeO; 9.37 to 18.40 wt.%, MnO; 8.17 to 15.31 wt.% and CaO; 0.01 to 4.82 wt.%. FeO contents of cassiterite are 0.49 to 4.75 wt.%, and show higher contents (4.]7 to 4.75 wt.%) in skarn stage (Stage I). Te and Se contents of native bismuth range from 0.00 to 1.06 wt.% and from 0.00 to 0.57 wt.%, respectively. Unidentified Bi-Te-S system mineral is Bi; 78.62 to 80.75 wt.%, Te; 12.26 to 14.76 wt.%, Cu; 0.00 to 0.42 wt.%, S; 5.68 to 6.84 wt.%, Se; 0.44 to 0.78 wt.%.

• Economic and Environmental Geology
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• v.25 no.4
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• pp.417-433
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• 1992

Lead-zinc-copper deposits of the Jeonheung and the Oksan mines around Euiseong area occur as hydrothermal quartz and calcite veins that crosscut Cretaceous sedimentary rocks of the Gyeongsang Basin. The mineralization occurred in three distinct stages (I, II, and III): (I) quartz-sulfides-sulfosalts-hematite mineralization stage; (II) barren quartz-fluorite stage; and (III) barren calcite stage. Stage I ore minerals comprise pyrite, chalcopyrite, sphalerite, galena and Pb-Ag-Bi-Sb sulfosalts. Mineralogies of the two mines are different, and arsenopyrite, pyrrhotite, tetrahedrite and iron-rich (up to 21 mole % FeS) sphalerite are restricted to the Oksan mine. A K-Ar radiometric dating for sericite indicates that the Pb-Zn-Cu deposits of the Euiseong area were formed during late Cretaceous age ($62.3{\pm}2.8Ma$), likely associated with a subvolcanic activity related to the volcanic complex in the nearby Geumseongsan Caldera and the ubiquitous felsite dykes. Stage I mineralization occurred at temperatures between > $380^{\circ}C$ and $240^{\circ}C$ from fluids with salinities between 6.3 and 0.7 equiv. wt. % NaCl. The chalcopyrite deposition occurred mostly at higher temperatures of > $300^{\circ}C$. Fluid inclusion data indicate that the Pb-Zn-Cu ore mineralization resulted from a complex history of boiling, cooling and dilution of ore fluids. The mineralization at Jeonheung resulted mainly from cooling and dilution by an influx of cooler meteoric waters, whereas the mineralization at Oksan was largely due to fluid boiling. Evidence of fluid boiling suggests that pressures decreased from about 210 bars to 80 bars. This corresponds to a depth of about 900 m in a hydrothermal system that changed from lithostatic (closed) toward hydrostatic (open) conditions. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S=2.9{\sim}9.6$ per mil) indicate that the ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids was ${\approx}8.6$ per mil. This ${\delta}^{34}S_{{\Sigma}S}$ value is likely consistent with an igneous sulfur mixed with sulfates (?) in surrounding sedimentary rocks. Measured and calculated hydrogen and oxygen isotope values of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values. Equilibrium thermodynamic interpretation indicates that the temperature versus $fs_2$ variation of stage I ore fluids differed between the two mines as follows: the $fs_2$ of ore fluids at Jeonheung changed with decreasing temperature constantly near the pyrite-hematite-magnetite sulfidation curve, whereas those at Oksan changed from the pyrite-pyrrhotite sulfidation state towards the pyrite-hematite-magnetite state. The shift in minerals precipitated during stage I also reflects a concomitant $fo_2$ increase, probably due to mixing of ore fluids with cooler, more oxidizing meteoric waters. Thermodynamic consideration of copper solubility suggests that the ore-forming fluids cooled through boiling at Oksan and mixing with less-evolved meteoric waters at Jeonheung, and that this cooling was the main cause of copper deposition through destabilization of copper chloride complexes.

• Economic and Environmental Geology
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• v.9 no.4
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• pp.177-212
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• 1976

The Shap granite encloses well developed quartz veins and veinlets containing molybdenite in association with other ore sulphide minerals. The preliminary study of the geochemical aspects of the granite stock and mineralisation of molybdenite in comparison with the porphyry deposits is carried out; the distribution of major, minor and ore metal elements in wall rocks, altered envelope and veins, and the molybdenum mineralisation, mainly in connexion with hydrothermal alteration are discussed. The molybdenite and other ore mineralisation, especially bismuthinite and chalcopyrite, are spatially closely related to the hydrothermal alteration adjacent to the veinings, and are dominant where the strong orthoclase alteration has taken place. A pattern of alteration and mineralisation can be recognised and forms the basic for the subdivision of the quarry into several distinct zones, which correspond with the sequence of alteration and mineralisation. The veins, veinlets and their alteration haloes can be further subdivided into a series of concentric zones.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.78.2-78.2
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• 2010

Cu(In,Ga)Se2 (CIGS)박막태양전지는 간단한구조와 가격경쟁력 및 고효율화 가능성에 대한 기대감에 의해 많은 연구가 수행되어오고 있다. 특히 높은 흡수계수와 적절한 밴드갭, 큰 결정크기와 같은 물질의 특성들이 장점으로 작용하고 있기 때문이다. 또한 CIGS박막태양전지는 다른 태양전지에 비해 광열화가 적다는 장점도 가지고 있다. CIGS 박막은 CuInSe2내의 In 사이트에 Ga을 도핑함으로서 형성이 되는데 그때의 밴드갭은 약 1.4eV이며 이를 형성하기 위해 많은 방법들이 제안되고 있는데, CIGS박막 형성 시 가장 중요시 여겨야 될 인자는 구성원소로부터 최적화된 조성비를 찾는 것이다. 이러한 관점에서 볼때 evaporation법이나 sputtering법같은 진공방식의 공정법이 비진공방식에 비해 최적의 조성비를 찾는 것이 수월할 것으로 생각된다. selenization을 하기전에, 동시증착이나 다층박막형성을 통해 Cu-In-Se의 조합이 일반적으로 이루어진다. 어떤방법이든 Se의 부가적인 공급이 이루어지는데 시작 전구체의 조합에서 그 해법을 제시하는 것에 대한 논의가 많이 부족한 현실로서, CuInSe2의 단일전구체에 의한 박막형성과 특성평가에 대해 구체적인 논의가 필요하다. 본 실험에서는 Cu-In-Se 전구체를 CuInSe2 단일 타겟에서부터 RF 마그네트론 스퍼터링법을 이용하여 박막증착을 하여 Se의 Rapid Thermal Process(RTA)법을 통해 Se이 순차적으로 공급되었다. 이때 형성되는 박막의 태양전지 흡수층 적용을 위한 광학적, 전기적 및 구조적에 대한 논의된다. Soda lime glass(SLG)와 Corning 1737 유리를 기판으로 하여 아세톤-에탄올을 이용, 초음파세척을 실시하였다. 스퍼터 공정을 하기전에 흡착된 물분자를 제거하기 위하여 약 30분간 $120^{\circ}C$로 열을 가해주었으며, 공정을 위한 총 아르곤 가스의 양은 약 50sccm이며 이때의 공정압력은 20mtorr로 고정하였다. 우선 RF power와 기판온도에 따른 단일전구체 형성을 관찰하기 위하여 각각 30~80W, RT~$400^{\circ}C$로 변화를 주어 박막을 형성한 후 모든 sample에 대하여 $500^{\circ}C$분위기에 effusion cell을 이용하여 Se 분위기에서 결정화를 실시하였다. 샘플의 두께는 Surface profiler로 측정하였고 단면은 전자주사현미경으로 관찰되었다. 동시에 SEM이미지를 통하여 morphology와 grain size 및 EDX를 통하여 조성분석을 하였다. 밴드갭, 투과율 및 흡수계수는 UV-VIS-NIR분광분석법을 통하여 수행되었으며, 전기적 특성분석을 위해 4-point-probe와 Hall effect측정을 수행하였다. 공정변수에 따른 단일타겟으로 얻어 결정화된 CuInSe2박막의 자세한 결과와 논의에 대하여 발표한다.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.79-79
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• 2010

다른 물질에 비해 많은 우수한 특성을 가지고 있는 CuInSe2(CIS)박막 태양전지는 많은 연구자들에 의해 개발되어 오고 있다. CIS의 대표적인 장점으로는 직접천이형 밴드갭, 높은 흡수계수, 열 안정화상태 및 p형으로의 전도성물질의 가능성 등 다양하다. 또한 간단한 구조를 이용하여 유리같은 싼 기판을 이용하기 때문에 저가형 태양전지로서 많은 각광을 받고 있다. CIGS태양전지는 CIS의 In 사이트에 Ga을 도핑함으로서 만들어지는데 밴드갭은 약 1.4eV이다. CIS박막을 만드는 많은 방법이 존재하나 구성원소로부터 최적화된 조성을 찾을수 있는 방법이 가장 중요한 요소 중의 하나로 인식되고 있으며, 이런점에서 증발법 및 스퍼터링법 등 같은 진공방식이 비진공방식에 비해 훨씬 간편하게 조성비를 맞출수 있다. 그 중에 스퍼터링법은 대면적 박막태양전지로의 가능성으로 비출어 볼때 산업화를 위한 좋은 후보군이 될 수 있다. Selenization을 하기전에 Cu-In-Se의 전구체 조합은 여러개의 타겟으로부터 동시 스퍼터링법이나 다층 전구체법을 사용하여 준비되는데 어떤 방법이 되던지 Se의 부가적인 공급은 불가피하다. 지금까지 많은 관련 연구의 대부분인 구조적, 조성비적 그리고 광학적인 특성평가에 집중되어 오고 있는데, 전기적특성평가의 경우는 면저항, 비저항 같은 간단한 결과 위주로 보고되어 오고 있다. 또한 캐리어농도와 이동도에 대한 보고가 있음에도 불구하고 이해되기에는 충분치 못한 면이 많다.본 발표에서는 태양전지 제조 전단계로서 소다라임유리기판(SLG)위에 Mo의 유무에 따라 CIS박막의 전기적인 특성 변화에 대한 내용을 담고 있다. 소다라임유리($2cm{\times}2cm$)를 기판으로 사용하여 아세톤-에탄올 용액에 초음파세척을 수행하고, Mo 후면전극을 DC 스퍼터링방식을 이용하여 증착을 한다. SLG와 Mo이 코팅된 SLG를 각각 RF 스퍼터 챔버에 이송한 후 수증기 제거를 위해 약 10분간 예열을 한다. 샘플에 대한 전기적특성은 Hall효과 측정장치에 의해 측정이 되며 전기전도도, 캐리어농도, 이동도 및 전도형에 대한 정보가 각각의 변수에 따라 조사된돠. 부가적으로 구조적, 조성비적인 특성을 SEM,XRD 및 EDX를 통해 조사를 하여 전기적 특성에 따른 관계성을 검토한다. SLG와 Mo가 코팅된 SLG위의 CIS박막은 전기적으로 약간 다른 특성을 보일 것으로 예측되며, 이러한 기대를 바탕으로 조성비가 이상적인 화학양론에 근접할 때 p형으로서 제시될 수 있다는 것을 보여줄 것이다.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.20 no.3
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• pp.107-112
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• 2010

The Cu$(In_{1-x}Ga_x)Se_2$ is the absorber material for thin film solar cell with high absorption coefficient of $1{\times}10^5cm^{-1}$. In the case of CIGS, the movable energy band gap from $CuInSe_2$ (1.00 eV) to $CuGaSe_2$ (1.68 eV) can be acquired while controlling Ga contain ratio. Generally, the co-evaporator method have used for development and fabrication of the CIGS absorption layer. However, this method should need many steps and lengthy deposition time with high temperature. For these reasons, in this paper, a new growth method of CIGS layer was attempted to hydride vapor transport (HVT) method. The CIGS mixed-source material reacted for HCl gas in the source zone was deposited on the substrate after transporting to growth zone. c-plane $Al_2O_3$ and undoped GaN were used as substrates for growth. The characteristics of grown samples were measured from SEM and EDS.

• Journal of Korea Soil Environment Society
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• v.5 no.2
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• pp.67-85
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• 2000

Fifty seven soil samples were collected from the paddy soil filled with tailings in the vicinity of the Seosung Pb-Zn mine. Those samples were analyzed for As, Cd, Co, Cr, Cu, Pb, and Zn in order to investigate heavy metal pollution levels in the paddy soil. Analyses of the soil samples were carried out using Inductively Coupled Plasma Atomic Emission Spectrometry(ICP-AES) . Paddy soils show pH range from 6.55 to 8.26. X-ray diffraction analyses of the paddy soil indicate that the soils consist predominantly ankerite, siderite, quartz, mica, and clay minerals with minor amounts of amphibole and chlorite. The mineral composition of the waste rocks consists of massive galena, sphalerite, and minor amounts of pyrite, arsenopyrite, chalcopyrite, calcite, siderite, Pb-sulfosalt, and marcasite. The paddy soils were significantly contaminated by heavy metals(average concentrations, As: 334.4 ppm, Cd: 37.6 ppm, Co: 15.7 ppm, Cu: 214.1 ppm, Pb: 4,612 ppm, and Zn: 4,468 ppm).