• Journal of the Korean Vacuum Society
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• v.22 no.1
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• pp.1-6
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• 2013

In this paper, to develop linear source for evaporating $600{\times}1,200mm$ size of large area CIGS absorber layer, we simulated linear thermal source and obtained ${\pm}5%$ thickness uniformity with various nozzle sizes and regular nozzle distance. Flux density was confirmed linear source length. Using this linear source, we tested thickness uniformity of Copper, Indium single layer which was obtained Cu ${\pm}5%$ and In ${\pm}5%$ thickness uniformity. And then CIGS absorber layers were evaporated with In-line single-stage co-evaporation. Large area CIGS absorber layers were confirmed composition uniformity of $$Cu{\leq_-}5%$$, $$In{\leq_-}7%$$, $$Ga{\leq_-}4%$$, $$Se{\leq_-}3%$$ with 600 mm width by XRF. Uniform shape of CIGS absorber layers was confirmed by SEM. XRD showed peaks which indicate chalcopyrite structure of CIGS absorber layers. Thus, developed linear source is suitable for evaporating CIGS absorber layer.

• Economic and Environmental Geology
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• v.22 no.3
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• pp.253-266
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• 1989

The Cu-Pb-Zn-Ag hydrothermal vein type deposits which comprise the Dongil and Dong-cheogogsan mines occur within the Cretaceous sedimentary rocks in the Euiseong Basin of the southern Korean peninsula. The ore mineralization is contained within three stage(I,II and III) quartz and calcite veins. Ore minerals occur as dominant chalcopyrite, galena, sphalerite, tetrahedrite and Pb, Ag, Sb and Bi-bearing sulfosalts. Stage I ore minerals were deposited between $400^{\circ}C$ and $200^{\circ}C$ from the fluid with moderate salinities(7.0 to 4.5 eq. wt. % NaCl). Evidence of boiling suggests pressure of less than 150 bars during stage I mineralization. This pressure corresponds to maximum depths of 650 m and 1700 m, respectively, assuming lithostatic and hydrostatic loads. The data on mineralogy, temperature and salinity, together with information on the solubility of Cu complex, suggest that Cu deposition is a result of boiling coupled with declining temperature from $350^{\circ}$ to $250^{\circ}C$ or declining log $a_{o_2}$(from -29.8 to -35.9 atm.)and increasing in pH. Pb, Ag, Sb and Bi-bearing sulfosalts were deposited by cooling and dilution at temperature of less than $250^{\circ}C$ from the ore fluid with less than -35.9 atm. of log $a_{o_2}$.

• Economic and Environmental Geology
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• v.50 no.4
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• pp.313-324
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• 2017

Tsogttsetsii area, an intrusive complex associated with Cu mineralization, is located in the South Gobi, Mongolia. We performed the cross geochemical and extended exploration survey in Tsogttsetsii area. Cu mineralization in Tsogttsetsii area is porphyry Cu type related with alkali granite intruded in Late Carboniferous to Early Permian. In the concentrated occurring to malachite appears extensively prophylitic alteration zone having a chlorite and epidote. As results of the survey, Cu contents of potable XRF and of chemical composition for altered rocks ranges 1.08 to 18.3% in the 30 points and 1.08 to 32.9% in the 13 points, respectively. Ore minerals identified in XRD analysis and polarizing microscope that samples of copper oxides were composed mainly of malachite, azurite, permingeatite and cuprite and the other minerals are pyrite, chalcopyrite, pyrargyrite, dickite, calcite, chlorite and epidote. Mineralization can be considered occurring to selectively some granite of the surrounding aplite and faults in the only upper part coming up the hydrothermal solution of the remaining residual magma after the aplite intrusion.

• Economic and Environmental Geology
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• v.31 no.5
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• pp.389-398
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• 1998

The Au-Ag deposit of the Oknam mine occurs as gold-silver-bearing rhodochrosite veins in biotite schist and phyllite of the Precambriam Yulri Group. Five stages of ore deposition are recognized, each showing a definite mineral assemblage. General mineral parageneses in veins (stage III) associated with gold and silver vary inwardly from the vein margin: arsenopyrite + pyrite $\Rightarrow$ sphalerite+chalcopyrite+galena+gold $\Rightarrow$ ga1ena+Ag-bearing minerals. Fluid inclusion data indicate that temperature and salinity of ore fluids overally decreased with time: $345^{\circ}{\sim}240^{\circ}C$ and 3.4~7.8 wt. % NaCl equiv during stage I (quartz vein mineralization), $313^{\circ}{\sim}207^{\circ}C$ and 2.3~8.7 wt.% NaCl equiv during manganese-bearing carbonate stages (II and III), and $328^{\circ}{\sim}213^{\circ}C$ and 3.6-5.4 wt.% NaCl equiv during stage IV (quartz vein mineralization). The ore fluids probably evolved through repeated pulses of boiling and later mixing with cooler and more dilute meteoric waters. Fluid inclusion data and geologic arguments indicate that pressures during the mineralization were in the range of 90 to 340 bars. Gold occurs as silver-rich electrums (21 to 29 atom. % Au) and was deposited at temperatures between $300^{\circ}$ and $240^{\circ}C$. Thermochemical calculations suggest that gold was deposited as a combined result of increase in pH and decreases in temperature, $fs_2$ and $fo_2$.

• Economic and Environmental Geology
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• v.25 no.3
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• pp.233-243
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• 1992

Ore mineralization of the Hwanghak copper deposit in the Ogsan area occurred in three stages of quartz (stage I and II) and calcite (stage III) veining along fissures in Early Cretaceous sedimentary rocks. Ore minerals are pyrite, pyrrhotite, chalcopyrite (dominant), sphalerite, hematite, galena, and Ag-, Pb-, and Bi-sulfosalts. These were deposited during the first stage at temperatures between $370^{\circ}C$ and < $200^{\circ}C$ from fluids with salinities between 0.5 and 7.6 equiv. wt. % NaCl. There is evidence of boiling and this suggests pressures of less than 180 bars during the first stage. Equilibrium thermodynamic interpretation accompanying with mineral paragenesis and fluid inclusion data indicates that copper precipitation in the hydrothermal system occurred due to cooling and changing in chemical conditions ($fs_2$, $fo_2$, pH). Gradual temperature decrease from $350^{\circ}$ to $250^{\circ}C$ of ore fluids by boiling and mixing with less-evolved meteoric waters mainly led to copper deposition through destabilization of copper chloride complexes. Sulfur isotope values of sulfide minerals decrease systematically with paragenetic time from calculated ${\delta}^{34}S_{H_2S}$ values of 8.2 to 4.7‰. These values, together with the observed change from sulfide-only to sulfide-hematite assemblages and fluid inclusion data, suggest progressively more oxidizing conditions, with a corresponding increase of the $sulfate/H_2S$ ratio of hydrothermal fluids. Measured and calculated hydrogen and oxygen isotope valutls of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values.

• Economic and Environmental Geology
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• v.46 no.2
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• pp.199-206
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• 2013

The Daehyun gold-silver deposit consists of two hydrothermal quartz veins that fill NE-trending fractures in the Cambro-Ordovician calcitic marble. I have sampled wallrock, hydrothermaly-altered rock and gold-silver ore vein to study the element dispersion and element gain/loss during wallrock alteration. The hydrothermal alteration doesn't remarkably recognized at this deposit and consists of mainly calcite, dolomite, quartz and minor epidote. The ore minerals composed of arsenopyrite, pyrrhotite, pyrite, sphalerite, stannite, chalcopyrite, galena, electrum, native bismuth and silver-bearing mineral. Based on analyzed data, the chemical composition of wallrock consists of mainly $SiO_2$, CaO, $CO_2$ with amounts of $Al_2O_3$, $Fe_2O_3(T)$ and MgO. The contents of $SiO_2$, $Fe_2O_3(T)$, MgO, CaO and $CO_2$ vary significantly with distance from ore vein. The element dispersion doesn't remarkably recognized during wallrock alteration and only occurs near the ore vein margin because of physical and chemical properties of wallrock. Remarkable gain elements during wallrock alteration are $Fe_2O_3(T)$, total S, Ag, As, Bi, Cd, Cu, Ni, Pb, Sb, Sn, W and Zn. Remarkable loss elements are $SiO_2$, MnO, MgO, CaO. $CO_2$ and Sr. Therefore, Our result may be used when geochemical exploration carry out at deposits hosted calcitic marble in the Hwanggangri metallogenic district.

• Economic and Environmental Geology
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• v.46 no.2
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• pp.153-163
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• 2013

The Ogcheon Au-Ag deposit consists of two quartz veins that fill the NE or NW-trending fissures in the metasedimentary rocks of unknown age. The quartz veins occur mainly in the massive type with partially breccia and cavity. They can be found along the strike for about minimum 50 m and varied in thickness from 0.1 to 0.3 m. The mineralogy of quartz veins from the Ogcheon deposit is mainly composed of hydrothermal alteration minerals such as pyrite, quartz, sericite, chlorite, clay minerals and sulfides including pyrite, pyrrhotite, arsenopyrite, sphalerite, chalcopyrite and galena. Fluid inclusion data from quartz indicate that homogenization temperatures and salinity of mineralization range from 184 to $362^{\circ}C$ and from 0.0 to 6.6 wt.% eq. NaCl, respectively. These suggest that ore forming fluids were progressively cooled and diluted from mixing with meteoric water. Sulfur(${\delta}^{34}S$: 0.4~8.4‰) isotope composition indicates that ore sulfur was derived from mainly magmatic source although there is a partial derivation from the host rocks. The calculated oxygen(${\delta}^{18}O$: 4.9~12.1‰) and hydrogen(${\delta}D$: -92~-74‰) isotope compositions suggest that magmatic and meteoric ore fluids were equally important for the formation of the Ogcheon deposit and then overlapped to some degree with another type of meteoric water during mineralization.

• 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.

• Geophysics and Geophysical Exploration
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• v.17 no.4
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• pp.247-252
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• 2014

Gagok Mine, which is skarn deposits, includes sulfide minerals such as sphalerite, galena, chalcopyrite, and pyrrhotite. To explore these minerals, spectral induced polarization (SIP) is relatively effective compared to other geophysical exploration methods because there is a strong IP effect caused by electrode polarization. In the SIP, the chargeability related to sulfide mineral contents and the time constant related to the grain size of the minerals are obtained. For this reason, we aim to compare difference in the mineralized characteristics between two orebodies in the Gagok Mine by using the chargeability and the time constant. For this study, we sampled ores from the south of Wolgok orebody and the north of Sungok orebody. In order to recognize the mineralization characteristics, the metal content of the samples was measured by a potable XRF and the SIP data of the samples were acquired by using a laboratory SIP measurement system. As a result, the metals in the samples such as Pb, Zn, Cu, and Fe were detected by the portable XRF measurement. In particular, the Fe and Zn contents were far higher than the other metals. The Fe and the Zn were caused by the sphalerite and the pyrrhotite through microscopy. The Wolgok orebody had higher sulfide mineral contents than the Sungok orebody and the result corresponded with the chargeability result. However, we considered that the Sungok orebody had a larger sulfide mineral grain size than the Wolgok orebody because the time constant of the Sungok orebody was larger.

• Journal of the Korean Electrochemical Society
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• v.13 no.2
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• pp.89-95
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• 2010

The chalcopyrite $Cu(In_xGa_{(1-x)})Se_2$ (CIGS) is considered to be one of the effective light-absorbing materials for thin film photovoltaic solar cells. We describe the electrodeposition of CIGS thin films in ambient laboratory conditions, and suggest the electrochemical conditions to prepare stoichiometric CIGS thin films of Ga/(In + Ga) = 0.3. In acidic solutions containing $Cu^{2+}$, $In^{3+}$, $Ga^{3+}$ and $Se^{4+}$ ions, the CIGS films of different Cu/In/Ga/Se chemical compositions were electrodeposited onto Mo/Glass substrate. The structure, morphology and chemical composition of electrodeposited CIGS films were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), and Energy dispersive X-ray spectroscopy (EDS), respectively.