• The Journal of the Korea institute of electronic communication sciences
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• v.15 no.4
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• pp.665-670
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• 2020

Buffer layer in CIGS thin-film solar cells improves energy conversion efficiency through band alignment between the absorption layer and the window layer. ZnS is a non-toxic II-VI compound semiconductor with direct-transition band gaps and n-conductivity as well as with excellent lattice matching for CIGS absorbent layers. In this study, the structural and optical properties of ZnS thin films, deposited by RF magnetron sputtering method and subsequently performed by the rapid thermal annealing treatment, were investigated for the buffer layer. The zincblende cubic structures along (111), (220), and (311) were shown in all specimens. The rapid thermal annealed specimens at the relatively low temperatures were polycrystalline structure with the wurtzite hexagonal structures along (002). Rapid thermal annealing at high temperatures changed the polycrystalline structure to the single crystal of the zincblende cubic structures. Through the chemical analysis, the zincblende cubic structure was obtained in the specimen with the ratio of Zn/S near stoichiometry. ZnS thin film showed the shifted absorption edge towards the lower wavelength as annealing temperature increased, and the mean optical transmittance in the visible light range increased to 80.40% under 500℃ conditions.

• Journal of Electrochemical Science and Technology
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• v.9 no.4
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• pp.308-319
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• 2018

Single step electrodeposition of $Cu_2ZnSnS_4$ (CZTS) for solar cell applications was studied using an aqueous thiocyanate based electrolyte. The sodium thiocyanate complexing agent was found to decrease the difference in the deposition potential of the elements. X-ray diffraction analysis of the samples indicates the formation of kesterite phase CZTS. UV-vis studies reveal the band gap of the deposits to be in the range of 1.2 - 1.5 eV. The thickness of the deposit was found to decrease with increase in pH of the electrolyte. Nearly stoichiometric composition was obtained for CZTS films coated at pH 2 and 2.5. I-V characterization of the film with indium tin oxide (ITO) substrate in the presence and the absence of light source indicate that the resistance decrease significantly in the presence of light indicating suitability of the deposits for solar cell applications. Results of electrochemical impedance spectroscopic studies reveal that the cathodic process for sulfur reduction is the slowest among all the elements.

• Resources Recycling
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• v.30 no.2
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• pp.14-23
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• 2021

To investigate the potential for leaching of heavy metals by bacteria from ores stacked on actual mining sites, leaching tests of a complex metallic ore (Pb-Zn-As ore) were conducted over 60 days using acidophile bacteria Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans under initial acidic conditions. Initially, a small amount of heavy metals was leached due to the initial acidic conditions. After 20 days, when A. thiooxidans in the reactor was adapted to the ore, the amount of leached heavy metals rapidly increased; the concentrations of leached arsenic, iron, and zinc reached a maximum of 2800, 3700, and 2500 mg/L, respectively. On the other hand, in the presence of A. ferrooxidans or in the control test without bacteria, heavy metals, except zinc, were barely detected in leaching. Through this study, it was confirmed that (i) bacteria could leach heavy metals at mining sites under acidic conditions and (ii) leaching of heavy metals from a high arsenic-containing ore by A. thiooxidans was more significant than that by A. ferrooxidans.

• Economic and Environmental Geology
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• v.30 no.6
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• pp.505-517
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• 1997

Lead and zinc mineralization of the Kwangsin mine was formed in quartz and carbonate veins that filled fault-related fractures in the limestone-rich Samtaesan Formation of the Chosun Supergroup and the phyllite-rich Suchangni Formation of unknown age. A K-Ar date of alteration sericite indicates that the Pb-Zn mineralization took place during Late Cretaceous (83.5 Ma), genetically in relation to the cooling of the nearby Muamsa Granite (83~87 Ma). Mineral paragenesis can be divided into three stages (I, II, III): (I) the deposition of barren massive white quartz, (II) the main Pb-Zn mineralization with deposition of white crystalline quartz and/or carbonates (rhodochrosite and dolomite), and (III) the deposition of post-ore barren calcite. Mineralogic and fluid inclusion data indicate that lead-zinc minerals in middle stage II (IIb) were deposited at temperatures between $182^{\circ}$ and $276^{\circ}C$ from fluids with salinities of 2.7 to 5.4 wt. % equiv. NaCl and with log $fs_2$ values of -15.5 to -11.8 atm. The relationship between homogenization temperature and salinity data indicates that lead-zinc deposition was a result of fluid boiling and later meteoric water mixing. Ore mineralization occurred at depths of about 600 to 700 m. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S_{CDT}=9.0{\sim}14.5$ ‰) indicate a relatively high ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids (up to 14 ‰), likely indicating an igneous source of sulfur largely mixed with an isotopically heavier sulfur source (possibly sulfates in surrounding sedimentary rocks). There is a remarkable decrease of calculated ${\delta}^{18}O$ value of water in hydrothermal fluids with increasing paragenetic time: stage I, 14.6~10.1 ‰; stage IIa, 5.8~2.2 ‰; stage IIb, 0.8~2.0 ‰; stage IIc, -6.1~-6.8 ‰, This indicates a progressive increase of meteoric water influx in the hydrothermal system at Kwangsin. Measured and calculated hydrogen and oxygen isotope values indicate that the Kwangsin hydrothermal fluids was formed from a circulating (due to intrusion of the Muamsa Granite) meteoric waters which evolved through interaction mainly with the Samtaesan Formation (${\delta}^{18}O=20.1$ to 24.9 ‰) under low water/rock ratios.

• 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.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.21 no.6
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• pp.411-416
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• 2020

An optical arrangement has been set inside a photo-spectrometer to measure the reflectance of IR optics materials in mid IR range. The optical arrangement consists of equally spaced 4 gold coated full reflecting mirrors with the incidence angle of 45°. Baseline beam intensity I_B has been measured while the beam proceeds through the 4 mirrors. Reflectance of a mirror has been estimated from the I_B. And the beam intensity I_S with the specimen in the optical path has been measured with the 4th mirror replaced with the specimen. Reflectance of the specimen has been estimated from the value of I_S/I_B. Then the estimated reflectance has been put in Fresnel equation relating reflectance and refractive index(RI) to estimate the RI of the material. Measurement has been made for sapphire, germanium, magnesium fluoride, and zinc sulfide. The estimated RI of the materials are closely matching with reference data and the maximum difference less than 2% over the wavelength range 3-5㎛ for all materials tested. As an FT-IR photo-spectrometer with a broadband wavelength infrared light source is used, this method has the advantage of measuring the refractive index at multiple wavelengths in a single measurement.

• 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.