• Journal of Surface Science and Engineering
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• v.57 no.3
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• pp.140-154
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• 2024

As the trend towards miniaturization in semiconductor integration process, the limitations of interconnection metals such as copper, tungsten have become apparent, prompting research into the emergence of new materials like cobalt and emphasizing the importance of studying the corresponding process conditions. During the chemical mechanical polishing (CMP) process, corrosion inhibitors are added to the slurry, forming passivation layers on the cobalt surface, thereby playing a crucial role in controlling the dissolution rate of the metal surface, enhancing both removal rate and selectivity. This review investigates the understanding of the cobalt polishing process and examines the characteristics and behavior of corrosion inhibitors, a type of slurry additive, on the cobalt surface. Among the corrosion inhibitors examined, benzotriazole (BTA), 1,2,4-triazole (TAZ), and potassium oleate (PO) all improved surface characteristics through their interaction with cobalt. These findings provide important guidelines for selecting corrosion inhibitors to optimize CMP processes for cobalt-based semiconductor materials. Future research should explore combinations of various corrosion inhibitors and the development of new compounds to further enhance the efficiency of semiconductor processes.

• Economic and Environmental Geology
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• v.40 no.4
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• pp.347-360
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• 2007

In order to evaluate the degree and extent of heavy metal pollution and the environmental impacts of abandoned Cu mines in Goseong-gun, soils and paddies were collected from the mine area and have been analysed for heavy metal contents. The heavy metal contents were much higher in mountain soils than in paddy soils. Total content of heavy metals decreased in order of Cu>Zn>Pb>As>Cr>Cd in mountain soils whereas Zn>Pb>Cu>Cr>As>Cd in paddy soils. The extractable amount of heavy metals by 0.1/1N HCl decreased in order of Cu>Pb>Zn>As>Cd>Cr in mountain soils whereas Pb>Cu>Zn>As>Cd>Cr in paddy soils. Although the extraction ratios were highly various depending on the sampling site, their average values were in order of Cd(16%)>Pb(10%)>Cu(9%)>As(4.5%)>Zn-Cr(${\le}2.5%$). The soils investigated were enriched in heavy metals relative to the averages of earth crust as In order of $As{\ge}Cd$>Pb>Zn>Cu>Cr. Pollution index calculated from total or extractable heavy metals of soils indicated that the heavy metal pollution was restricted to mountain soils around abandoned Cu mines, especially the Samsan I mine. The metal contents of brown rice showed no significantly contaminated level as follows; As $nd{\sim}0.87mg/kg,\;Cd\;0.02{\sim}0.34mg/kg,\;Cu\;1.01{\sim}6.25mg/kg,\;Mn\;13.4{\sim}43.2mg/kg,\;Pb\;0.09{\sim}2.83mg/kg,\;and\;Zn\;16.5{\sim}79.1mg/kg$. From the extraction and dispersion properties of heavy metal with the soil pH ($4.5{\sim}7.8$), it can be deduced the conclusion that the heavy metal pollution is spreading in the study area mainly by the detrital migration of waste ore and gangue minerals rather than the dissolution and circulation of heavy metal.

• Mineral and Industry
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• v.26
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• pp.1-12
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• 2013

In this study, an accelerated carbonation process was applied to stabilize hazardous heavy metals of industrial solid waste incineration (ISWI) bottom ash and fly ash, and to reduce $CO_2$ emissions. The most commonly used method to stabilize heavy metals is accelerated carbonation using a high water-to-solid ratio including oxidation and carbonation reactions as well as neutralization of the pH, dissolution, and precipitation and sorption. This process has been recognized as having a significant effect on the leaching of heavy metals in alkaline materials such as ISWI ash. The accelerated carbonation process with $CO_2$ absorption was investigated to confirm the leaching behavior of heavy metals contained in ISWI ash including fly and bottom ash. Only the temperature of the chamber at atmospheric pressure was varied and the $CO_2$ concentration was kept constant at 99% while the water-to-solid ratio (L/S) was set at 0.3 and $3.0dm^3/kg$. In the result, the concentration of leached heavy metals and pH value decreased with increasing carbonation reaction time whereas the bottom ash showed no effect. The mechanism of heavy metal-stabilization is supported by two findings during the carbonation reaction. First, the carbonation reaction is sufficient to decrease the pH and to form an insoluble heavy metal-material that contributes to a reduction of the leaching. Second, the adsorbent compound in the bottom ash controls the leaching of heavy metals; the calcite formed by the carbonation reaction has high affinity of heavy metals. In addition, approximately 5 kg/ton and 27 kg/ton $CO_2$ were sequestrated in ISWI bottom ash and fly ash after the carbonation reaction, respectively.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.81.2-81.2
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• 2012

To fabricate a metal mold for injection molding, hot-embossing and imprinting process, mechanical machining, electro discharge machining (EDM), electrochemical machining (ECM), laser process and wet etching ($FeCl_3$ process) have been widely used. However it is hard to get precise structure with these processes. Electrochemical etching has been also employed to fabricate a micro structure in metal mold. A through mask electrochemical micro machining (TMEMM) is one of the electrochemical etching processes which can obtain finely precise structure. In this process, many parameters such as current density, process time, temperature of electrolyte and distance between electrodes should be controlled. Therefore, it is difficult to predict the result because it has low reliability and reproducibility. To improve it, we investigated this process numerically and experimentally. To search the relation between processing parameters and the results, we used finite element simulation and the commercial finite element method (FEM) software ANSYS was used to analyze the electric field. In this study, it was supposed that the anodic dissolution process is predicted depending on the current density which is one of major parameters with finite element method. In experiment, we used stainless steel (SS304) substrate with various sized square and circular array patterns as an anode and copper (Cu) plate as a cathode. A mixture of $H_2SO_4$, $H_3PO_4$ and DIW was used as an electrolyte. After electrochemical etching process, we compared the results of experiment and simulation. As a result, we got the current distribution in the electrolyte and line profile of current density of the patterns from simulation. And etching profile and surface morphologies were characterized by 3D-profiler(${\mu}$-surf, Nanofocus, Germany) and FE-SEM(S-4800, Hitachi, Japan) measurement. From comparison of these data, it was confirmed that current distribution and line profile of the patterns from simulation are similar to surface morphology and etching profile of the sample from the process, respectively. Then we concluded that current density is more concentrated at the edge of pattern and the depth of etched area is proportional to current density.

• Economic and Environmental Geology
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• v.42 no.5
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• pp.445-455
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• 2009

Microbiological sulfate reduction is the transformation of sulfate to sulfide catalyzed by the activity of sulfate-reducing bacteria using sulfate as an electron acceptor. Low solubility of metal sulfides leads to precipitation of the sulfides in solution. The effects of microbiological sulfate reduction on in-situ precipitation of arsenic and copper were investigated for the heavy metal-contaminated soil around the Songcheon Au-Ag mine site. Total concentrations of As, Cu, and Pb were 1,311 mg/kg, 146 mg/kg, and 294 mg/kg, respectively, after aqua regia digestion. In batch-type experiments, indigenous sulfate-reducing bacteria rapidly decreased sulfate concentration and redox potential and led to substantial removal of dissolved As and Cu from solution. Optimal concentrations of carbon source and sulfate for effective microbial sulfate reduction were 0.2~0.5% (w/v) and 100~200 mg/L, respectively. More than 98% of injected As and Cu were removed in the effluents from both microbial and chemical columns designed for metal sulfides to be precipitated. However, after the injection of oxygen-rich solution, the microbial column showed the enhanced long-term stability of in-situ precipitated metals when compared with the chemical column which showed immediate increase in dissolved As and Cu due to oxidative dissolution of the sulfides. Black precipitates formed in the microbial column during the experiments and were identified as iron sulfide and copper sulfide. Arsenic was observed to be adsorbed on surface of iron sulfide precipitate.

• Economic and Environmental Geology
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• v.37 no.1
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• pp.133-142
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• 2004

The purpose of this study is to evaluate a laboratory test on arsenic removal effciency for ARD(Acid Rock Drain-age) using limestone and apatite, and on heavy metals removal efficiencies for AMD(Acid Mine Drainage) using apatite and fish bone. As a result of the laboratory test, pH, arsenic removal rate of limestone & apatite are inversely proportional to flow rates and apatite removes 100% of arsenic while limestone removes 37% of arsenic at 0.6$m{ell}$/min/kg flow rate in case of ARD treatment. And the dissolution amount of apatite is twenty five times higher than that of limestone. In case of AMD treatment, fish bone shows higher dissolution rate than apatite, and pH of outlet water reacted with fish bone is higher than that reacted with apatite. The heavy metal removal rates of fish bone are also higher than that of apatite except arsenic removal rate. The precipitate resulted from fish bone reaction with AMD seems to be biological sludge type while that resulted from apatite with AMD is inorganic solid which can settle easily compared with the biological sludge and can be cemented by gypsum. As the results, apatite can be used as a precipitant for the polluted mine waters showing wide range of pH and fish bone can be used for highly contaminated AMD.

• Economic and Environmental Geology
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• v.35 no.6
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• pp.553-565
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• 2002

Seasonal variations in vertical distributions of metals were investigated in the contaminated paddy soils around Siheung Cu-Pb-Zn and Deokeum Au-Ag mines. Geochemical behavior of metals was also evaluated with respect to redox changes during the cultivation of rice. Two microcosms simulating the rice-growing paddy field were set up in the laboratory. The raw paddy soils from two sites showed differences in mineralogy, metal concentrations and gecochemical parameters, and it is suggested that high proportions of exchangeable fractions in metals may give high dissolution rates at Deokeum. In both microcosms of Siheung and Deokeum, redox differences between surface and subsurface of paddy soils were maintained during the flooded period of 18 weeks. Siheung soil had neutral to alkaline pH conditions, while strongly acidic conditions and high Eh values were found at the surface soil of Deokeum. The concentrations of dissolved Fe and Mn were higher in the subsurface pore waters than in interface and upper waters from both microcosms, indicating reductive dissolution under reducing conditions. On the contrary, dissolved Pb and Zn had high concentrations at the surface under oxidizing conditions. From the Siheung microcosm, release of dissolved metals into upper waters was decreased. presumably by the trap effect of Fe- and Mn-rich layers at the interface. However, in the Deokeum microcosm, significant amounts of Pb and Zn were released into upper water despite the relatively lower contents in raw paddy soil, and seasonal variations in the chemical fractionation of metals were observed between flooded and drained conditions. Under acidic conditions, rice may uptake high amounts of metals from the surface of paddy soils during the flooded periods, and increases of exchangeable phases may also increase the bioavailability of heavy metals in the drained conditions.

• Journal of Soil and Groundwater Environment
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• v.11 no.1
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• pp.23-36
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• 2006

Experimental leaching of tailings was performed as a function of times (1, 2, 4, 7, 14, 21 and 30 days) in the laboratory using reaction solutions equilibrated to three different pH set-points (pHs 1,3 and 5). The initial pHs of 5 and 3 stabilized at either 4.6-6.1 or 2.8-3.5 in 2 days and decrease gradually with time afterwards. The results of the leaching tests indicate that the significant increase in the sulfate concentrations and in acidity after 7 days of leaching results from the oxidation of sulfide minerals. There were no significant variations in the extractable Pb found in the leach solutions of pH 5 and 3 within the reaction time (1-30 days), while Zn, Cd and Cu concentrations tend to significantly increase with time. In tailings leaching at an initial pH=1, two trends were observed: i) The 'Zn-type' (Zn, Cd and Cu), with increasing concentrations between days 1 and 30, corresponding to the expected trend when continuous dissolution is the dominant process, ii) the 'Pb-type' (Pb), with decreasing concentrations over time, suggesting rapid dissolution of a Pb source followed by the precipitation of 'anglesite' in relation to the large increase in dissolved sulfates. The high sulfate concentrations were coupled with high concentrations of released Fe, Zn and Cd. Release of Zn and Cd and acidity from these leaching experiments can potentially pose adverse impact to surface and groundwater qualities in the surrounding environment. The kinetic problems could be the important factor which leads to increasing concentrations of trace metals in the runoff water.

• Resources Recycling
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• v.18 no.5
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• pp.26-36
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• 2009

A recovery process of Ruthenium from waste electronic scrap has been investigated by means of nitric acid leaching as a part of development for scrap pretreatment process to obtaining an optimum conditions for removal of removing various impurities such as Pb, Bi, Zn, Al, Bi, Ag Fe, Co, Zr, Si. From the experiments, 90% of Pb leached with 250 g/l pulp density in 10-15% nitric acid. Leaching behavior of Ba was also similar to that of the Pb, but those of other metal impurities, such as Zn, Al, Bi, Ag, Fe, Co, Zr, showed different behavior, in which the dissolution rate increased as the concentration of nitric acid in solution is increased up to the 10% $HNO_3$ in solution and then it was constant above 10% $HNO_3$ concentrations. Meanwhile, the dissolution of Ru in $HNO_3$ solution was less then 100ppm, and that the total content of Ru in undissolved residue scrap was resulted in an increment of 50%.

• Economic and Environmental Geology
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• v.35 no.1
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• pp.55-66
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• 2002

There are several abandoned coal mines around Donghae mine area in the Taebaek coal field. Two major creeks, Soro and Sanae, are contaminated with the colored precipitates formed from the coal mine drainages. Bed rocks of the study area consist of limestone, shale, and sandstone. Limestone consisted mainly of calcite and dolomite, and shale of quartz, pyropyllite and chlorite, and sandstone of quatz and illite. Coal coal spoil dumps composed mainly of pyrite and chlorite. The oxidative dissolution of sulfide minerals leads to acid mine drainage and adds the metal ions in the stream water. The ion concentrations of Fe, Ca, Mg, Al, Si, SO$_{4}$in the stream polluted by AMD are generally higher than those in the unpolluted stream water. High concentrations of Ca and Mg, Al and Si can be resulted from dissolution of carbonate minerals such as calcite, dolomite and aluminosilicates such as chlorite, pyrophyllite. Although the Fe, Al, Si, SO$_{4}$ contents are considerbly high in the acid water released from the mine adits, they become decreased downstream due to dilution of unpolluted water and precipitation of oxide/hydroxide and sulfate minerals on the bottom of stream.