• Bulletin of the Korean Chemical Society
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• v.27 no.10
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• pp.1572-1576
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• 2006

A dimeric precursor, $[Cu(dmae)(OCOCH_3)(H_2O)]_2$ for the CVD of copper metal films, (dmaeH = N,N-dimethylaminoethanol) was synthesized by the reaction of copper(II) acetate monohydrate ($Cu(OCOCH_3)_2{\cdot}H_2O$) and dmaeH in toluene. The product was characterized by m.p. determination, elemental analysis and X-ray crystallography. Molecular structure of $[Cu(dmae)(OCOCH_3)(H_2O)]_2$ shows that a dimeric unit $[Cu(dmae)(OCOCH_3)(H_2O)]_2$ is linked to another through hydrogen bond and it undergoes facile decomposition at 300 C to deposit granular copper metal film under nitrogen atmosphere. The decomposition temperature, thermal behaviour, kinetic parameters, evolved gas pattern of the complex, morphology, and the composition of the film were also investigated.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.23 no.2
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• pp.108-113
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• 2013

Chalcopyrite material $CuInSe_2$ (CIS) is known to be a very prominent absorber layer for high efficiency thin film solar cells. Current interest in the photovoltaic industry is to identify and develop more suitable materials and processes for the fabrication of efficient and cost-effective solar cells. Various processes have been being tried for making a low cost CIS absorber layer, this study obtained the CIS nanoparticles using commercial powder of 6 mm pieces for low cost CIS absorber layer by high frequency ball milling and cryogenic milling. And the CIS absorber layer was prepared by paste coating using milled-CIS nanoparticles in glove box under inert atmosphere. The chalcopyrite $CuInSe_2$ thin films were successfully made after selenization at the substrate temperature of $550^{\circ}C$ in 30 min, CIS solar cell of Al/ZnO/CdS/CIS/Mo structure prepared under various deposition process such as evaporation, sputtering and chemical vapor deposition respectively. Finally, we achieved CIS nanoparticles solar cell of electric efficient 1.74 % of Voc 29 mV, Jsc 35 $mA/cm^2$ FF 17.2 %. The CIS nanoparticles-based absorber layers were characterized by using EDS, XRD and HRSEM.

• Journal of Soil and Groundwater Environment
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• v.20 no.7
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• pp.103-111
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• 2015

Soil washing with ethylenediaminetetraacetic acid (EDTA) is highly effective in the remediation of soils contaminated with heavy metals. The EDTA recycling process is a requisite for reducing the operating cost. The applicability of Na₂S addition on the precipitation of heavy metals from the spent soil washing solution and thereby recycling of EDTA was investigated. Addition of Na₂S into the single metal-EDTA and the mixed metal-EDTA solutions ([Na₂S]/[metal-EDTA] ratio = 30, reaction time = 30 min and pH = 7~9) was highly effective in the separation of Cu and Pb from metal-EDTA complexes, but not for Ni. The Zn removal efficiency varied with pH and slightly increased upto 40% as the reaction time increased from 0 to 240 min which was longer than those for Cu and Pb. Ca(OH)₂ was subsequently added to induce further precipitation of Zn and Ni and to reduce the Na₂S dose. At the [Na₂S]/[metal-EDTA] ratio of 10, the removal efficiencies of all heavy metals excluding Ni were above 98% with the dose of Ca(OH)₂ at 0.002, 0.006 and 0.008 g into 100 mL of Cu-, Pb- and Zn-EDTA solutions, respectively. However, Ca(OH)₂ addition was not effective for Ni-EDTA solution. A further research is needed to improve metal removal efficiency and subsequent EDTA recycling for the real application in field-contaminated soils.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.48-48
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• 2007

P-type transparent conducting $CuGaO_2$ thin films have been prepared by DC/RF sputtering using Quartz(0001) and sapphire(0001) substrates. The target was fabricated by heating a stoichiometric mixture of CuO and $Ga_2O_3$ at 1373K for 12h under $N_2$ atmosphere. The film were deposited under mixture gas of Ar and $O_2(Ar:O_2=4:1)$ during 10~30min. and the as-deposited films were annealed at 1123K and $N_2$ atmosphere. Room temperature conductivity and the activation energy of the sintered body in the temperature range of 223K ~ 423K were 0 004S/cm, 1.9eV, respectively. XRD revealed that all of the as-deposited films were amorphous. Heating of the films deposited on Quartz substrates above 1123K resulted in crystallization with a second phase of $CuSiO_3$, which was assumed owing to reaction with Quartz substrate. The single phase of $CuGaO_2$ was obtained at the film deposited on the sapphire substrates. The transmittance after annealing of DC- and RF-sputtered films were 55~75% at 550nm. From the transmittance and reflectance measurement. the direct band gap of the DC/RF-sputtered films were 3.63eV and 3.57eV. and there was little difference between DC and RF sputtered films.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.04b
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• pp.38-41
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• 2004

The oxidizer plays an important role in the metal chemical mechanical polishing(CMP) slurry. Currently, the oxidizer used in CMP slurry is nearly divided into several kinds such as $Fe(NO_3)_3$, $H_2O_2$, $KIO_3$, and $H_5IO_6$. It is generally known that oxidizer character of $H_2O_2$ is more effective than other oxidizers. In this work, we have been studied the characteristics for the $H_2O_2$ concentration of copper slurry, which can applicable in the recent semiconductor manufacturing process. Also, it plays an important role in the planarization of copper films using copper slurries during micro-electronic device fabrication. In this work, we confirmed that removal rate of Cu/TaN changed by $H_2O_2$ concentration on copper slurry. And we used $KMnO_4$ in the measurement method of $H_2O_2$. In analysis results, we confirmed that the difference of results is large. We thought that the difference was due to organic component existence. So in titration method of $H_2O_2$ concentration, we used $Na_2S_2O_3$ instead of $KMnO_4$ as solution. Consequently, using the titration method, we could calculate correct data reduced error. And $H_2O_2$ concentration has been adjusted to the target concentration of 0.1 wt%.

• Analytical Science and Technology
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• v.20 no.6
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• pp.483-487
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• 2007

Electrochemistry of 1.0 mM bis(1,10-phenanthroline)copper(II) $(Cu(ph){_2}^{2+})$ in 100 mM NaCl solution including 27 mM $MgCl_2$ with and without sodium dodecyl sulfate (SDS) is studied. In the presence of SDS, $E_{pa}$ and $E_{1/2}$ of $Cu(ph){_2}^{2+}$ by adding $Mg^{2+}$ shifts to a positive direction compared to the SDS free. The intersection of two lines on ${\Delta}E_p$ vs -log[SDS] plot is determined as a critical micelle concentration (CMC). When $Mg^{2+}$ is added, it seems that the double layer became more compact. And the formation of micelles is retarded.

• Journal of Soil and Groundwater Environment
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• v.16 no.1
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• pp.42-50
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• 2011

Potential risk of heavy metals to various receptors including humans depends on the bioavailability of the heavy metals in soil. In this study, the heavy metal extraction methods using 0.1N HCl and aqua regia were compared with the Tessier's sequential extraction method to assess whether these two methods can be used to determine the plant-available heavy metal concentrations. The contamination characteristics of copper (Cu), cadmium (Cd), lead (Pb), and arsenic (As) found in soils collected from 75 sites around the closed Janghang smelter were analyzed by extracting heavy metals using 0.1 N HCl, aqua regia, and the Tessier's sequential extraction method. The portion of metals bioavailable to plants is considered as the sum of the fraction 1 (exchangeable) and the fraction 2 (carbonates binding) of the Tessier's 5-step sequential extraction method, which were determined to be 3.1 ${\pm}$ 3.82, 0.6 ${\pm}$ 0.15, 20.6 ${\pm}$ 18.78, and 7.0 ${\pm}$ 6.48 mg/kg for Cu, Cd, Pb, and As, respectively, in this study. When the extraction using aqua regia and the Tessier's extraction method were compared, the extracted Cu and Pb concentrations did not show significant differences, whereas the extracted Cd and As concentrations showed significant differences. These results indicate that the portion of Cd and As in the fraction 5 of the Tessier's sequential extraction can not be extracted using aqua regia. Using aqua regia, which is the official test method, higher concentrations of Cu, Cd, Pb and As were extracted than the sum of the fraction 1 and 2. The results show that only 9, 40, 39 and 10% of Cu, Cd, Pb and As using aqua regia can be uptaken by plants (i.e., plant-available). Using 0.1N HCl, the portion of Cd equivalent to about 66% the fraction 1 could be extracted, while, with Pb, the portion of the fraction 1 and about 90% of the fraction 2 could be extracted. With As, the portion equivalent to the fraction 1, 2 and 79% of the fraction 3 was extracted, while with Cu, the portion equivalent to the fraction 1, 2, 3 and 20% of the fraction 4 was extracted using 0.1N HCl.

• Korean Journal of Materials Research
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• v.8 no.9
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• pp.837-842
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• 1998

As the size of the integrated circuit is scaled down the importance of Si cleaning has been emphasized. One of the major concerns is abut the removal of metallic impurities such as Cu and Fe on Si surface. In this study, we intentionally contaminated Cu and Fe on the Si wafers and cleaned the wafer by cleaning splits of the chemical mixture of $\textrm{H}_2\textrm{O}_2$ and HF and the combination of HF treatment with UV/$\textrm{O}_3$ treatment. The contamination level was monitored by TXRF. Surface microroughness of the Si wafers was measured by AFM. The Si wafer surface was examined by SEM. AES analysis was carried out to analyze the chemical composition of Cu impurities. The amount of Cu impurities after intentional contamination was abut the level of $\textrm{10}^{14}$ atoms/$\textrm{cm}^2$. The amount of Cu was decreased down to the level of $\textrm{10}^{10}$ atoms/$\textrm{cm}^2$ by cleaning splits. The repeated treatment exhibited better Cu removal efficiency. The surface roughness caused by contamination and removal of Cu was improved by repeated treatment of the cleaning splits. Cu were adsorbed on Si surface not in a thin film type but in a particle type and its diameter was abut 100-400${\AA}$ and its height was 30-100${\AA}$. Cu was contaminated on Si surface by chemical adsorption. In the case of Fe the contamination level was $\textrm{10}^{13}$ atoms/$\textrm{cm}^2$ and showed similar results of above Cu cleaning. Fe was contaminated on Si surface by physical adsorption and as a particle type.

• Journal of Korea Foundry Society
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• v.31 no.1
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• pp.26-30
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• 2011

For the fabrication of bulk near-net-shape Ti-Ni-Cu shape memory alloys, consolidation of Ti-Ni-Cu alloy powders are useful because of their brittle property. In the present study, $Ti_{50}Ni_{30}Cu_{20}$ shape memory alloy powders were prepared by gas atomization and martensitic transformation temperatures and microstructures of those powders were investigated as a function of powder size. The size distribution of the powders was measured by conventional sieving, and sieved powders with the specific size range of 25 to $150\;{\mu}m$ were chosen for this examination. XRD analysis showed that the B2-B19 martensitic transformation occurred in the powders. In DSC curves of the as-atomized $Ti_{50}Ni_{30}Cu_{20}$ powders as a function of powder size, only one clear peak was found on each cooling and heating curve. The martensitic transformation start temperature($M_s$) of the $25-50\;{\mu}m$ powders was $31.5^{\circ}C$. The $M_s$ increased with increasing powder size and the difference of $M_s$ between $25-50\;{\mu}m$ powders and $100-150\;{\mu}m$ powders is only $1^{\circ}C$. The typical microstructure of the rapidly solidified powders showed cellular morphology and very small pores were observed in intercellular regions.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.239-240
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• 2008

As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.