• Proceedings of the Korea Crystallographic Association Conference
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• 2002.11a
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• pp.45-47
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• 2002

반도체 소자의 고집적화 및 고속화가 요구됨에 따라 MOSFET 구조의 게이트 절연막으로 사용되고 있는 SiO₂ 박막의 두께를 감소시키려는 노력이 이루어지고 있다. 0.1㎛ 이하의 소자를 위해서는 15Å 이하의 두께를 갖는 SiO₂가 요구된다. 하지만 두께감소는 절연체의 두께와 지수적인 관계가 있는 누설전류를 증가시킨다[1-3]. 따라서 같은 게이트 개패시턴스를 유지하면서 누설전류를 감소시키기 위해서는 높은 유전상수를 갖는 두꺼운 박막이 요구되는 것이다. 그러므로 약 25정도의 높은 유전상수를 갖고 5.2～7.8 eV 정도의 비교적 높은 bandgap을 갖으며, 실리콘과 열역학적으로 안정한 물질로 알려진 HfO2[4-5]가 최근 큰 관심을 끌고 있다. 본 연구에서는 HfO₂ 박막을 실제 소자에 적용하기 위하여 전극 및 열처리에 따른 HfO₂ 박막의 미세구조 및 전기적 특성에 관한 연구를 수행하였다. 이를 위해, HfO₂ 박막을 reactive DC magnetron sputtering 방법으로 증착하고, XRD, TEM, XPS를 사용하여 ZrO₂ 박막의 미세구조를 관찰하였으며, MOS 캐패시터 구조의 C-V 및 I-V 특성을 측정하여 HfO₂ 박막의 전기적 특성을 관찰하였다. HfO₂ 타겟을 스퍼터링하면 Ar 스퍼터링에 의해 에너지를 가진 산소가 기판에 스퍼터링되어 Si 기판과 반응하기 때문에 HfO₂ 박막 형성과 더불어 Si 기판이 산화된다[6]. 그래서 HfO₂같은 금속 산화물 타겟 대신에 순수 금속인 Hf 타겟을 사용하고 반응성 기체로 O₂를 유입시켜 타겟이나 시편위에서 high-k 산화물을 만들면 SiO/sub X/ 계면층을 제어할 수 있다. 이때 저유전율을 갖는 계면층은 증착과 열처리 과정에서 형성되고 특히 500℃ 이상에서 high-k/Si를 열처리하면 계면 SiO₂층은 증가하는 데, 이것은 산소가 HfO₂의 high-k 박막층을 뚫고 확산하여 Si 기판을 급속히 산화시키기 때문이다. 본 방법은 증착에 앞서 Si 표면을 희석된 HF를 이용해 자연 산화막과 오염원을 제거한 후 Hf 금속층과 HfO₂ 박막을 직류 스퍼터링으로 증착하였다. 우선 Hf 긍속층이 Ar 가스 만의 분위기에서 증착되고 난 후 공기중에 노출되지 않고 연속으로 Ar/O₂ 가스 혼합 분위기에서 반응 스퍼터링 방법으로 HfO₂를 형성하였다. 일반적으로 Si 기판의 표면 위에 자연적으로 생기는 비정질 자연 산화막의 두께는 10～15Å이다. 그러나 Hf을 증착한 후 단면 TEM으로 HfO₂/Si 계면을 관찰하면 자연 산화막이 Hf 환원으로 제거되기 때문에 비정질 SiO₂ 층은 관찰되지 않았다. 본 실험에서는 HfO2의 두께를 고정하고 Hf층의 두께를 변수로 한 게이트 stack의 물리적 특성을 살펴보았다. 선증착되는 Hf 금속층을 0, 10, 25Å의 두께 (TEM 기준으로 한 실제 물리적 두께) 로 증착시키고 미세구조를 관찰하였다. Fig. 1(a)에서 볼 수 있듯이 Hf 금속층의 두께가 0Å일때 13Å의 HfO₂를 반응성 스퍼터링 방법으로 증착하면 HfO₂와 Si 기판 사이에는 25Å의 계면층이 생기며, 이것은 Ar/O₂의 혼합 분위기에서의 스퍼터링으로 인한 Si-rich 산화막 또는 SiO₂ 박막일 것이다. Hf 금속층의 두께를 증가시키면 계면층의 성장은 억제되는데 25Å의 Hf 금속을 증착시키면 HfO₂ 계면층은 10Å미만으로 관찰된다. 그러므로 Hf 금속층이 충분히 얇으면 플라즈마내 산소 라디칼, 이온, 그리고 분자가 HfO₂ 층을 뚫고 Si 기판으로 확산되어 SiO₂의 계면층을 성장시키고 Hf 금속층이 두꺼우면 SiO/sub X/ 계면층을 환원시키면서 Si 기판으로의 산소의 확산은 막기 때문에 계면층의 성장은 억제된다. 따라서 HfO₂/Hf(Variable)/Si 계에서 HfO₂ 박막이 Si 기판위에 직접 증착되면, 순수 HfO₂ 박막의 두께보다 높은 CET값을 보이고 Hf 금속층의 두께를 증가시키면 CET는 급격하게 감소한다. 그러므로 HfO₂/Hf 박막의 유효 유전율은 단순 반응성 스퍼터링에 의해 형성된 HfO₂ 박막의 유전율보다 크다. Fig. 2에서 볼 수 있듯이 Hf 금속층이 너무 얇으면 계면층의 두께가 두꺼워 지고 Hf 금속층이 두꺼우면 HfO₂층의 물리적 두께가 두꺼워지므로 CET나 EOT 곡선은 U자 형태를 그린다. Fig. 3에서 Hf 10초 (THf=25Å) 에서 정전 용량이 최대가 되고 CET가 20Å 이상일 때는 high-k 두께를 제어해야 하지만 20Å 미만의 두께를 유지하려면 계면층의 두께를 제어해야 한다.

• The Korean Journal of Pesticide Science
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• v.2 no.3
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• pp.70-78
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• 1998

Dissipation, adsorption and desorption of oxadiazon were examined in two soils containing different amounts of soil organic matter. In addition, reactivity of oxadiazon with humic monomers was searched to clarify binding mechanism of oxadiazon to soil organic matter in the presence of a laccase of Myceliophthera thermophila. Half lives of oxadiazon were 38 days in Soil I and 45 days in Soil II. Freundlich constant, k values of fresh soils were higher than those of oxidized soils. Adsorption rates of oxadiazon were increased 17.1% in Soil I and 9.3% in Soil II in the presence of a laccase but no significant increase was observed in oxidized soils. Desorption rates of oxadiazon in fresh soils were lower than those in oxidized soils. Desorption rates of adsorbed oxadiazon in soils addes with the enzyme were not changed in oxidized soils but decreased in fresh soils. The herbicide oxadiazon alone underwent no transformation by a laccase but in the presence of catechol, guaiacol and gallic acid as humic monomer, transformation rates of it were from 20% to 24%.

• Polymer(Korea)
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• v.25 no.1
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• pp.6-14
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• 2001

The monomer N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium$(PF_6)_2$ was electrochemically polymerized on glassy carbon electrode surface. This polymer film electrode has electroactive sites on its bipyridinium ions distributed at the polymer strands. The formal potentials of the electrodes were -0.41V and -0.81V(vs. SSCE) for each step at phosphate buffer(pH=5.70). The diffusion coefficients of the dopants ions into the polymer matrix were $1.57{\times}10^{-4}$ and $4.35{\times}10^{-5}cm^2s^{-1}$ for first and second redox couple, respectively. The rate constants of electron transfer at $V^{2+/+}$ of the first step was a $57.53s^{-1}$, which was 22 times higher than $V^{+/0}$ one having $2.63s^{-1}$ in the solution. The charge transfer resistance of the polymer film was influenced by the dopant ion of the electrolyte. Thus the resistances were 22.63, 16.81, 12.44 and $11.36k{\Omega}$ for $LiClO_4,\;NaClO_4,\;KClO_4$, and phosphate buffer, respectively. The reaction order of the electropolymerization was first order and the rate constant of the polymerization was $1.31{\times}10^{-1}s^{-1}$ as determined by EQCM method. The G.C./p-BPB type electrode doped with phosphate ions showed a stability and reproducibility in CV procedure over 20 cycles.

• Economic and Environmental Geology
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• v.39 no.2 s.177
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• pp.151-162
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• 2006

Characteristics and changes of groundwater qualify were investigated in a riverbank filtration area at Daesan-myeon, Changwon City, Korea. The total dissolved solids (TDS) in groundwater samples collected in October were much less than that in March, indicating the mixing with recharged water from precipitation, as well as the changes of dissolved oxygen profiles at monitoring wells from March to October. Redox processes at depths appeared to trigger Fe and Mn contamination of groundwater in riverbank deposits. Amorphous oxyhydroxides md carbonate minerals such as $MnCO_3$ were probably the reactive phases for dissolved Fe and Mn, respectively. Groundwater contamination by nitrate-nitrogen $(NO_3-N)$ was controlled by the redox processes and subsequent denitrification at the sampled depths. Distribution of $NO_3-N$ concentrations at monitoring wells suggested that the nitrate contaminants were originated from agricultural facilities on the riverbank deposits. Some of monitoring wells, DS-2, D-2, DS-3, SJ-1, and SJ-3, were only partially penetrated into the sand/gravel aquifer, and subsequently, could not fully function to detect the water quality changes for the pumping wells. Proper measures, with regulating agricultural activities in the riverbank deposits, should be carried out to prevent groundwater contamination of the riverbank filtration area.

• Journal of the Korean Chemical Society
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• v.37 no.10
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• pp.881-887
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• 1993

A cobalt(II) ion-selective carbon-paste electrode (CPE) was constructed with ${\iota}$-sparteine. Cobalt(II) ion in aqueous solution was chemically deposited through the complexation with ${\iota}$-sparteine onto the CPE. The surface of CPEs were characterized by cyclic voltammetry and differential pulse voltammetry in an acetate buffer solution, separately. Exposure of the CPEs to an acid solution could regenerate surface to reuse it for the deposition. In more than 5 deposition / measurement / regeneration cycles, the response was reproducible and linear up to $5.0{\times}10^{-6}$M with linear sweep voltammetry. The peaks at 0.17V / 0.27V were correspond to the redox of Co(II)-SP complex deposited on CPE. The anodic peak of which appeared after scan over the cathodic peak of 0.17 V to more negative scan. In case of using the differencial pulse voltammetry (DPV), we have obtained the linear response $2.0{\times}10^{-7}$M with relative standard deviation ${\pm}5.6%$. The detection limit was $1.0{times}10^{-7}$M for 20 minutes of the deposition. We have also investigated the interference effect of various metal ions, which are expected to form the complex with the ligand on the electrode.

• Journal of the Korean Vacuum Society
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• v.22 no.3
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• pp.138-143
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• 2013

Recently, ZnO nanoparticles have been studied in various application fields due to their physico-chemical properties. In this study, we have researched on the ZnO photocatalytic activity by redox reaction. ZnO nanoparticles have low photocatalytic activity in comparison with $TiO_2$ nanoparticles because it has the disadvantage that the formation of $Zn(OH)_2$ in water solvent. Therefore, we were synthesized ZnO nanoparticles by spray-pyrolysis method, and then studied on stability in water solvent. At the results, the water treated-ZnO nanoparticles showed higher photocatalytic activity than non-treated ZnO nanoparticles because molecular $H_2O$ was increased onto the ZnO surface under the water treatment. Also, we confirmed that the ZnO nanoparticles synthesized by spray-pyrolysis method is very stable in the water solvent.

• Journal of the Korean Applied Science and Technology
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• v.30 no.1
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• pp.166-172
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• 2013

The purpose of this study is to evaluate the treatment ability of refractory organics in hot rolling precess waste water by redox(reduction and oxidation) reaction. Metal is oxidized in an aqueous solution to generate electron which can reduce water to generate hydroxy radical. These hydroxy radical is very effective to conduct hydrogen abstraction reaction and addition reaction to the carbon - carbon unsaturated link. The surface area of metal alloy reaction material is more than enough to get equilibrium at a single treatment. The efficiency of COD treatment by redox reaction showed maximum at mild pH of pH 7 and pH 6. But it was not effective in acidic atmosphere of pH 3, 4, 5 and basic atmosphere of pH 8 or over. Redox reaction system in much more helpful in a commercial coagulation sedimentation treatment than exclusive system.

• Applied Chemistry for Engineering
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• v.21 no.2
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• pp.178-182
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• 2010

Simultaneous removal reaction for NOx, soot over Pt catalysts using various $TiO_2$ as support was studied. The catalytic tests ware carried out injectin NO, soot, NO and soot simultaneously on each catalysts. As results, it showed different NOx removal efficiency and soot oxidation rate according to various kinds of $TiO_2$. Onset temperature of soot oxidation has a correlation to $NO_2$ generated for the independently performed NOx. It was investigated that NO to $NO_2$ oxidation was intimately related to crystallite size and surface area, and it has a tremendous impact on Pt aggregation on the catalyst surface and catalyst' reducibility. Therefore, we concluded that major index of the reaction was physico-chemical properties of catalyst' supports.

• Journal of Korean Society of Environmental Engineers
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• v.32 no.6
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• pp.599-608
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• 2010

The effect of silica(fumed) on nitrate reduction by zero-valent iron(ZVI) was studied using batch experiment. The reduction of nitrate was tested in three different aqueous media including de-ionized water, artificial groundwater and real groundwater contaminated by nitrate. Kinetics of nitrate reduction in groundwater were faster than those in de-ionized water, and first-order rate constant($k_{obs}$) of ZVI/silica(fumed) process was about 2.5 time greater than that of ZVI process in groundwater. Amendment of Silica(fumed) also decreased ammonium presumably through adsorption on silica surface. The pHs in all processes increased due to oxidation of ZVI, but the increase was lower in groundwater due to buffering capacity of groundwater. The result also showed amount of reduced nitrate increased as initial nitrate concentration increased in groundwater. Separate adsorption isotherm experiments indicated that fumed silica itself had some degree of adsorption capacity for ammonium. The overall results indicated that silica(fumed) might be a promising material for enhancing nitrate reduction by ZVI.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.443-454
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• 2013

Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically $V^{5+}$, $Co^{2+}$, and $Ni^{2+}$-incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated.