• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.84-84
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• 2012

소자가 고집적화 됨에 따라, 비저항이 낮고 electro migration (EM), Stress Migration (SM) 특성이 우수한 구리(Cu)를 배선재료로서 사용하고 있다. 그러나, 구리는 Si과 $SiO_2$의 내부로 확산이 빠르게 일어나, Si 소자 내부에 deep donor level을 형성하고, 누설 전류를 증가시키는 등 소자의 성능을 저하시킬 수 있는 문제점을 가지고 있다. 그러나, electroplating 을 이용하여 증착한 Cu 박막은 일반적으로 확산 방지막으로 쓰이는 TiN, TaN, 등의 물질과의 접착 (adhesion) 특성이 나쁘다. 따라서, Cu CMP 에서 증착된 Cu 박막의 벗겨지거나(peeling), EM or SM 저항성 저하 등의 배선에서의 reliability 문제를 야기하게된다. 따라서 Cu 와 접착 특성이 좋은 새로운 확산방지막 또는 adhesion layer의 필요성이 대두되고 있다. 본 연구에서는 이러한 Cu 배선에서의 접착성 문제를 해결하고자 Metal organic chemical vapor deposition (MOCVD)을 이용하여 제조한 코발트(Co) 박막을 $Cu/TaN_x$ 사이의 접착력 개선을 위한 adhesion layer로 적용하려는 시도를 하였다. Co는 비저항이 낮고, Cu 와 adhesion이 좋으며, Cu direct electroplating 이 가능하다는 장점을 가지고 있다. 하지만, 수소 분위기에서 $C_{12}H_{10}O_6(Co)_2$ (dicobalt hexacarbonyl tert-butylacetylene, CCTBA) 전구체에 의한 MOCVD Co 박막의 경우 탄소, 산소와 같은 불순물이 다량 함유되어 있어, 비저항, surface roughness 가 높아지게 된다. 따라서 구리 전착 초기에 구리의 핵 생성(nucleation)을 저해하고 핵 생성 후에도 응집(agglomeration)이 발생하여 연속적이고 얇은 구리막 형성을 방해한다. 이를 해결하기 위해, MOCVD Co 박막 증착 시 수소 반응 가스에 암모니아를 추가로 주입하여, 수소/암모니아의 분압을 1:1, 1:6, 1:10으로 변화시켜 $Co/TaN_x$ 박막의 특성을 비교 분석하였다. 각각의 수소/암모니아 분압에 따른 $Co/TaN_x$ 박막을 TEM (Transmission electron microscopy), XRD (X-ray diffraction), AES (Auger electron spectroscopy)를 통해 물성 및 조성을 분석하였고, AFM (Atomic force microscopy)를 이용하여, surface roughness를 측정하였다. 실험 결과, $Co/TaN_x$ 박막은 수소/암모니아 분압 1:6에서 90 ${\mu}{\Omega}-cm$의 낮은 비저항과 0.97 nm 의 낮은 surface roughness 를 가졌다. 뿐만 아니라, MOCVD 에 의해 증착된 Co 박막이4-6 % concentration 의 탄소 및 산소 함량을 가지는 것으로 나타났고, 24nm 크기의 trench 기판 위에 약 6nm의 $Co/TaN_x$ 박막이 매우 균일하게 형성된 것을 확인 할 수 있었다. 이러한 결과들은, 향후 $Co/TaN_x$ 박막이 Cu direct electroplating 공정이 가능한 diffusion barrier로서 성공적으로 사용될 수 있음을 보여준다.

• Clean Technology
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• v.19 no.4
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• pp.416-422
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• 2013

In environmental friendly aspects, the synthesis of glycerol carbonate from glycerol using carbon monoxide and oxygen gases which were produced in petrochemical plants was studied. The oxidative carbonylation of glycerol under batch reaction system was performed on parameter conditions such as effect of various metals (Cu, Pd, Fe, Sn, Zn, Cr), oxidizing agents, mole ratio of carbon monoxide to oxygen, catalyst amount, solvent types, reaction temperature and time and dehydrating agents. In particular copper chloride catalysts showed the excellent activities, and the glycerol carbonate yields over CuCl and $CuCl_2$ catalysts were the maximum of 44% and 64%, respectively at the following reaction conditions: solvent as nitrobenzene, mole ratio of 1:3:0.15 (glycerol:carbon monoxide:catalyst), mole ratio of 2:1 (carbon monoxide:oxygen), the total pressure of 30 bar at 413 K for 4 hr. It was found that reactivity were significantly different depending on the oxidation number of Cu catalysts, and oxygen plays an important role as oxidizing agents in producing H2O during oxidation reaction after carbonylation of glycerol.

• Korean Journal of Heritage: History & Science
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• v.43 no.3
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• pp.102-121
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• 2010

Three bronze bells excavated from the Hoeamsa temple site were investigated for their microstructures and chemical compositions in an effort to understand the technology applied in fabrication, which may represent the related industry established in the early Joseon period. The result shows that the bells were cast from alloys of approximately 85% copper-8% tin-7% lead. The chemical analysis for ten trace elements shows that they were all kept below 0.3 weight %, suggesting that the alloys were made of relatively well-refined copper, tin and lead. The presence of sulfur and iron indicates that chalcopyrite or chalcocite may have been used in the smelting of copper. Evidence has been found that the bells were cast by pouring the liquid metal from the top of the sand molds that were set up in an upright position. No additional treatments, thermal or mechanical, other than a little grinding were applied upon the completion of casting. After the shaping process, a balancing plate was attached to the top of the bell using a steel connection ring. The connection assembly was then fixed to the main body by using molten bronze as a solder. The surface inscription was found carved using different techniques. The differences in the order of strokes and the calligraphic style indicate that the carving was carried out by more than one master. In the absence of documentary evidence on past bronze technology, the present bronze bells with known chronology, provenance and the main agent of production, prove to be a rare and valuable archaeological material for the understanding of the related technology in use in the early Joseon period.

• Applied Chemistry for Engineering
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• v.20 no.2
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• pp.223-226
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• 2009

In this study, we investigated the recovery of copper and synthetic fuel from the waste wire by low temperature pyrolysis which can overcome problems of the recent incineration methods. Through thermal decomposition process of waste wire, we achieved the big advantage of getting usable resources as the forms of copper and fuel with a very high value. The TG/DTA and small-scale reaction experiments were carried out to determine an optimum temperature for waste wire pyrolysis. And the pyrolysis was done at 350, 450, and $550^{\circ}C$, respectively, and heating rate of the TG/DTA was $5^{\circ}C/min$ untill $700^{\circ}C$. The result shows that the optimum temperature range for dehydrochlorination of PVC was $280{\sim}350^{\circ}C$, as a lower temperature range than $400{\sim}550^{\circ}C$ of PE and PP. Practically over 95% of copper metal and synthetic fuel, which has the 8027 kcal/kg as a calorific value, were recovered from the waste wire samples.

• Applied Chemistry for Engineering
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• v.10 no.2
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• pp.259-262
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• 1999

The copper-catalyzed reaction of silicon with methanol was carried out in a mixed bed reactor to obtain tetramethyl orthosilicate (TMOS). In order to determine the kinetics of the reaction per active site on the silicon surface, a flow rate transition technique was employed. A kinetic study showed the reaction was in Linear relationship with the amount of contact mass and independent on the concentration of methanol. This result indicated that the rate-determining step was not the chemical process involving methanol, but the formation of silicon intermediate on the contact mass. On the basis of optimum experimental conditions, the maximum TMOS formation rate per g-silicon is 0.030 (g/min) at $210^{\circ}C$, in which activation energy was 8.5 kcal/mol and reaction rate equation was $k=4.09{\times}10^4\;exp$ ($-4.73{\times}10^3/T$).

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2018.06a
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• pp.30-30
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• 2018

스마트 도금공장을 구축하기 위해서는 도금액 내부의 화학 물질 농도 변화를 측정할 수 있는 화학 센서 기술이 필수적으로 요구된다. 와트욕은 대표적인 고속 니켈 도금액 중 하나로 기본적으로 황산니켈, 염화니켈, 보릭산의 염과 함께 케리어(type-1 광택제), 광택제(type 2-광택제), 응력 제어제 등의 유기 첨가제로 구성되어 있다. 이러한 유기 첨가제는 전차된 니켈층의 두께 균일도, 조도, 미세 구조, 내부 응력 등 다양한 특성을 제어하며, 정밀한 농도 관리가 필수적으로 요구되나, 분석 기술의 부재로 인하여 지금까지도 대부분의 액관리는 할셀법이나 작업자의 경험에 의존하고 있다. Cyclic voltammetry stripping(CVS) 방법은 전기화학 분석 과정에서 나타나는 첨가제의 가속, 감속 특성 등과 여기에 수반되는 stripping peak의 변화를 이용하여 개별 첨가제의 농도를 측정하는 방법이며, 지금까지 인쇄회로기판의 비아필 공정, 전해 동박 제조, 반도체 배선 등 구리도금 산업 전반에 걸쳐 첨가제 관리에 효과적으로 적용되고 있다. 그러나 수소 발생으로 인한 stripping 효율 문제로 인하여 니켈, 주석, 아연 등 표준 환원 전위가 높은 금속 도금액 내부 첨가제 농도 측정은 아직 어려운 상황이다. 본 연구에서는 이 문제를 극복하기 위해 염소를 과량 첨가한 구리 도금액을 CVS 분석의 base 용액으로 이용하여 니켈 도금액 내부 여러 광택제 (polyetylene glycol(PEG) 계열, thiourea 계열, 2-butyne-1,4-diol 등) 농도를 측정하는 법을 제시하였다. 제시된 방법은 CVS 분석 과정에서 구리-염소 사이의 상호 작용으로 인해 생성되는 3가지 stripping peak의 상대적인 크기 변화가 첨가제 농도에 따라 영향을 받는다는 사실에 기반하였다. 본 연구에서는 여기에 관한 원인에 대해 고찰하였으며, 제시된 방법을 통해 광택제 계열 첨가제 농도 측정을 선택적으로 할 수 있다는 것을 증명하였다.

• Korean Journal of Materials Research
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• v.11 no.3
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• pp.184-184
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• 2001

The effect of neutral ligand(L) on the precursor characteristics of (hfac)Cu(I)-L and on Cu MOCVD Process was studied. The neutral ligands of (hac)Cu(I)-L$_{x}$, such as ATMS(allytrimethylsilane), VTMS(vinyltrimethylsilane), VCH(vinylcyclohexane), MP(4-methyl-1-pentene), ACP(allylcyclopentane), and DMB(3,3-dimethyl-1-butene) were investigated. When the dissociation temperature of Cu(I)-L bond is low, low temperature deposition below $100^{\circ}C$ is possible and the resistivity of the film is low. But thermal stability of the precursor is low in this case. The resistivity is almost the same regardless of L at the deposition temperature range of $125~175^{\circ}C$. The resistivity is increased as the molecular weight of L becomes higher above $225^{\circ}C$ The vapor pressure of the precursor was closely related to the boiling point of L, the lower the boiling point of L, the higher the vapor pressurere.

• Korean Journal of Materials Research
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• v.11 no.3
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• pp.185-190
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• 2001

The effect of neutral ligand(L) on the precursor characteristics of (hfac)Cu(I)-L and on Cu MOCVD Process was studied. The neutral ligands of (hac)Cu(I)-L$_{x}$, such as ATMS(allytrimethylsilane), VTMS(vinyltrimethylsilane), VCH(vinylcyclohexane), MP(4-methyl-1-pentene), ACP(allylcyclopentane), and DMB(3,3-dimethyl-1-butene) were investigated. When the dissociation temperature of Cu(I)-L bond is low, low temperature deposition below $100^{\circ}C$ is possible and the resistivity of the film is low. But thermal stability of the precursor is low in this case. The resistivity is almost the same regardless of L at the deposition temperature range of $125~175^{\circ}C$. The resistivity is increased as the molecular weight of L becomes higher above $225^{\circ}C$ The vapor pressure of the precursor was closely related to the boiling point of L, the lower the boiling point of L, the higher the vapor pressurere.

• Korean Journal of Materials Research
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• v.5 no.6
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• pp.657-666
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• 1995

Chemical vapor deposition of copper from the Cu(hfac)$_2$, Cu(II) hexafluoroacetylacetonate precursor, has been thermodynamically investigated by the minimization of Gibbs free energy of the system. For the Cu(hfac)$_2$-Ar system, carbon incorporation into the deposited films was observed in all the process conditions, which is presumably inherent from the thermal decomposition of the Cu(hfac)$_2$, precursor. For the Cu(hfac)$_2$-H$_2$system, lower temperatures were required than those of the Cu(hfac)$_2$-Ar system for the depositon of the copper films. Furthermore, we identified that the appearances of the condensed phases were sequentially changed from the codeposits of C(s)+CuF(s) to C(s)+CuF(s)+Cu(s), C(s)+Cu(s), Cu(s), and C(s), when the H$_2$input ratio and th reaction temperature were increased.

• Journal of the Korean Institute of Gas
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• v.26 no.5
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• pp.16-21
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• 2022

The reaction rate of a catalyst for producing hydrogen using the methanol steam reforming reaction was studied. It was prepared by impregnating copper, which is often used in methanol synthesis, as the main active metal, using hydrotalcite, which has excellent porosity and thermal stability, high specific surface area, weak Lewis acid point, and basicity, as a support. Activation energy and Pre-exponential factors were identified. In this study, the activation energy of the hydrotalcite catalyst impregnated with 20 wt% copper was calculated to be 97.4 kJ/mol and the Pre-exponential was 5.904 × 10¹⁰. Process simulation was performed using the calculated values and showed a similar tendency to the experimental results.