• Korean Journal of Materials Research
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• v.34 no.3
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• pp.163-169
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• 2024

As the limitations of Moore's Law become evident, there has been growing interest in advanced packaging technologies. Among various 3D packaging techniques, Cu-SiO₂ hybrid bonding has gained attention in heterogeneous devices. However, certain issues, such as its high-temperature processing conditions and copper oxidation, can affect electrical properties and mechanical reliability. Therefore, we studied depositing only a heterometal on top of the Cu in Cu-SiO₂ composite substrates to prevent copper surface oxidation and to lower bonding process temperature. The heterometal needs to be deposited as an ultra-thin layer of less than 10 nm, for copper diffusion. We established the process conditions for depositing a Co film using a Co(EtCp)₂ precursor and utilizing plasma-enhanced atomic layer deposition (PEALD), which allows for precise atomic level thickness control. In addition, we attempted to use a growth inhibitor by growing a self-assembled monolayer (SAM) material, octadecyltrichlorosilane (ODTS), on a SiO₂ substrate to selectively suppress the growth of Co film. We compared the growth behavior of the Co film under various PEALD process conditions and examined their selectivity based on the ODTS growth time.

• Journal of the Microelectronics and Packaging Society
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• v.19 no.1
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• pp.61-66
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• 2012

Chemical Mechanical Planarization (CMP) is a polishing process used in the microelectronic fabrication industries to achieve a globally planar wafer surface for the manufacturing of integrated circuits. Pad conditioning plays an important role in the CMP process to maintain a material removal rate (MRR) and its uniformity. For metal CMP process, highly acidic slurry containing strong oxidizer is being used. It would affect the conditioner surface which normally made of metal such as Nickel and its alloy. If conditioner surface is corroded, diamonds on the conditioner surface would be fallen out from the surface. Because of this phenomenon, not only life time of conditioners is decreased, but also more scratches are generated. To protect the conditioners from corrosion, thin organic film deposition on the metal surface is suggested without requiring current conditioner manufacturing process. To prepare the anti-corrosion film on metal conditioner surface, vapor SAM (self-assembled monolayer) and FC (Fluorocarbon) -CVD (SRN-504, Sorona, Korea) films were prepared on both nickel and nickel alloy surfaces. Vapor SAM method was used for SAM deposition using both Dodecanethiol (DT) and Perfluoroctyltrichloro silane (FOTS). FC films were prepared in different thickness of 10 nm, 50 nm and 100 nm on conditioner surfaces. Electrochemical analysis such as potentiodynamic polarization and impedance, and contact angle measurements were carried out to evaluate the coating characteristics. Impedance data was analyzed by an electrical equivalent circuit model. The observed contact angle is higher than 90o after thin film deposition, which confirms that the coatings deposited on the surfaces are densely packed. The results of potentiodynamic polarization and the impedance show that modified surfaces have better performance than bare metal surfaces which could be applied to increase the life time and reliability of conditioner during W CMP.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.27-27
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• 2011

For the design of real applicable molecular devices, current-voltage properties through molecular nanostructures such as metal-molecule-metal junctions (molecular junctions) have been studied extensively. In thiolate monolayers on the gold electrode, the chemical bonding of sulfur to gold and the van der Waals interactions between the alkyl chains of neighboring molecules are important factors in the formation of well-defined monolayers and in the control of the electron transport rate. Charge transport through the molecular junctions depends significantly on the energy levels of molecules relative to the Fermi levels of the contacts and the electronic structure of the molecule. It is important to understand the interfacial electron transport in accordance with the increased film thickness of alkyl chains that are known as an insulating layer, but are required for molecular device fabrication. Thiol-tethered RuII terpyridine complexes were synthesized for a voltage-driven molecular switch and used to understand the switch-on mechanism of the molecular switches of single metal complexes in the solid-state molecular junction in a vacuum. Electrochemical voltammetry and current-voltage (I-V) characteristics are measured to elucidate electron transport processes in the bistable conducting states of single molecular junctions of a molecular switch, Ru(II) terpyridine complexes. (1) On the basis of the Ru-centered electrochemical reaction data, the electron transport rate increases in the mixed self-assembled monolayer (SAM) of Ru(II) terpyridine complexes, indicating strong electronic coupling between the redox center and the substrate, along the molecules. (2) In a low-conducting state before switch-on, I-V characteristics are fitted to a direct tunneling model, and the estimated tunneling decay constant across the Ru(II) terpyridine complex is found to be smaller than that of alkanethiol. (3) The threshold voltages for the switch-on from low- to high-conducting states are identical, corresponding to the electron affinity of the molecules. (4) A high-conducting state after switch-on remains in the reverse voltage sweep, and a linear relationship of the current to the voltage is obtained. These results reveal electron transport paths via the redox centers of the Ru(II) terpyridine complexes, a molecular switch.

• Proceedings of the Materials Research Society of Korea Conference
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• 2009.05a
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• pp.49.2-49.2
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• 2009

최근, 플루이딕스칩 제작에 있어서 가격이 저렴하며 구조물 형성이 쉽다는 장점으로 인하여 유리 기판을 플라스틱 기판으로 대체하려는 연구가 많이 진행하고 있다. 하지만 플라스틱 기판은 유리 기판에 비하여 많은 장점을 갖고 있음에도 불구하고, 기판 표면이 소수성이기 때문에 유체의 흐름을 저하시키는 문제점이 있다. 기존의 플라스틱 기판을 친수성으로 개질하는 방법으로는 화학적처리, 자외선 조사, 산소플라즈마 처리 등의 방법이 있었으나, 화학적처리 방법은 공정의 민감성과 폐기물로 인한 양산적용의 한계가 있고, 자외선 조사법 및 산소 플라즈마 처리는 친수성이 영구적이지 않다는 결정적인 문제점이 있다. 이는 플라스틱 플루이딕스칩의 신뢰도를 크게 저해하여 상용화에 큰 문제점으로 작용한다. 이러한 문제점을 극복하기 위한 새로운 방법의 친수성 표면처리가 요구되어 지고 있다. 본 연구에서는, 기존 플라스틱 기판의 친수성 표면처리 방법들의 문제점들을 개선하고자 플라스틱 기판의 변형을 야기하지 않는 저온 PE-CVD 방식을 이용하여 균질한 두께의 $SiO_2$박막을 형성 하였으며, 형성된 박막을 liquid self-assembled monolayer(L-SAM)방식을 이용하여 아민 표면으로 개질하였다. 이를 통해, 플라스틱 채널 상에서 유체의 원활한 흐름, 형성된 아민 표면에 단백질 및 DNA와 같은 생체 물질 고정화의 용이성 및 영구적 표면개질의 특성을 얻을 수 있었다. 이뿐만 아니라, 플라스틱 기판 외에도 재료에 관계없이 모든 물질의 표면을 생체 안정성이 뛰어난 친수성 표면으로 개질 할 수 있으며, 알데히드 및 카르복시산 등의 다양한 작용기로 변형이 쉽다는 장점이 있다. 개질된 친수성 표면의 평가를 위하여 시간에 따른 접 촉각 및 형광 스캐너(Fluorescence Scanner)를 이용하여 영구적인 친수성 특성 및 생체물질 적합성을 파악하였다. 또한, L-SAM 조건에 따른 아민의 형성정도를 측정하기 위하여 XPS(X-ray Photoelectron Spectroscopy) 분석을 실시 하였다. 최적화된 표면처리를 실제 플라스틱 플루이딕스칩에 적용하여, 유체의 흐름을 관찰 하였다.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.672-678
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• 2006

A new approach to fabricate an enzyme electrode was described based on the immobilization of horseradish peroxidase (HRP) on dithiobis-N-succinimidyl propionate (DTSP) self-assembled monolayer (SAM) formed on gold-nanoparticles (Au-NPs) which were electrochemically deposited onto glassy carbon electrode (GCE) surface. The overall surface area and average size of Au-NPs could be controlled by varying deposition time and were examined by Field Emission-Scanning Electron Microscope (FE-SEM). The $O_2$ reduction capability of the surface demonstrated that Au-NPs were thermodynamically stable enough to stay on GCE surface. The immobilized HRP electrode based on Au-NPs/GCE presented faster, more stable and sensitive amperometric response in the reduction of hydrogen peroxide than a HRP immobilized on DTSP/gold plate electrode not containing Au-NPs. The effects of operating potential, mediator concentration, and pH of buffer electrolyte solution on the performance of the HRP biosensor were investigated. In the optimized experimental conditions, the HRP immobilized GCE incorporating smaller-sized Au-NPs showed higher electrocatalytic activity due to the high surface area to volume ratio of Au-NPs in the biosensor. The HRP electrode showed a linear response to $H_2O_2$ in the concentration range of 1.4 $\mu$M-3.1 mM. The apparent Michaelis-Menten constant ($K _M\; ^{app}$) determined for the immobilized HRP electrodes showed a trend to be decreased by decreasing size of Au-NPs electrodeposited onto GCE.

• 한국생물공학회:학술대회논문집
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• 2003.04a
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• pp.74-78
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• 2003

Multi-channel images of 11-MUA and 11-MUOH self-assembled monolayers were obtained by using two-dimensional surface plasmon resonance (SPR) absorption. Patterning process was simplified by exploiting direct photo-oxidation of thiol bonding (photolysis) instead of conventional photolithography. Sharper images were resolved by using a white light source in combination with a narrow bandpass filter in the visible region, minimizing the diffraction patterns on the images. The line profile calibration of the image contrast caused by different resonance conditions at each points on the sensor surface (at a fixed incident angle) enables us to discriminate the monolayer thickness in sub-nanometer scale. Furthermore, there is no signal degradation such as photo bleaching or quenching which are common in the detection methods based on the fluorescence.

• Journal of Sensor Science and Technology
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• v.15 no.3
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• pp.192-198
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• 2006

In this study, the light addressable potentiometric sensors (LAPS) with $Si_{3}N_{4}/SiO_{2}/Si$, and $Ta_{2}O_{5}/SiO_{2}/Si$ structures were fabricated. The penicillinsae was immobilized on the devices to hydrolyze the penicillin using self-assembled monolayer (SAM) method. Then response characteristics according to the penicillin concentrations were measured and compared. The measuring system was simplified by using LabVIEW. The pH response characteristics of fabricated devices are 56 mV/pH ($Si_{3}N_{4}$ sensing membrane) and 61 mV/pH ($Ta_{2}O_{5}$ sensing membrane). The sensitivity of sensor by enzyme reaction result of the enzyme reaction were 60 mV/decade and 74 mV/decade for $Si_{3}N_{4}/SiO_{2}/Si$ and $Ta_{2}O_{5}/SiO_{2}/Si$ structure, respectively, in the range of $0.1\;mM{\sim}10\;mM $of the penicillin concentration.

• Journal of Sensor Science and Technology
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• v.22 no.2
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• pp.144-149
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• 2013

In this research, we developed a biosensor to detect lung cancer-specific biomarker using Anodic Aluminum Oxide (AAO) chip based on interference and nano surface plasmon resonance (nanoSPR). The nano-porous AAO chip was fabricated $2{\mu}m$ of pore-depth by two-step anodizing method for surface uniformity. NanoSPR has sensitivity to the refractive index (RI) of the surrounding medium and also provides simple and label-free detection when specific antibodies are immobilized to the Au-deposited surface of nano-porous AAO chip. To detect the lung cancer-specific biomarker, antibodies were immobilized on the surface of the chip by Self Assembled Monolayer (SAM) method. Since then lung cancer-specific biomarker was applied atop the antibodies immobilized layer. The specific reaction of the antigen-antibody contributed to the change in the refractive index that cause shift of resonance spectrum in the interference pattern. The Limit of Detection (LOD) was 1 fg/ml by using our nano-porous AAO biosensor chip.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.114-114
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• 2008

반도체 device의 성능을 향상시키기 위하여 패턴은 더욱 더 고 집적화 되고 배선 또한 다층배선 구조를 가지게 되었으며 요구되는 선폭 또한 더욱 미세화 되어 CMP 공정이 도입되게 되었다. 이러한 CMP 공정에 사용되는 소모품으로는 크게 세 가지의 중요한 부분으로 나눌 수 있다. 그것은 slurry와 pad, conditioner이다. 그중에 pad conditioning 공정은 CMP 공정시 pad의 마모에 따라 감소하는 removal rate(RR)값을 회복시키기 위한 공정으로 마모된 pad의 표면을 활성화 시켜주는 중요한 공정이다. 하지만 pad conditioning 공정을 장시간 진행하게 되면 conditioner 표면에 오염물이 발생하게 되며, 오염물로 인하여 wafer표면에 scratch 및 defect을 발생시키는 원인이 될 수 있다. 이러한 문제점을 보완하기 위하여 conditioner의 표면을 변화시켜 공정중의 오염이 발생하지 않도록 하는 것이 중요하다. 본 논문에서는 oxide CMP 실험을 통하여 conditioner표면에 오염물이 발생함을 확인하였으며 energy dispersive spectroscopy(EDS) 분석을 통하여 주오염물의 성분이 oxide slurry중 silica임을 확인하였다. Conditioner의 표면을 소수성으로 만들기 위하여 self assembled monolayer(SAM) 방법을 이용하여 표면에 코팅을 하였으며, 소수성 박막이 코팅된 conditioner와 코팅되지 않은 conditioner의 비교 실험을 통하여 오염 정도를 비교하였다.

• Korean Chemical Engineering Research
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• v.49 no.3
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• pp.330-337
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• 2011

In this research, the preparation processes for making a series of $\omega$-mercapto alkylamine 1 and $\omega$-mercapto alkanoic acid 2 useful for studying of the self-assembled monolayer(SAM) are described. The preparation methods of the first goal materials, $\omega$-mercapto alkylamines 1 were carried out as follows: First, $\omega$-phthalimide alkanol 3 was synthesized from commercially available potassium phthalimide derivatives and $\omega$-bromoalkanol in DMF at $80{^{\circ}C}$ via substitution reaction. After refluxing $\omega$-phthalimide alkanol 3 with hydrazine hydrate in ethanol followed by treating with c-HCl, $\omega$-aminoalkanol 4 was obtained in 76-98% yield, accompanied with side-product 5. Bromination of hydroxyl moiety of $\omega$-aminoalkanol 4 using aqueous hydrobromic acid furnished $\omega$-bromoamine 6 in 34-97% yields. Substitution reaction 6 with thiourea in 95% ethanol gave $\omega$-aminoalkanthiuronium 7, which was treated with aqueous strong base and aqueous strong sulfuric acid gave desired products, $\omega$-mercapto alkylamines 1 through overall 5 steps. The second target material, $\omega$-mercapto alkanoic acid 2 was prepared via 2 steps. $\omega$-bromo alkanoic acid was reacted with thiourea to give $\omega$-thiourea alkanoic acid 7 in 69-85%, which was treated with aqueous strong base and strong acid to furnish $\omega$-mercapto alkanoic acid 2 in 50-98%. The fabricated long-chain alkylthiol(LCAT) can be used as linkers to immobilize protein, enzyme and various kinds of biomolecules on the surface of metallic materials(Au, Pt, Ti) by SAM, and can be useful chemical tools for the application study on the surface modification of metallic materials.