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Study of Magnetic Field Shielded Sputtering Process as a Room Temperature High Quality ITO Thin Film Deposition Process

  • Lee, Jun-Young;Jang, Yun-Sung;Lee, You-Jong;Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.288-289
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    • 2011
  • Indium Tin Oxide (ITO) is a typical highly Transparent Conductive Oxide (TCO) currently used as a transparent electrode material. Most widely used deposition method is the sputtering process for ITO film deposition because it has a high deposition rate, allows accurate control of the film thickness and easy deposition process and high electrical/optical properties. However, to apply high quality ITO thin film in a flexible microelectronic device using a plastic substrate, conventional DC magnetron sputtering (DMS) processed ITO thin film is not suitable because it needs a high temperature thermal annealing process to obtain high optical transmittance and low resistivity, while the generally plastic substrates has low glass transition temperatures. In the room temperature sputtering process, the electrical property degradation of ITO thin film is caused by negative oxygen ions effect. This high energy negative oxygen ions(about over 100eV) can be critical physical bombardment damages against the formation of the ITO thin film, and this damage does not recover in the room temperature process that does not offer thermal annealing. Hence new ITO deposition process that can provide the high electrical/optical properties of the ITO film at room temperature is needed. To solve these limitations we develop the Magnetic Field Shielded Sputtering (MFSS) system. The MFSS is based on DMS and it has the plasma limiter, which compose the permanent magnet array (Fig.1). During the ITO thin film deposition in the MFSS process, the electrons in the plasma are trapped by the magnetic field at the plasma limiters. The plasma limiter, which has a negative potential in the MFSS process, prevents to the damage by negative oxygen ions bombardment, and increases the heat(-) up effect by the Ar ions in the bulk plasma. Fig. 2. shows the electrical properties of the MFSS ITO thin film and DMS ITO thin film at room temperature. With the increase of the sputtering pressure, the resistivity of DMS ITO increases. On the other hand, the resistivity of the MFSS ITO slightly increases and becomes lower than that of the DMS ITO at all sputtering pressures. The lowest resistivity of the DMS ITO is $1.0{\times}10-3{\Omega}{\cdot}cm$ and that of the MFSS ITO is $4.5{\times}10-4{\Omega}{\cdot}cm$. This resistivity difference is caused by the carrier mobility. The carrier mobility of the MFSS ITO is 40 $cm^2/V{\cdot}s$, which is significantly higher than that of the DMS ITO (10 $cm^2/V{\cdot}s$). The low resistivity and high carrier mobility of the MFSS ITO are due to the magnetic field shielded effect. In addition, although not shown in this paper, the roughness of the MFSS ITO thin film is lower than that of the DMS ITO thin film, and TEM, XRD and XPS analysis of the MFSS ITO show the nano-crystalline structure. As a result, the MFSS process can effectively prevent to the high energy negative oxygen ions bombardment and supply activation energies by accelerating Ar ions in the plasma; therefore, high quality ITO can be deposited at room temperature.

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원자층 증착법을 이용한 고 단차 Co 박막 증착 및 실리사이드 공정 연구

  • Song, Jeong-Gyu;Park, Ju-Sang;Lee, Han-Bo-Ram;Yun, Jae-Hong;Kim, Hyeong-Jun
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2012.05a
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    • pp.83-83
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    • 2012
  • 금속 실리사이드는 낮은 비저항, 실리콘과의 좋은 호환성 등으로 배선 contact 물질로 널리 연구되고 있다. 특히 $CoSi_2$는 선폭의 축소와 관계없이 일정하고 낮은 비저항과 열적 안정성이 우수한 특성 등으로 배선 contact 물질로 활발히 연구되고 있다. 금속 실리사이드를 실리콘 평면기판에 형성시키는 방법으로는 열처리를 통한 금속박막과 실리콘 기판 사이에 확산작용을 이용한 SALICIDE (self-algined silicide) 기술이 대표적이며 CoSi2도 이와 같은 방법으로 형성할 수 있다. Co 박막을 증착하는 방법에는 물리적 기상증착법 (PVD)과 유기금속 화학 증착법 등이 보고되어있지만 최근 급격하게 진행 중인 소자구조의 나노화 및 고 단차화에 따라 기존의 증착 기술은 낮은 단차 피복성으로 인하여 한계에 부딪힐 것으로 예상되고 있다. ALD(atomic layer deposition)는 뛰어난 단차 피복성을 가지고 원자단위 두께조절이 용이하여 나노 영역에서의 증착 방법으로 지대한 관심을 받고 있다. 앞선 연구에서 본 연구진은 CoCp2 전구체과 $NH_3$ plasma를 사용하여 Plasma enhanced ALD (PE-ALD)를 이용한 고 순도 저 저항 Co 박막 증착 공정을 개발 하고 이를 SALICIDE 공정에 적용하여 $CoSi_2$ 형성 연구를 보고한 바 있다. 하지만 이 연구에서 PE-ALD Co 박막은 플라즈마 고유의 성질로 인하여 단차 피복성의 한계를 보였다. 이번 연구에서 본 연구진은 Co(AMD)2 전구체와 $NH_3$, $H_2$, $NH_3$ plasma를 반응 기체로 사용하여 Thermal ALD(Th-ALD) Co 및 PE-ALD Co 박막을 증착 하였다. 고 단차 Co 박막의 증착을 위하여 Th-ALD 공정에 초점을 맞추어 Co 박막의 특성을 분석하였으며, Th-ALD 및 PE-ALD 공정으로 증착된 Co 박막의 단차를 비교하였다. 연구 결과 Th-ALD Co 박막은 95% 이상의 높은 단차 피복성을 가져 PE-ALD Co 박막의 단차 피복성에 비해 크게 향상되었음을 확인하였다. 추가적으로, Th-ALD Co 박막에 고 단차 박막의 증착이 가능한 Th-ALD Ru을 capping layer로 이용하여 CoSi2 형성을 확인하였고, 기존의 PVD Ti capping layer와 비교하였다. 이번 연구에서 Co 박막 및 $CoSi_2$ 의 특성 분석을 위하여 X선 반사율 분석법 (XRR), X선 광전자 분광법 (XPS), X선 회절 분석법 (XRD), 주사 전자 현미경 (SEM), 주사 투과 전자 현미경 (STEM) 등을 사용하였다.

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$La_2O_3/HfO_2$ 나노 층상구조를 이용한 MIM capacitor의 특성 향상

  • O, Il-Gwon;Kim, Min-Gyu;Park, Ju-Sang;Kim, Hyeong-Jun
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2012.05a
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    • pp.82.1-82.1
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    • 2012
  • 란타늄 산화물 ($La_2O_3$) 박막은 하프늄 산화물 ($HfO_2$) 박막보다 높은 유전 상수와 높은 밴드 오프셋으로 인해 dynamic random access memory(DRAM)에서 유전체 재료로써 연구되어 왔다. 그리고 Lanthanum이 도핑된 HfO2이 더 높은 유전 상수와 낮은 누설 전류 밀도를 갖는 다는 사실이 이전에 보고 된 바 있다. 본 연구에서 우리는 ALD를 이용하여, TiN 하부 전극 위에 $La_2O_3$의 위치를 달리하는 $La_2O_3/HfO_2$의 나노 층상조직 구조(두께 10 nm)를 금속 - 절연체 - 금속 (MIM) 구조로 제작 하였다. ALD는 좋은 comformality와 넓은 지역 균일성을 가지며, 원자수준의 두께를 조절할 수 있다는 장점을 갖고 있다. 또한, 다양한 화학 물질들을 이용한 복합적 계층구조를 만들 수 있는 점과 $HfO_2$$La_2O_3$ 계층의 수직 위치를 정확하게 조절할 수 있는 점으로 본 연구에 적합한 증착 방법이다. HfO2 속에 $La_2O_3$ 층을 깊이에 따라 삽입함으로써 $HfO_2$ 계층에 La 도핑의 효과와 더불어 TiN 하부 전극 위의 $La_2O_3$$HfO_2$의 차이점을 확인 하였다. $HfO_2$$250^{\circ}C$에서 TDMAH와 물을 사용하여, $La_2O_3$은 동일한 온도에서 $La(iPrCp)_3$와 물을 사용하여 제작되었다. 화학적 구성 및 binding 구조는 X선 광전자 분광법 (XPS)을 통해 분석하였다. 전기적 특성(유전 상수 및 누설 전류)은 Capacitance-Voltage (CV)와 Current-Voltage (IV) 측정으로 확인하였다. 결과적으로, $La_2O_3$ 또는 $HfO_2$을 한 종류만 사용한 절연층의 전기적 특성보다, $La_2O_3/HfO_2$의 나노 층상조직 구조가 더 나은 특성 (누설 전류 밀도 : $5.5{\times}10^{-7}\;A/cm^2$ @-1MV/cm, EOT : 14.6)을 갖는다는 것을 확인했고, 더불어 $La_2O_3$의 흡습 성질로 인한 화학 구조와 전기적 특성의 일부 차이를 확인하였다. 본 연구에서는 $HfO_2$ 속에 $La_2O_3$층이 TiN 하부 전극 바로 위에 위치할 때, 즉, 공기 중에 노출되지 않은 $La_2O_3/HfO_2$ 구조에서 가장 좋은 특성의 MIM capacitor를 얻을 수 있었다.

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Corrosion Stability of Iron Artifacts after Treating with Water Treatment (수처리제를 사용한 철제유물의 부식 안정성 연구)

  • Jeong, Ji Hae
    • Journal of Conservation Science
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    • v.33 no.5
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    • pp.381-390
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    • 2017
  • Desalination is the main focus of the stabilization of iron artifacts. However, drawbacks such as re-corrosion are noted due to the uncertainty in the elimination of the corrosive factors and artifacts. Several studies have been carried out on the effects of corrosion inhibitors to overcome these shortcomings. In this study, the effects of type 3 water treatment on corrosion inhibitors were investigated. Surfaces of samples that contained film corrosion inhibitors on their surfaces were analyzed. The results revealed that the surface rust was removed from the sample of type 1 No. 2 that was mainly composed of phosphate. The average weight reduction rates of re-corrosion samples were 0.58, 0.03, and 0.07% for type 1 No. 2, type 2 No. 2, and type 3 No. 2 respectively. The changes in the $Cl^-$ ion, a corrosive agent were found to be 28.60, -4.08, and -1.94 ppm for type 1 No. 2, type 2 No. 2, and type 3 No. 2 respectively. The water-treated films were analyzed by X-ray photoelectron spectroscopy (XPS). It was found that type 2 No. 2 had less Fe the basis metal, than that in type 3 No. 2 indicating much better film. Moreover, Si content was higher in type 2 No. 2, based on the silicate content, than in type 3 No. 2. They are speculated to be the reason or the formation of a better film. Type 1 No. 2, which is mainly composed of phosphate, would be inappropriate as a metal artifact conservation treatment. It was determined that type 2 No. 2 and type 3 No. 2 water treatments, which are mainly composed of silicate, provided excellent corrosion inhibiting effects. Corrosion inhibitors could be used as emergency treatment agents during the excavation of iron artifacts.

A Study on Mechanical Interfacial Properties of Copper-plated Carbon Fibers/Epoxy Resin Composites (구리도금된 탄소섬유/에폭시 수지 복합재료의 기계적 계면 특성에 관한 연구)

  • Hong, Myung-Sun;Bae, Kyong-Min;Choi, Woong-Ki;Lee, Hae-Seong;Park, Soo-Jin;An, Kay-Hyeok;Kim, Byung-Joo
    • Applied Chemistry for Engineering
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    • v.23 no.3
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    • pp.313-319
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    • 2012
  • In this work, the electroplating of copper was introduced on PAN-based carbon fibers for the enhancement of mechanical interfacial strength of carbon fibers-reinforced composites. The surface properties of carbon fibers were determined by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and contact angle measurements. Its mechanical interfacial properties of the composites were studied by interlaminar shear strength (ILSS) and critical stress intensity factor ($K_{IC}$). From the results, it was found that the mechanical interfacial properties of Cu-plated carbon fibers-reinforced composites (Cu-CFRPs) enhanced with increasing the Cu plating time, Cu content and COOH group up to Cu-CFRP-30. However, the mechanical interfacial properties of the Cu-CFRPs decreased dramatically in the excessively Cu-plated CFRPs sample. In conclusion, the presence of Cu particles on carbon fiber surfaces can be a key factor to determine the mechanical interfacial properties of the Cu-CFRPs, but the excessive Cu content can lead the failure due to the interfacial separation between fibers and matrices in this system.

Electrosorption Behavior of $TiO_2$/Activated Carbon Composite for Capacitive Deionization (축전식 이온제거에 대한 $TiO_2$/Activated Carbon 화합물의 전기흡착 거동)

  • Lee, Jeong-Won;Kim, Hong-Il;Kim, Han-Joo;Park, Soo-Gil
    • Applied Chemistry for Engineering
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    • v.21 no.3
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    • pp.265-271
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    • 2010
  • Desalination effects of capacitive deionization (CDI) process was studied using $TiO_2$/activated carbon electrode. In order to enhance the wettability of electrode and decrease a electrode resistance, $TiO_2$ was coated on activated carbon. By means of $TiO_2$ coating on activated carbon, electric double layer to adsorption content in CDI process was increased. It was identified from TEM, XRD, and XPS that the activated carbon based on $TiO_2$ composite was fabricated successfully by means of sol-gel method. As a results of cyclic voltammetry and impedance, it was identified that $TiO_2$/activated carbon electrode has more electric double later capacitance and less diffusion resistance than activated carbon. Also charge-discharge and ion conductivity profiles showed that the ion removal ratios of $TiO_2$/activated carbon electrode in NaCl electrolyte of $1000\;{\mu}S/cm$ more increased about 39% than that of activated carbon. In conclusion it was possible to identify that the carbon electrode coated $TiO_2$ as electrode material was more effective than raw carbon electrode.

Synthesis of MnO2 Nanowires by Hydrothermal Method and their Electrochemical Characteristics (수열합성법을 이용한 망간 나노와이어 제조 및 이의 전기화학적 특성 연구)

  • Hong, Seok Bok;Kang, On Yu;Hwang, Sung Yeon;Heo, Young Min;Kim, Jung Won;Choi, Bong Gill
    • Applied Chemistry for Engineering
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    • v.27 no.6
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    • pp.653-658
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    • 2016
  • In this work, we developed a synthetic method for preparing one-dimensional $MnO_2$ nanowires through a hydrothermal method using a mixture of $KMnO_4$ and $MnSO_4$ precursors. As-prepared $MnO_2$ nanowires had a high surface area and porous structure, which are beneficial to the fast electron and ion transfer during electrochemical reaction. The microstructure and chemical structure of $MnO_2$ nanowires were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Brunauer-Emmett-Teller measurements. The electrochemical properties of $MnO_2$ nanowire electrodes were also investigated using cyclic voltammetry and galvanostatic charge-discharge with a three-electrode system. $MnO_2$ nanowire electrodes showed a high specific capacitance of 129 F/g, a high rate capability of 61% retention, and an excellent cycle life of 100% during 1000 cycles.

Silver nanowires and nanodendrites synthesized by plasma discharge in solution for the catalytic oxygen reduction in alkaline media

  • Kim, Hoe-Geun;Song, Myeon-Gyu;Kim, Dong-U;Lee, Sang-Yul
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2018.06a
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    • pp.62-62
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    • 2018
  • Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

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Influence of Acid and Base Surface Treatment of Multi-Walled Carbon Nanotubes on Mechanical Interfacial Properties of Carbon Fibers-Reinforced Composites (산-염기 표면처리된 MWNTs의 첨가가 탄소섬유 강화 복합재료의 기계적 계면특성에 미치는 영향)

  • Jung, Gun;Nah, Chang-Woon;Seo, Min-Kang;Byun, Joon-Hyung;Lee, Kyu-Hwan;Park, Soo-Jin
    • Polymer(Korea)
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    • v.36 no.5
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    • pp.612-616
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    • 2012
  • In this work, the effect of chemical treatments of multi-walled carbon nanotubes (MWNTs) on the mechanical interfacial properties of carbon fiber fabric-reinforced composites was investigated. The surface properties of the MWNTs were determined by acid and base values, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) analyses. The mechanical interfacial properties of the composites were assessed by interlaminar shear stress (ILSS) and critical stress intensity factor ($K_{IC}$). The chemical treatments based on acid and base reactions led to a significant change of surface characteristics of the MWNTs, especially A-MWNTs/carbon fibers/epoxy composites had higher mechanical properties than those of B-MWNTs and non-treated MWNTs/carbon fibers/epoxy composites. These results were probably due to the improvement of interfacial bonding strength, resulting from the acid-base interaction and hydrogen bonding between the epoxy resins and the MWNT fillers.

Recycling Properties of Visible-Light Driven CdZnS/ZnO Photocatalyst Prepared by a Simple Precipitation Method (단순 침전법으로 제조한 가시광선용 CdZnS/ZnO 광촉매의 재활용 특성)

  • Lee, Gun Dae;Park, Seong Soo;Jin, Youngeup;Hong, Seong Soo
    • Clean Technology
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    • v.23 no.2
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    • pp.196-204
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    • 2017
  • CdZnS/ZnO composite was prepared through low-temperature precipitation and drying method. The property of CdZnS/ZnO as a recyclable photocatalyst for the degradation of rhodamine B (RhB) under visible light irradiation was examined. The sample was characterized by XRD, FE-SEM, XPS, UV-vis DRS and photoluminescence techniques before and after repeated reaction to investigate the change of properties during the photocatalytic reaction. During repeated reaction, the CdZnS/ZnO showed an improved photocatalytic activity and recycle stability. Among two feasible reaction pathways for photocatalytic degradation of RhB, the cleavage of conjugated chromophore was found to predominate over N-dealkylation of chromophore skeleton in the present work. The results indicate that the CdZnS/ZnO, prepared by a simple precipitation method, can be used as a visible-light driven photocatalyst with enhanced cycle stability and activity.