• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.352.2-352.2
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• 2014

In this present work, we report a Cu-Mn alloy as a materials for the self-forming barrier process. And we investigated diffusion barrier properties of self-formed layer on low-k dielectrics with or without UV curing treatment. Cu alloy films were directly deposited onto low-k dielectrics by co-sputtering, followed by annealing at various temperatures. X-ray diffraction revealed Cu (111), Cu (200) and Cu (220) peaks for both of Cu alloys. The self-formed layers were investigated by transmission electron microscopy. In order to compare barrier properties between Mn-based interlayer interlayer, thermal stability was measured with various low-k dielectrics. X-ray photoelectron spectroscopy analysis showed that chemical compositions of self-formed layer. The compositions of the Mn based self-formed barriers after annealing were determined by the C concentration in the dielectric layers.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.214.2-214.2
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• 2013

Device performance for the 45 and 32 nm node CMOS technology requires the integration of ultralow-k materials. To lower the dielectric constant for PECVD and spin-on materials, partial replacement of the solid network with air (k=1.01) appears to be more intuitive and direct option. This can be achieved introducting of second "labile" phase during depositoin that is removed during a subsequent UV curing and annealing step. Besides, with shrinking line dimensions the resistivity of barrier films cannot meet the International Technology Roadmap for Semiconductors (ITRS) requirements. To solve this issue self-forming diffusion barriers have drawn attention for great potential technique in meeting all ITRS requirments. In this present work, we report a Cu-V alloy as a materials for the self-forming barrier process. And we investigated diffusion barrier properties of self-formed layer on low-k dielectrics with or without UV curing treatment. Cu alloy films were directly deposited onto low-k dielectrics by co-sputtering, followed by annealing at various temperatures. X-ray diffraction revealed Cu (111), Cu (200) and Cu (220) peaks for both of Cu alloys. The self-formed layers were investigated by transmission electron microscopy. In order to compare barrier properties between V-based interlayer on low-k dielectric with UV curing and interlayer on low-k dielectric without UV curing, thermal stability was measured with various heat treatment temperature. X-ray photoelectron spectroscopy analysis showed that chemical compositions of self-formed layer. The compositions of the V based self-formed barriers after annealing were strongly dominated by the O concentration in the dielectric layers.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2009년도 제38회 동계학술대회 초록집
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• pp.229-229
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• 2010

With the scaling down of ultra large integrated circuits (ULSI) to the sub-50 nm technology node, the need for an ultra-thin, continuous and conformal diffusion barrier and Cu seed layer is increasing. However, diffusion barrier and Cu seed layer formation with a physical vapor deposition (PVD) method has become difficult as the technology node is reduced to 30 nm and beyond. Recent work on self-forming barrier processes using PVD Cu alloys have attracted great attention due to the capability of conformal ultra-thin barrier formation using a simple technique. However, as in the case of the conventional barrier and Cu seed layer, PVD of the Cu alloy seed layer will eventually encounter the difficulty in conformal deposition in narrow line trenches and via holes. Atomic layer deposition (ALD) has been known for its good step coverage and precise thickness control, and is a candidate technique for the formation of a thin conformal barrier layer and Cu seed layer. Conformal Cu-Mn seed layers were deposited by plasma enhanced atomic layer deposition (PEALD) at low temperature ($120^{\circ}C$), and the Mn content in the Cu-Mn alloys were controlled form 0 to approximately 10 atomic percent with various Mn precursor feeding times. Resistivity of the Cu-Mn alloy films decreased by annealing due to out-diffusion of Mn atoms. Out-diffused Mn atoms were segregated to the surface of the film and interface between a Cu-Mn alloy and $SiO_2$, resulting in self-formed $MnO_x$ and $MnSi_xO_y$, respectively. No inter-diffusion was observed between Cu and $SiO_2$ after annealing at $500^{\circ}C$ for 12 h, indicating an excellent diffusion barrier property of the $MnSi_xO_y$. The adhesion between Cu and $SiO_2$ was enhanced by the formation of $MnSi_xO_y$. Continuous and conductive Cu-Mn seed layers were deposited with PEALD into 32 nm $SiO_2$ trench, enabling a low temperature process, and the trench was perfectly filled using electrochemical plating (ECD) under conventional conditions. Thus, it is the resultant self-forming barrier process with PEALD Cu-Mn alloy film as a seed layer for plating Cu that has further potential to meet the requirement of the smaller than 30 nm node.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.409-409
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• 2013

최근, 집적 소자의 미세화에 따라 늘어난 배선 신호 지연 및 상호 간섭, 그리고 소비 전력의 증가는 초고집적 소자 성능 개선에 한계를 가져온다. 이에 따라 기존의 알루미늄(Al)/실리콘 절연 산화막은 구리(Cu)/저유전율 박막(low-k)으로 대체되고 있고, 이는 소자 성능 개선에 큰 영향을 미친다. 그러나 Cu는 Si과 low-k 내부로 확산이 빠르게 일어나 소자의 비저항을 높이고, 누설 전류를 일으키는 등 소자의 성능을 저하시킬 수 있는 문제점을 가지고 있다. 이러한 Cu의 확산을 막기 위하여 Ta, TaN 등과 같은 확산방지막에 대한 연구가 활발히 진행되어 왔으나, 배선 공정의 집적화와 low-k 대체에 따른 공정 및 신뢰성 문제로 인해 새로운 확산방지막의 개발이 필요하게 되었다. 이를 위해, 본 연구에서는 Cu-V 합금을 사용하여 low-k 기판 위에 확산방지막을 자가 형성 시키는 공정에 대한 연구를 진행하였다. 다양한 low-k 기판에서 열처리조건에 따른 Cu-V 합금의 특성을 확인하기 위해 4-point probe를 통한 비저항 평가와 XRD (X-ray diffraction) 분석이 이뤄졌다. 또한, TEM (transmission electron microscope)을 이용하여 $300^{\circ}C$에서 1 시간 동안 열처리를 거쳐 자가형성된 V-based interlayer가 low-k와 Cu의 계면에서 균일하게 형성된 것을 확인하였다. 형성된 V-based interlayer의 barrier 특성을 평가하고자 Cu-V합금/low-k/Si 구조와 Cu/low-k/Si 구조의 leakage current를 비교 분석하였다. Cu/low-k/Si 구조는 비교적 낮은 온도에서 leakage current가 급격히 증가하는 양상을 보였으나, Cu-V 합금/low-k/Si 구조는 $550^{\circ}C$의 thermal stress 에서도 leakage current의 변화가 거의 없었다. 이러한 결과를 바탕으로 열처리를 통해 자가형성된 V-based interlayer의 Cu/low-k 간 확산방지막으로서 가능성을 검증하였다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.41.2-41.2
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• 2011

Recently, scaling down of ULSI (Ultra Large Scale Integration) circuit of CMOS (Complementary Metal Oxide Semiconductor) based electronic devices become much faster speed and smaller size than ever before. However, very narrow interconnect line width causes some drawbacks. For example, deposition of conformal and thin barrier is not easy moreover metallization process needs deposition of diffusion barrier and glue layer. Therefore, there is not enough space for copper filling process. In order to overcome these negative effects, simple process of copper metallization is required. In this research, Cu-V thin alloy film was formed by using RF magnetron sputter deposition system. Cu-V alloy film was deposited on the plane $SiO_2$/Si bi-layer substrate with smooth and uniform surface. Cu-V film thickness was about 50 nm. Cu-V layer was deposited at RT, 100, 150, 200, and $250^{\circ}C$. XRD, AFM, Hall measurement system, and XPS were used to analyze Cu-V thin film. For the barrier formation, Cu-V film was annealed at 200, 300, 400, 500, and $600^{\circ}C$ (1 hour). As a result, V-based thin interlayer between Cu-V film and $SiO_2$ dielectric layer was formed by itself with annealing. Thin interlayer was confirmed by TEM (Transmission Electron Microscope) analysis. Barrier thermal stability was tested with I-V (for measuring leakage current) and XRD analysis after 300, 400, 500, 600, and $700^{\circ}C$ (12 hour) annealing. With this research, over $500^{\circ}C$ annealed barrier has large leakage current. However V-based diffusion barrier annealed at $400^{\circ}C$ has good thermal stability. Thus, thermal stability of vanadium-based thin interlayer as diffusion barrier is good for copper interconnection.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제40회 동계학술대회 초록집
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• pp.189-190
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• 2011

Cu가 기존 배선물질인 Al을 대체함에 따라 resistance-capacitance (RC) delay나 electromigration (EM) 등의 문제들이 어느 정도 해결되었다. 그러나 지속적인 배선 폭의 감소로 배선의 저항 증가, EM 현상 강화 그리고 stability 악화 등의 문제가 지속적으로 야기되고 있다. 이를 해결하기 위한 방법으로 Cu alloy seed layer를 이용한 barrier 자가형성 공정에 대한 연구를 진행하였다. 이 공정은 Cu 합금을 seed layer로 사용하여 도금을 한 후 열처리를 통해 SiO2와의 계면에서 barrier를 자가 형성시키는 공정이다. 이 공정은 매우 균일하고 얇은 barrier를 형성할 수 있고 별도의 barrier와 glue layer를 형성하지 않아 seed layer를 위한 공간을 추가로 확보할 수 있는 장점을 가지고 있다. 또한, via bottom에 barrier가 형성되지 않아 배선 전체 저항을 급격히 낮출 수 있다. 합금 물질로는 초기 Al이나 Mg에 대한 연구가 진행되었으나, 낮은 oxide formation energy로 인해 SiO2에 과도한 손상을 주는 문제점이 제기되었다. 최근 Mn을 합금 물질로 사용한 안정적인 barrier 형성 공정이 보고 되고 있다. 하지만, barrier 형성을 하기 위해 300도 이상의 열처리 온도가 필요하고 열처리 시간 또한 긴 단점이 있다. 본 실험에서는 co-sputtering system을 사용하여 Cu-V 합금을 형성하였고, barrier를 자가 형성을 위해 300도에서 500도까지 열처리 온도를 변화시키며 1시간 동안 열처리를 실시하였다. Cu-V 공정 조건 확립을 위해 AFM, XRD, 4-point probe system을 이용하여 표면 거칠기, 결정성과 비저항을 평가하였다. Cu-V 박막 내 V의 함량은 V target의 plasma power density를 변화시켜 조절 하였으며 XPS를 통해 분석하였다. 열처리 후 시편의 단면을 TEM으로 분석하여 Cu-V 박막과 SiO2 사이에 interlayer가 형성된 것을 확인 하였으며 EDS를 이용한 element mapping을 통해 Cu-V 내 V의 거동과 interlayer의 성분을 확인하였다. PVD Cu-V 박막은 기판 온도에 큰 영향을 받았고, 200 도 이상에서는 Cu의 높은 표면에너지에 의한 agglomeration 현상으로 거친 표면을 가지는 박막이 형성되었다. 7.61 at.%의 V함량을 가지는 Cu-V 박막을 300도에서 1시간 열처리 한 결과 4.5 nm의 V based oxide interlayer가 형성된 것을 확인하였다. 열처리에 의해 Cu-V 박막 내 V은 SiO2와의 계면과 박막 표면으로 확산하며 oxide를 형성했으며 Cu-V 박막 내 V 함량은 줄어들었다. 300, 400, 500도에서 열처리 한 결과 동일 조성과 열처리 온도에서 Cu-Mn에 의해 형성된 interlayer의 두께 보다 두껍게 성장 했다. 이는 V의 oxide formation nergyrk Mn 보다 작으므로 SiO2와의 계면에서 산화막 형성이 쉽기 때문으로 판단된다. 또한, V+5 이온 반경이 Mn+2 이온 반경보다 작아 oxide 내부에서 확산이 용이하며 oxide 박막 내에 여기되는 전기장이 더 큰 산화수를 가지는 V의 경우 더 크기 때문으로 판단된다.

• 한국환경보건학회지
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• 제36권3호
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• pp.236-246
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• 2010

In preparative anti-corrosive coating experiments, polyaniline was obtained by reacting an oxidizing agent with the monomer aniline. Further, the primer coating was prepared using a variety of widely-used materials such as urethane resin. For the top coating, epoxy resin and acrylic urethane resin were used. Characteristics of the coatings were assessed according to KS and ASTM specifications, and the structure of the polyaniline was characterized using FT-IR and TGA. For analysis of anti-corrosive properties in salt-spray experiments, measurements of the oxidation state of iron and surface atomic analysis were conducted using XPS and SEM-EDX. Unlike general anti-corrosive coatings which exhibit anti-corrosive effects only as a primer coating, the anti-corrosive coatings using polyaniline as the anti-corrosive pigment showed a marked synergistic effect with the top coatings. In other words, the top coatings not only produce a fine view effect, but also increase, through interaction with the primer coatings, the resistance to diffusion of corrosive factors from the external environment. It was also found that, unlike the heavy metal oxide-forming layer of the passive barrier alone, the polyaniline anti-corrosive pigment oxidized iron at the interface with the iron substrate to form a passive barrier in the oxidic layer, and itself formed a potential barrier layer with anti-corrosive factors from the external environment. Although the passive layer was damaged, the damaged area did not become completely oxidized iron; on the contrary, it showed a tendency to reduction. This can be interpreted such that a passive layer is formed again on the damaged area, and that at the same time there is a tendency to self-healing.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.100-101
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• 2012

The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

• Asia Marketing Journal
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• 제13권3호
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• pp.25-53
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• 2011

이번 연구는 실제 기업 자료를 기반으로 고객보상 프로그램이 고객 유지(retention)에 미치는 영향을 살펴보았다. 특히 고객보상 프로그램의 효과를 보다 명확히 확인하기 위해 유사실험설계(quasi-experimental design)를 사용하였다. 그리고 1년이 넘는 장기적인 시간 프레임 속에서 고객보상 프로그램의 도입 시점을 전후로 소비자 집단을 구분하고 이들 집단의 비교를 통해 고객보상 프로그램의 효과를 파악하였다. 이러한 연구 설계를 고려한 이유는 종적 자료를 사용한 선행 연구들이 고객보상 프로그램의 도입 시점 이후부터 가입 고객과 비가입 고객을 대상으로 프로그램의 효과를 측정하였기 때문에 자기선택오류(self-selection bias)의 가능성이 존재하였기 때문이다. 이번 연구는 고객보상 프로그램의 도입 시점을 전후로 두 집단을 비교하기 위해 자료를 특정 시점을 기준으로 절단(censoring)하였다. 생존분석(survival analysis)은 다른 분석기법에 비해 불완전한 자료가 포함되더라도 분석이 상대적으로 용이하므로 이번 연구의 분석방법으로 선택하였다. 분석 결과 고객보상 프로그램을 실시하기 전에는 소비자들의 거래기간이 평균 179일이었으나 고객보상 프로그램을 도입한 이후에는 227일로 약 50일 정도 더 늘어났다. 이러한 차이는 통계적으로 유의한 것으로 나타나 연구 가설을 지지하였다. 또한 콕스 비례위험모형을 사용하여 고객보상 프로그램과 영향 변수들의 상호작용효과를 확인한 결과 기존고객들은 고객보상 프로그램이 도입된 후 신규고객들에 비해 회사와의 거래기간이 유의하게 증가한 것으로 나타났으며 긍정적인 서비스(예: 30일 이내 입회)를 경험한 고객들도 회사와의 거래기간이 유의하게 증가하는 것으로 나타났다. 한편 부정적인 서비스(예: 30일 이후 입회)를 경험한 고객이라 하더라도 고객보상 프로그램을 도입한 이후에는 회사와의 거래기간이 증가하였다. 이번 연구에서 나타난 결과들을 정리하면 고객보상 프로그램은 고객과 긍정적인 관계를 형성하는 데 기여할 뿐만 아니라 이탈 장벽까지 구축해 줌으로써 기업의 경쟁력을 강화시키는 수단으로서의 가치가 있다고 생각할 수 있다.