• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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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.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.98-98
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• 2013

완전화 박막이란 사용자가 원하는 용도에 맞게 최적의 성능을 구현하도록 제조된 박막을 의미하며 금속이나 화합물 박막을 제조하되 각종 구조 제어 Tool이나 증착 공정을 변화시켜 나노화와 다층화 또는 치밀화를 통해 구현될 수 있다. 최근 고성능의 증착 및 제어 Tool이 개발되고 빗각증착(Oblique Angle Deposition)이나 스침각 증착(Glancing Angle Deposition) 방법 등의 기술이 개발되면서 사용자 목적에 최적인 박막 소재를 제공하여 User-friendly한 응용을 위한 연구개발이 활발히 진행되고 있다. 완전화 박막 제조에 대한 시도는 1990년대에 일본에서 시작되었다. 일본에서는 산학연이 공동으로 참여하는 NEDO 프로그램을 통해 경질코팅을 이용한 Protective Layer를 제조하여 차단 방식에 의한 내식성 구현 연구를 수행하였다. 유럽에서는 제 7차 European Framework Program (7th FT)을 통해 2007년부터 CORRAL (Corrosion Protection with Perfect Atomic Layer) 프로젝트를 만들어 완전화 박막 연구를 진행하고 있다. 상기 프로젝트는 얇은 자연 산화막이 Bulk의 부식을 방지해주는 것에 착안하여 HIPIMS나 Filtered Arc 또는 ALD 공정을 이용하여 자연 산화막과 유사한 Defect-free 산화막을 제조하여 Barrier형 내식성 박막을 구현하는 것을 목표로 하고 있다. 본 연구에서는 완전화 박막 구현을 위한 연구동향을 파악하고 완전화 박막 제조를 위한 기술적 과제와 몇 가지의 시도에 대한 기초 연구 자료를 소개한다.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.24 no.3
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• pp.106-110
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• 2014

The passivation property of $Al_2O_3$ thin film formed using atomic layer deposition (ALD) for the application of crystalline Si solar cells was investigated using microwave photoconductance decay (${\mu}$-PCD). After post-annealing at $400^{\circ}C$ for 5 min, $Al_2O_3$ thin film exhibited the structural stability having amorphous nature without the interfacial reaction between $Al_2O_3$ and Si. The post-annealing at $400^{\circ}C$ for 5 min led to an increase in the relative effective lifetime of $Al_2O_3$ thin film. This could be associated with the field effective passivation combined with surface passivation of textured Si. The capacitance-voltage (C-V) characteristics of the metal-oxide-semiconductor (MOS) with $Al_2O_3$ thin film post-annealed at $400^{\circ}C$ for 5 min was carried out to evaluate the negative fixed charge of $Al_2O_3$ thin film. From the relationship between flatband voltage ($V_{FB}$) and equivalent oxide thickness (EOT), which were extracted from C-V characteristics, the negative fixed charge of $Al_2O_3$ thin film was calculated to be $2.5{\times}10^{12}cm^{-2}$, of which value was applicable to the passivation layer of n-type crystalline Si solar cells.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.160-160
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• 2010

Organic electronic devices require a passivation layer to ensure sufficient lifetime. Specifically, flexible organic electronic devices need a barrier layer that transmits less than $10^{-6}\;g/m^2/day$ of water and $10^{-5}\;g/m^2/day$ of oxygen. To increase the lifetime of organic electronic device, therefore, it is indispensable to protect the organic materials from water and oxygen. Severe groups have reported on multi-layerd barriers consisting inorganic thin films deposited by plasma enhenced chemical deposition (PECVD) or sputtering. However, it is difficult to control the formation of granular-type morphology and microscopic pinholes in PECVD and sputtering. On the contrary, atomic layer deoposition (ALD) is free of pinhole, highly uniform, conformal films and show good step coverage. In this study, the passivation layer was deposited using single-process PEALD. The passivation layer, in our case, was a bilayer system consisting of $Al_2O_3$ films and a $TiO_2$ buffer layer on a poly (ether sulfon) (PES) substrate. Because the deposition temperature and plasma power have a significant effect on the properties of the passivation layer, the characteristics of the $Al_2O_3$ films were investigated in terms of density under different deposition temperatures and plasma powers. The effect of the $TiO_2$ buffer layer also was also addressed. In addition, the water vapor transmission rate (WVTR) and organic light-emitting diode (OLEDs) lifetime were measured after forming a bilayer composed of $Al_2O_3/TiO_2$ on a PES substrate.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.120.2-120.2
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• 2013

반도체 소자의 소형화로 신개념 화학증착공정 구현을 위한 장비와 화학증착소재의 개발이 활발이 연구되고 있다. 특히 증착소재의 물리적 화학적 특성을 파악하고 가장 적합한 소재를 선택하기 위한 연구도 변행되고 있다. 많은 연구자들이 소재 평가를 위해 가스크로마토그래피, 질량분석기, 적외선 분광기 등을 이용한 화학증착소재의 특성을 파악하기 위해 노력하고 있다. 하지만 실제 화학기상증착(Chemical Vapor Deposition)법과 원자층증착(Atomic Layer Deposition)법 공정에서 웨이퍼 표면에서의 화학증착소재의 흡착거동에 대한 연구는 거의 전무한 실정이다. 따라서 본 연구에서는 개선된 Attenuated Total Reflectance(ATR)분광계를 이용하여 표면에 흡착된 소재의 흡착거동에 대해 분석을 수행하였다. 평가에 사용된 화학증착소재는 C-Zr (Tris (dimethylamino) cyclopentadienyl zirconium)이며, Fourier Transform Infrared Spectroscopy (FT- IR)시스템 내에 설치된 ATR 분광계 표면에 흡착된 C-Zr 증착소재를 다양한 공정조건(온도 및 반응가스, 플라즈마 파워 등)에서의 거동 변화를 연구하였다.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.377-377
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• 2012

Microprocessor technology now relies on copper for most of its electrical interconnections. Because of the high diffusivity of copper, Atomic layer deposition (ALD) $TaN_x$ is used as a diffusion barrier to prevent copper diffusion into the Si or $SiO_2$. Another problem with copper is that it has weak adhesion to most materials. Strong adhesion to copper is an essential characteristic for the new barrier layer because copper films prepared by electroplating peel off easily in the damascene process. Thus adhesion-enhancing layer of cobalt is placed between the $TaN_x$ and the copper. Because, cobalt has strong adhesion to the copper layer and possible seedless electro-plating of copper. Until now, metal film has generally been deposited by physical vapor deposition. However, one draw-back of this method is poor step coverage in applications of ultralarge-scale integration metallization technology. Metal organic chemical vapor deposition (MOCVD) is a good approach to address this problem. In addition, the MOCVD method has several advantages, such as conformal coverage, uniform deposition over large substrate areas and less substrate damage. For this reasons, cobalt films have been studied using MOCVD and various metal-organic precursors. In this study, we used $C_{12}H_{10}O_6(Co)_2$ (dicobalt hexacarbonyl tert-butylacetylene, CCTBA) as a cobalt precursor because of its high vapor pressure and volatility, a liquid state and its excellent thermal stability under normal conditions. Furthermore, the cobalt film was also deposited at various $H_2/NH_3$ gas ratio(1, 1:1,2,6,8) producing pure cobalt thin films with excellent conformality. Compared to MOCVD cobalt using $H_2$ gas as a reactant, the cobalt thin film deposited by MOCVD using $H_2$ with $NH_3$ showed a low roughness, a low resistivity, and a low carbon impurity. It was found that Co/$TaN_x$ film can achieve a low resistivity of $90{\mu}{\Omega}-cm$, a low root-mean-square roughness of 0.97 nm at a growth temperature of $150^{\circ}C$ and a low carbon impurity of 4~6% carbon concentration.

• JSTS:Journal of Semiconductor Technology and Science
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• v.15 no.2
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• pp.267-275
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• 2015

In this paper, ZnO films were prepared by atomic layer deposition (ALD) and CdS films were deposited using chemical bath deposition (CBD) to form ZnO/CdS heterojunction. More accurate mapping of band arrangement of the ZnO/CdS heterojunction has been performed by analyzing its electrical and optical characteristics in depth by various methods including transmittance, x-ray photoemission spectroscopy (XPS), and ultraviolet photoemission spectroscopy (UPS). The optical bandgap energies ($E_g$) of ZnO and CdS were 3.27 eV and 2.34 eV, respectively. UPS was capable of extracting the ionization potential energies (IPEs) of the materials, which turned out to be 8.69 eV and 7.30 eV, respectively. The electron affinity (EA) values of ZnO and CdS calculated from IPE and $E_g$ were 5.42 eV and 4.96 eV, respectively. Energy-band structures of the heterojunction could be accurately drawn from these parameters taking the conduction band offset (CBO) into account, which will substantially help acquisition of the full band structures of the thin films in the CIGS solar-cell device and contribute to the optimal device designs.

• Proceedings of the Korean Society Of Semiconductor Equipment Technology
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• 2007.06a
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• pp.193-198
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• 2007

The NiSi is very promising candidate for the metallization in 60nm CMOS process such as FUSI(fully silicided) gate and source/drain contact because it exhibits non-size dependent resistance, low silicon consumption and mid-gap workfunction. Ni film was first deposited by using ALD (atomic layer deposition) technique with Bis-Ni precursor and $H_2$ reactant gas at $220^{\circ}C$ with deposition rate of $1.25{\AA}/cycle$. The as-deposited Ni film exhibited a sheet resistance of $5{\Omega}/{\square}$. RTP (repaid thermal process) was then performed by varying temperature from $400^{\circ}C$ to $900^{\circ}C$ in $N_2$ ambient for the formation of NiSi. The process window temperature for the formation of low-resistance NiSi was estimated from $600^{\circ}C$ to $800^{\circ}C$ and from $700^{\circ}C$ to $800^{\circ}C$ with and without Ti capping layer. The respective sheet resistance of the films was changed to $2.5{\Omega}/{\square}$ and $3{\Omega}/{\square}$ after silicidation. This is because Ti capping layer increases reaction between Ni and Si and suppresses the oxidation and impurity incorporation into Ni film during silicidation process. The NiSi films were treated by additional thermal stress in a resistively heated furnace for test of thermal stability, showing that the film heat-treated at $800^{\circ}C$ was more stable than that at $700^{\circ}C$ due to better crystallinity.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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• pp.96-96
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• 2016

나노섬유(nanofiber), 나노선(nanowire), 그리고 나노튜브(nanotube)와 같은 1차원 구조의(one-dimensional structure) 나노재료는 벌크(bulk) 및 박막(film) 재료와는 다르게 물리적, 화학적으로 특이한 성질을 가지고 있으며, 이러한 성질은 나노재료의 구조, 형상, 크기 등에 큰 영향을 받는다. 첫 째, 전기방사(electrospinning) 공정을 이용한 나노섬유의 합성; 용액의 특성, 전기장 세기, 방사시간 등의 변수를 조절하게 되면 방출되는 재료의 형상을 입자 혹은 섬유상의 형태로 얻을 수 있으며, 전기방사를 통해 합성된 나노재료의 소결 온도 및 시간을 달리함으로써 나노입자의 크기를 조절할 수 있다. 또한, 템플레이트 합성법(template synthesis) 및 이중노즐(coaxial nozzle)을 이용해 속이 빈 형태인 중공(hollow) 구조의 나노섬유를 얻을 수 있으며, 전기방사에 사용되는 전구물질에 원하는 금속 및 산화물을 첨가함으로써 복합체(composite) 나노섬유를 얻을 수 있다. 둘 째, VLS(Vapor-Liquid-Solid) 공정을 이용한 나노선의 성장; 온도, 압력, 전구물질의 양, 그리고 시간 등의 변수를 조절하게 되면 원하는 직경 및 길이를 갖는 나노선을 성장시킬 수 있다. 그리고 ALD(Atomic Layer Deposition)를 이용해 나노선에 추가적인 층을 형성함으로써 코어-셀 구조를 형성할 수 있으며, 감마선, UV와 같은 공정을 이용해 귀금속 촉매를 나노선에 기능화 시킬 수도 있다. 코어-셀 구조를 갖는 나노선/나노섬유는 코어 혹은 셀 층의 전자나 홀의 이동을 유발하여 전자공핍층(electron depletion layer) 또는 정공축적층(hole accumulation layer)을 확대 및 축소시켜 센서의 초기저항을 증가시키거나 감소시키는 역할로써 이용되고 있으며, 특히, 셀 층의 두께가 셀 층 재료의 Debye length와 유사한 크기를 갖게 되면, 셀 층은 완전공핍층(fully depleted layer)을 형성해 최대의 감도를 나타낼 수 있다. 본 연구에서는 다양한 제조 공정을 통해 제작될 수 있는 1차원 나노-구조물을 가스센서에 적용하는 사례들을 소개하고, 이러한 가스센서의 감응성능을 향상시키기 위한 방법의 한 가지로 원자층증착법으로 나노선/나노섬유의 표면에 셀층을 형성하여 감응성 향상 메커니즘 및 관련 주요 변수들을 조사하고자 한다.

• JSTS:Journal of Semiconductor Technology and Science
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• v.14 no.1
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• pp.40-47
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• 2014

In this paper, $Al_2O_3$ film deposited by thermal atomic layer deposition (ALD) with diluted $NH_4OH$ instead of $H_2O$ was suggested for passivation layer and anti-reflection (AR) coating of the p-type crystalline Si (c-Si) solar cell application. It was confirmed that the deposition rate and refractive index of $Al_2O_3$ film was proportional to the $NH_4OH$ concentration. $Al_2O_3$ film deposited with 5 % $NH_4OH$ has the greatest negative fixed oxide charge density ($Q_f$), which can be explained by aluminum vacancies ($V_{Al}$) or oxygen interstitials ($O_i$) under O-rich condition. $Al_2O_3$ film deposited with $NH_4OH$ 5 % condition also shows lower interface trap density ($D_{it}$) distribution than those of other conditions. At $NH_4OH$ 5 % condition, moreover, $Al_2O_3$ film shows the highest excess carrier lifetime (${\tau}_{PCD}$) and the lowest surface recombination velocity ($S_{eff}$), which are linked with its passivation properties. The proposed $Al_2O_3$ film deposited with diluted $NH_4OH$ is very promising for passivation layer and AR coating of the p-type c-Si solar cell.