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New Approaches for Overcoming Current Issues of Plasma Sputtering Process During Organic-electronics Device Fabrication: Plasma Damage Free and Room Temperature Process for High Quality Metal Oxide Thin Film

  • Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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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.

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Fabrication of Schottky Device Using Lead Sulfide Colloidal Quantum Dot

  • Kim, Jun-Kwan;Song, Jung-Hoon;An, Hye-Jin;Choi, Hye-Kyoung;Jeong, So-Hee
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.189-189
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    • 2012
  • Lead sulfide (PbS) nanocrystal quantum dots (NQDs) are promising materials for various optoelectronic devices, especially solar cells, because of their tunability of the optical band-gap controlled by adjusting the diameter of NQDs. PbS is a IV-VI semiconductor enabling infrared-absorption and it can be synthesized using solution process methods. A wide choice of the diameter of PbS NQDs is also a benefit to achieve the quantum confinement regime due to its large Bohr exciton radius (20 nm). To exploit these desirable properties, many research groups have intensively studied to apply for the photovoltaic devices. There are several essential requirements to fabricate the efficient NQDs-based solar cell. First of all, highly confined PbS QDs should be synthesized resulting in a narrow peak with a small full width-half maximum value at the first exciton transition observed in UV-Vis absorbance and photoluminescence spectra. In other words, the size-uniformity of NQDs ought to secure under 5%. Second, PbS NQDs should be assembled carefully in order to enhance the electronic coupling between adjacent NQDs by controlling the inter-QDs distance. Finally, appropriate structure for the photovoltaic device is the key issue to extract the photo-generated carriers from light-absorbing layer in solar cell. In this step, workfunction and Fermi energy difference could be precisely considered for Schottky and hetero junction device, respectively. In this presentation, we introduce the strategy to obtain high performance solar cell fabricated using PbS NQDs below the size of the Bohr radius. The PbS NQDs with various diameters were synthesized using methods established by Hines with a few modifications. PbS NQDs solids were assembled using layer-by-layer spin-coating method. Subsequent ligand-exchange was carried out using 1,2-ethanedithiol (EDT) to reduce inter-NQDs distance. Finally, Schottky junction solar cells were fabricated on ITO-coated glass and 150 nm-thick Al was deposited on the top of PbS NQDs solids as a top electrode using thermal evaporation technique. To evaluate the solar cell performance, current-voltage (I-V) measurement were performed under AM 1.5G solar spectrum at 1 sun intensity. As a result, we could achieve the power conversion efficiency of 3.33% at Schottky junction solar cell. This result indicates that high performance solar cell is successfully fabricated by optimizing the all steps as mentioned above in this work.

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Effect of the Concentration of Citrate on the Growth of Aqueous Chemical Bath Deposited ZnO and Application of the Film to Cu(In,Ga)Se2 Solar Cells (Citrate 농도에 따른 수용액 화학조 증착 ZnO 성장 및 ZnO 박막의 Cu(In,Ga)Se2 태양전지 응용)

  • Cho, Kyung Soo;Jang, Hyunjun;Oh, Jae-Young;Kim, Jae Woo;Lee, Jun Su;Choi, Yesol;Hong, Ki-Ha;Chung, Choong-Heui
    • Korean Journal of Materials Research
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    • v.30 no.4
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    • pp.204-210
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    • 2020
  • ZnO thin films are of considerable interest because they can be customized by various coating technologies to have high electrical conductivity and high visible light transmittance. Therefore, ZnO thin films can be applied to various optoelectronic device applications such as transparent conducting thin films, solar cells and displays. In this study, ZnO rod and thin films are fabricated using aqueous chemical bath deposition (CBD), which is a low-cost method at low temperatures, and environmentally friendly. To investigate the structural, electrical and optical properties of ZnO for the presence of citrate ion, which can significantly affect crystal form of ZnO, various amounts of the citrate ion are added to the aqueous CBD ZnO reaction bath. As a result, ZnO crystals show a nanorod form without citrate, but a continuous thin film when citrate is above a certain concentration. In addition, as the citrate concentration increases, the electrical conductivity of the ZnO thin films increases, and is almost unchanged above a certain citrate concentration. Cu(In,Ga)Se2 (CIGS) solar cell substrates are used to evaluate whether aqueous CBD ZnO thin films can be applicable to real devices. The performance of aqueous CBD ZnO thin films shows performance similar to that of a sputter-deposited ZnO:Al thin film as top transparent electrodes of CIGS solar cells.

Fabrication and Characterization of Organic Solar Cells with Gold Nanoparticles in PEDOT:PSS Hole Transport Layer (PEDOT:PSS 정공 수송층에 금 나노입자를 첨가한 유기태양전지의 제작 및 특성 연구)

  • Kim, Seung Ho;Choi, Jae Young;Chang, Ho Jung
    • Journal of the Microelectronics and Packaging Society
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    • v.20 no.2
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    • pp.39-46
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    • 2013
  • In this paper, organic solar cells(OSCs) based on bulk-heterojunction structures were fabricated by spin coating method using polymer P3HT and fullerene PCBM as a photoactive layer. The fabricated OSCs had a simple glass/ITO/PEDOT:PSS/P3HT:PCBM/Al structures. The photoactive layer of mixed P3HT:PCBM was formed with 1:1 weight ratio. The hole transport layer(HTL) was used conducting polymer PEDOT:PSS concentration with gold nanoparticles. The annealing temperature and concentration of nanoparticles in HTL were verified to improve the OSC characterization. The percentage of gold nanoparticles in HTL were 0.5 wt% and 1.0 wt%, and the surface morphology, electrical properties and absorption intensities were investigated. The devices were 0.5 wt%, and the highest 3.1% of the powder conversion efficiency(PCE), 10.2 $mA/cm^2$ of the maximum short circuit current density($J_{SC}$), 0.535V of the open circuit voltage($V_{OC}$) and 55.8% of the fill factor(F.F) could be obtained when the nanoparticle concertration was 0.5 wt%. The annealing temperature of HTL was $110^{\circ}C$, $130^{\circ}C$, $150^{\circ}C$ in vacuum oven and measured the absorption intensities, surface morphology, crystallinity and electrical properties were investigated. The best property was obtained in HTL annealed at $130^{\circ}C$ for gold nanoparticles of 0.5 wt%, showing that $J_{SC}$, $V_{OC}$, F.F and PCE were about 12.0 $mA/cm^2$, 0.525V, 64.2% and 4.0%, respectively.

Microstructure and Magnetic Properties of Zn1-xCoxO Thin Films Grown by Sol-Gel Process (Sol-Gel 법으로 제작한 Zn1-xCoxO 박박의 미세조직 및 자기적 특성)

  • Ko, Yoon-Duk;Tai, Weon-Pil;Kim, Eung-Kwon;Kim, Ki-Chul;Choi, Choon-Gi;Kim, Jong-Min;Song, Joon-Tae;Park, Tae-Seok;Suh, Su-Jeung;Kim, Young-Sung
    • Journal of the Korean Ceramic Society
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    • v.42 no.7 s.278
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    • pp.475-482
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    • 2005
  • Zn$_{l-x}$Co$_{x}$O (x = 0.05 - 0.20) films were grown on Coming 7059 glass by sol-gel process. A homogeneous and stable Zn$_{l-x}$Co$_{x}$O sol was prepared by dissolving zinc acetate dihydrate (Zn(CH$_{3}$COO)$_{2}$$\cdot$2H$_{2}$O), cobalt acetate tetrahydrate ((CH$_{3}$)$_{2}$$\cdot$CHOH) and aluminium chloride hexahydrate (AlCl$_{3}$ $\cdot$ 6H$_{2}$O) as solute in solution of isopropanol ((CH$_{3}$)$_{2}$$\cdot$CHOH) and monoethanolamine (MEA:H$_{2}$NCH$_{2}$CH$_{2}$OH). The films grown by spin coating method were postheated in air at 650°C for 1 h and annealed in the condition of vacuum (5 $\times$ 10$^{-6}$ Torr) at 300$^{\circ}C$ for 30 min and investigated the nature of c-axis preferred orientation and physical properties with different Co concentrations. Znl_xCOxO thin films with different Co concentrations were well oriented along the c-axis, but especially a highly c-axis oriented Zn$_{l-x}$Co$_{x}$O thin film was grown at 10 at$\%$ Co concentration. The transmittance spectra showed that Zn$_{l-x}$Co$_{x}$O thin films occur typical d-d transitions and sp-d exchange interaction became activated with increasing Co concentration. The electrical resistivity of the films at 10 at$\%$ Co had the lowest value due to the highest c-axis orientation. X-ray photoelectron spectroscopy and alternating gradient magnetometer analyses indicated that no Co metal cluster was formed, and the ferromagnetic properties appeared, respectively. The characteristics of the electrical resistivity and room temperature ferromagnetism of Zn$_{l-x}$Co$_{x}$O thin films suggested the possibility for the application to dilute magnetic semiconductors.

The Low-field Tunnel-type Magnetoresistance Characteristics of Thin Films Deposited on Different Substrate (기판 효과에 따른 저 자장 영역에서의 자기저항 효과에 관한 연구)

  • Lee, Hi-Min;Shim, In-Bo;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.12 no.2
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    • pp.41-45
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    • 2002
  • The low-field tunnel-type magnetoresistance (MR) properties of sol-gel derived $La_{0.7}Pb_{0.3}MnO_3(LPMO)$ thin film deposited on different substrate have been investigated. Polycrystalline thin films were fabricated by spin-coating on $SiO_2/Si(100)$ substrate and that with yttria-stabilized zirconia (YSZ) buffer layer, while c-axis-oriented thim film was grown on $LaAlO_3(001)$ (LAO) single crystal substrate. The full width half maximum (FWHM) of the rocking curve scan of LPMO/LAO film is $0.32^{\circ}$. Tunnel-type MR ratio is 0.52 % in $LPMO/SiO_2/Si$(100) film and that of $LPMO/YSZ/SiO_2/Si$(100) film is as high as 0.68 %, whereas that of LPMO/LAO(001) film is less than 0.4 % under the applied field of 500 Oe at 300 K. Well-pronounced MR hysteresis was registered with an MR peak in the vicinity of the coercive field. The low-field tunnel-type MR characteristics of thin films deposited on different substrates originates from the behavior of grain boundary properties.

Effect of processing parameters on TiO2 film by room temperature granule spray in vacuum (상온진공과립분사에 의한 TiO2 코팅층에 미치는 공정변수의 영향)

  • Kim, Han-Gil;Park, Yoon-Soo;Bang, Kook-Soo;Park, Dong-Soo;Park, Chan
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.27 no.1
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    • pp.22-27
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    • 2017
  • $TiO_2$ films, thickness of $1{\sim}30{\mu}m$ were deposited on glass substrate at room temperature by room temperature granule spray in vacuum. The starting powder was calcinated at $600^{\circ}C$ for 4 h using $Al_2O_3$ crucible in the furnace. The particle size of the $TiO_2$, $1.5{\mu}m$ was measured by a particle size analyzer. The effect of different process parameters such as number of pass, gas flow rate and feeder voltage was studied. As the number of passes increased, the film thickness increased proportionally due to adequate kinetic energy conserved. The effect of three different flow rates (i.e. 15, 25, and 35 LPM) on deposited film was investigated. As gas flow rate increased, the film thickness increased up to 25 LPM and then decreased. Higher feeder voltage with low flow rate of 15 LPM resulted in unsufficient coating thickness due to insufficient kinetic energy. Microstructure of $TiO_2$ films was investigated by scanning electron microscope and high resolution tramission electron microscope.

Preparation and Application of Nanofiltration Membranes (NF막 제조 및 응용공정)

  • 이규호;오남운;제갈종건
    • Proceedings of the Membrane Society of Korea Conference
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    • 1998.06a
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    • pp.135-153
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    • 1998
  • Nanofiltration (NF) is a recently introduced term in membrane separation. In 1988, Eriksson was one of the first authors using the word 'nanofiltration' explicitly. Some years before, FilmTech started to use this term for their NF50 membrane which was supposed to be a very loose reverse osmosis membrane or a very tight ultrafiltration membrane. Since then, this term has been introduced to indicate a specific boundary of membrane technology in between ultrafiltration and reverse osmosis. The application fields of the NF membranes are very broad as follows: Demeneralizing water, Cleaning up contaminated groundwater, Ultrapure water production, Treatment of effleunts containing heavy metals, Offshore oil platforms, Yeast production, Pulp and paper mills, Textile production, Electroless copper plating, Cheese whey production, Cyclodextrin production, Lactose production. The earliest NF membrane was made by Cadotte et al, using piperazine and trimesoyl chloride as monomers for the formation of polyamide active layer of the composite type membrane. They coated very thin interfacially potymerized polyamide on the surface of the microporous polysulfone supports. The NF membrane exhibited low rejections for monovalent anions (chloride) and high rejections for bivalent anions (sulphate). This membrane was called NS300. Some of the earliest NF membranes, like the NF40 membrane of FilmTech, the NTR7250 of Nitto-Denko and the UTC20 and UTC60 of Toray, are formed by a comparable synthesis route as the NS300 membrane. Commercially available NF membranes nowadays are as follows: ASP35 (Advanced Membrane Technology), MPF21; MPF32 (Kiryat Weizmann), UTC20; UTC60; UTC70; UTC90 (Toray), CTA-LP; TFCS (Fluid Systems), NF45; NF70 (FilmTec), BQ01; MX07; HG01; HG19; SX01; SX10 (Osmonics), 8040-LSY-PVDI (Hydranautics), NF CA30; NF PES 10 (Hoechst), WFN0505 (Stork Friesland). The typical ones among the commercially available NF membranes are polyamide composite membrane consisting of interfacially polymerized polyamide active layer and microporous support. While showing high water fluxes and high rejections of multivalent ions and small organic molecules, these membranes have relatively low chemical stability. These membranes have low chlorine tolerance and are unstable in acid or base solution. This chemical instability is appearing to be a big obstacle for their applications. To improve the chemical stability, we have tried, in this study, to prepare chemically stable NF membranes from PVA. The ionomers and interfacially polymerized polyamide were used for the modification of'the PVA membranes. For the detail study of the active layer, homogeneous NF membranes made only from active layer materials were prepared and for the high performance, composite type NF membranes were prepared by coating the active layer materials on microporous polysulfone supports.

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Wear and corrosion coatings by MO-PACVD and dual plasma processes (MO-PACVD 및 복합 플라즈마 공정에 의한 내마모 내식성 코팅)

  • 김선규
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 1999.10a
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    • pp.3-4
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    • 1999
  • 최근 산업이 고속도화, 고능률화 및 고정멸화의 추세로 발전함에 따라 우수한 내마모성, 인성, 고온 안정성 및 내구성을 갖는 공구 및 금형을 요구하게 되었다. 그러나 이와같은 성질들은 어떤 단일 재료에서는 얻을 수 없으며 적당한 기판공구나 금혈위에 내마모성 보호피막을 coating함으로 비교적 저렴하게 얻을 수 있다. 화학증착법으로 TiC, TiN등을 증착시킬때에는 $1000^{\circ}C$정도의 반응온도가 필요하며 이러한 증착온도는 모재가 초경합금일때는 문제가 안되나 강재일 경우 모재의 연화와 칫수변화의 문제를 야기시킨다. 최근에는 플라즈마를 사용하여 증착반응온도를 $550^{\circ}C$ 이하로 낮추는 플라즈마 화학 증착볍(PACVD)이 대두되고 있다. 그러나 이 방법어서 는 뚱착하려는 금속원소가 TiCl4의 형태로 공급되고 있으므로 생성된 층이 염소를 포함하고 있다. 이 층에 잔존하는 염소는 층의 기계적 성질을 저하시키고 층내의 stress를 유발시킨다. 또한 HCI개스의 생성으로 인하여 펌프 및 장비의 부식이 촉진 된다 이러한 결점을 극복하기 위하여 금속유기화합물 전구체(metallo-organic precursor)로 $TiCl_4$를 대체하고자 하는 연구가 활발하게 진행되고 있으며 본 연구실에서 이에 대하여 연구한 결과를 소개하고자 한다. diethylamino titanium을 전구체로 사용하여 $H_2,\;N_2,\;Ar$분위기하에서 pulsed d.c.를 사용하는 MO-PACVD에 의하여 $150~250^{\circ}C$의 저온에서 Al 2024 기판에 TiCN층 형 성을 하였다. 전구체 증발온도는 $74~78^{\circ}C$의 온도범위어야 하며 고경도의 코탱층은 54% duty, 14.2kHz, 450V의 조건에서 얻어졌으며 duty, 주파수, 전압이 증가함에 따라 경도는 저하되었다. 이때의 표면 morphology를 SEM으로 조사한바 dome structure가 크게 발달되었음을 알 수 있었다. 본 실험의 온도 범위내에서 얻은 TiCN 증착반응의 활성화에너지는 7.5Kcal/mol이었다. 증착된 TiCN층은 우수한 내마모섣을 나타내었으며 스크래치테스트 결과 17N의 엄계하중을 나타내었다. 본 연구에서 변화 시킨 duty, 주파수, 전압의 범위에서는 층의 밀착력은 크게 변화하지 않았다. titanium isopropoxide를 전구체로 사용하여 Hz, Nz 분위기하에서 d.c.를 사용하는 MO-PACVD에 의하여 Ti(NCO) 코팅층을 SKDll, SKD61, SKH9 공구강에 형성시키는 공정을 개발하였다. 최적의 Ti(NCO) 코탱층을 얻기 위해 유입전구체 부피%의 양은 향착압력의 5%를 넘지 않아야 되고 수소와 젤소 가스비가 1:1일 때 가장 높은 코팅층의 경도값을 나타내었다. 수소와 질소 가스비가 3:7일 때 TiFeCr(NCO)의 복화합물 코팅층이 형성됨을 알 수 있었고 500t의 증착온도에서 얻은 Ti(NCO) 코팅층이 높은 경도값과 좋은 내식성을 나타내었다. 또한 이와같은 Ti(NCO) 코팅공정과 본 실험실에서 개발한 확산층만 형성시키는 plsma nitriding 공정을 결합하여 복합코탱층을 형성하였는데 이 복합코팅층은 고경도와 우수한 내마모성, 내식성 뿐만 아니라 10)N 이상의 뛰어난 밀착력을 나타내었다. 현재 많이 사용되고 있는 PVD법은 step coverage가 좋지 않은 점과 cost intensive p process라는 단점이 있다. MO-PACVD법은 이러한 문제를 해결할 수 있는 방법으로서 앞으로 지속적인 도전이 요구되는 분야이다.

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Design and Analysis of a Laser Lift-Off System using an Excimer Laser (엑시머 레이저를 사용한 LLO 시스템 설계 및 분석)

  • Kim, Bo Young;Kim, Joon Ha;Byeon, Jin A;Lee, Jun Ho;Seo, Jong Hyun;Lee, Jong Moo
    • Korean Journal of Optics and Photonics
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    • v.24 no.5
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    • pp.224-230
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    • 2013
  • Laser Lift-Off (LLO) is a process that removes a GaN or AIN thin layer from a sapphire wafer to manufacture vertical-type LEDs. It consists of a light source, an attenuator, a mask, a projection lens and a beam homogenizer. In this paper, we design an attenuator and a projection lens. We use the 'ZEMAX' optical design software for analysis of depth of focus and for a projection lens design which makes $7{\times}7mm^2$ beam size by projecting a beam on a wafer. Using the 'LightTools' lighting design software, we analyze the size and uniformity of the beam projected by the projection lens on the wafer. The performance analysis found that the size of the square-shaped beam is $6.97{\times}6.96mm^2$, with 91.8 % uniformity and ${\pm}30{\mu}m$ focus depth. In addition, this study performs dielectric coating using the 'Essential Macleod' to increase the transmittance of an attenuator. As a result, for 23 layers of thin films, the transmittance total has 10-96% at angle of incidence $45-60^{\circ}$ in S-polarization.