• Title/Summary/Keyword: Barrier film

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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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Diffusion barrier properties of MOCVD TiN thin film for AI planarization technology (AI planarization 기술에서 MOCVD TiN 박막의 barrier 특성)

  • 홍정의;김창렬;김준기;변정수;나관구;김우식
    • Journal of the Korean Vacuum Society
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    • v.4 no.S1
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    • pp.21-27
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    • 1995
  • AI planarization 공정을 위한 barrier로서 CVD 및 PVD 방법에 의해 증착된 TiN 박막의 특성에 대하여 연구하였다. CVD TiN은 TDMAT source를 사용한 MOCVD방법으로 증착하였으며, PVD TiN은 1:1 aspect ratio(A/R)를 갖는 collimator를 사용한 reactive wputtering법으로 증착하였다. AES, SEM을 이용하여 CVD TiN과 PVD TiN의 조성을 분석하고 barrier 특성을 평가하였다. CVD TiN, PVD TiN 모두 400$\AA$의 두께와 RTA 처리에 의해서 AI planarization에 대한 양호한 barrier 특성을 확보할 수 있었다.

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A bilayer diffusion barrier of atomic layer deposited (ALD)-Ru/ALD-TaCN for direct plating of Cu

  • Kim, Soo-Hyun;Yim, Sung-Soo;Lee, Do-Joong;Kim, Ki-Su;Kim, Hyun-Mi;Kim, Ki-Bum;Sohn, Hyun-Chul
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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    • pp.239-240
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    • 2008
  • As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.

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Thermal Stability of TiN/Ti Barrier Metals with Al Overlayers and Si Substrates Modified under Different Annealing Histories (형성조건에 따른 TiN/Ti Barrier Metal의 Al 및 Si 과의 열적 안정성)

  • 신두식;오재응;유성룡;최진석;백수현;이상인;이정규;이종길
    • Journal of the Korean Institute of Telematics and Electronics A
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    • v.30A no.7
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    • pp.47-59
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    • 1993
  • The thermal stability of "stuffed" TiN/Ti barrier matals with different annealing history has been studied to improve the contact reliability of Al/Si contacts in 16M DRAM. The annealing conditions before the Al deposition such as film thickness, the annealing temperature and the annealing ambient have been varied. For TiN(900A)/Ti(300A) annealed at 450 in nitrogen ambient to form a "stuffed barrier" by inducing oxygen atoms into grain boundaries, there is no observation of Al penetrations into Si substrates after the post heat treatment of up to 700 even though there are massive amounts of Al found in TiN film after the post heat treatment of 600 indicating that TiN has a "sponge-like" function due to its ability to absorb several amounts of aluminum at elevated temperature. The TiN/Ti diffusion barrier annealed at 550 has, however, failed after the post heat treatment at 600. The thinner diffusion barriers with TiN(300A)/Ti(100A) failed after the post heat treatment at 600.he post heat treatment at 600.

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Fabrication of Organic-Inorganic Superlattice Films Toward Potential Use For Gas Diffusion Barrier

  • Yun, Gwan-Hyeok;Muduli, Subas Kumar;Seong, Myeong-Mo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.394-394
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    • 2012
  • We fabricated organic-inorganic superlattice films using molecular layer deposition (MLD) and atomic layer deposition (ALD). The MLD is a gas phase process in the vacuum like to atomic layer deposition (ALD) and also relies on a self-terminating surface reaction of organic precursor which results in the formation of a monolayer in each sequence. In the MLD process, 'Alucone' is very famous organic thin film fabricated using MLD. Alucone layers were grown by repeated sequential surface reactions of trimethylaluminum and ethylene glycol at substrate temperature of $80^{\circ}C$. In addition, we developed UV-assisted $Al_2O_3$ with gas diffusion barrier property better than typical $Al_2O_3$. The UV light was very effective to obtain defect-free, high quality $Al_2O_3$ thin film which is determined by water vapor transmission rate (WVTR). Ellipsometry analysis showed a self-limiting surface reaction process and linear growth of each organic, inorganic film. Composition of the organic films was confirmed by infrared (IR) spectroscopy. Ultra-violet (UV) spectroscopy was employed to measure transparency of the organic-inorganic superlattice films. WVTR is calculated by Ca test. Organic-inorganic superlattice films using UV-assisted $Al_2O_3$ and alucone have possible use in gas diffusion barrier for OLED.

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Effect of Clay Type and Concentration on Optical, Tensile and Water Vapor Barrier Properties of Soy Protein Isolate/Clay Nanocomposite Films

  • Rhim, Jong-Whan
    • KOREAN JOURNAL OF PACKAGING SCIENCE & TECHNOLOGY
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    • v.15 no.3
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    • pp.99-104
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    • 2009
  • Soy protein isolate (SPI)-based nanocomposite films with three different types of nanoclays, such as Cloisite $Na^+$, Cloisite 20A, and Cloisite 30B, were prepared using a solution casting method, and their optical, tensile, and water vapor barrier properties were determined to investigate the effect of nano-clay type on film properties. Among the tested nanoclays, Cloisite $Na^+$, a hydrophilic montmorillonite (MMT), exhibited the highest transparency with least opaqueness, the highest tensile strength, and the highest water vapor barrier properties, indicating Cloisite $Na^+$ is the most compatible with SPI polymer matrix to form nanocomposite films. The film properties of SPI/Cloisite $Na^+$ nanocomposite films were strongly dependent on the concentration of the clay. Film properties such as optical, tensile, and water vapor barrier properties improved significantly (p<0.05) as the concentration of clay increased. However, the effectiveness of addition of the clay reduced above a certain level (i.e., 5wt%), indicating that there is an optimum amount of clay addition to exploit the full advantage of nanocmposite films.

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Effect of Thermal Barrier Coating and Film Cooling Condition on the Cooling Performance of Liquid-propellant Rocket Engine Combustor (액체로켓 엔진 연소기의 열차폐 코팅 및 막냉각 조건에 따른 냉각 성능 변화 해석)

  • Joh, Miok;Kim, Seong-Ku;Choi, Hwan-Seok
    • Journal of the Korean Society of Propulsion Engineers
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    • v.18 no.2
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    • pp.52-59
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    • 2014
  • The effect of ceramic thermal barrier coating thickness on the cooling performance of a liquid-propellant rocket engine combustor has been investigated through combustion/cooling performance analysis whose results verified against measured data from hot-firing tests. Also have been confirmed the effects of film cooling amount near the face plate on the coolant temperature and on the thermal barrier coating surface temperature. Some important points to be considered for designing cooling schemes for regeneratively cooled rocket engine combustor have been drawn and reviewed from present study and further verification of the analysis tool should be performed in the future.

The Effect of Diffusion Barrier and thin Film Deposition Temperature on Change of Carbon Nanotubes Length (탄소나노튜브 길이 변화에 대한 확산방지층과 박막 증착 온도의 영향)

  • Hong, Soon-kyu;Lee, Hyung Woo
    • Journal of Powder Materials
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    • v.24 no.3
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    • pp.248-253
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    • 2017
  • In this study, we investigate the effect of the diffusion barrier and substrate temperature on the length of carbon nanotubes. For synthesizing vertically aligned carbon nanotubes, thermal chemical vapor deposition is used and a substrate with a catalytic layer and a buffer layer is prepared using an e-beam evaporator. The length of the carbon nanotubes synthesized on the catalytic layer/diffusion barrier on the silicon substrate is longer than that without a diffusion barrier because the diffusion barrier prevents generation of silicon carbide from the diffusion of carbon atoms into the silicon substrate. The deposition temperature of the catalyst and alumina are varied from room temperature to $150^{\circ}C$, $200^{\circ}C$, and $250^{\circ}C$. On increasing the substrate temperature on depositing the buffer layer on the silicon substrate, shorter carbon nanotubes are obtained owing to the increased bonding force between the buffer layer and silicon substrate. The reason why different lengths of carbon nanotubes are obtained is that the higher bonding force between the buffer layer and the substrate layer prevents uniformity of catalytic islands for synthesizing carbon nanotubes.