• KOREAN JOURNAL OF PACKAGING SCIENCE & TECHNOLOGY
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• v.28 no.2
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• pp.81-87
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• 2022

Paper is a promising alternative to petroleum-based plastic materials for sustainable packaging applications. However, paper exhibits poor gas and water vapor barrier properties, which restrict its effective application in the packaging industry. To enhance the properties of papers, sodium caseinate (CasNa)/transglutaminase (TG) coating solutions with various TG contents were prepared and coated on the papers. The chemical and morphological structures, mechanical properties, seal strength, and water vapor barrier properties of the coated papers were thoroughly investigated. The paper properties depended significantly on the chemical and morphological structures. Pristine CasNa and CasNa/TG coating solutions were evenly coated on the paper surfaces, without any cracks. The chemical structure of the CasNa/TG coated papers was slightly influenced by TG addition, resulting in increased elongation at break and enhanced water barrier properties. To promote the use of CasNa-coated papers in packaging applications, additional investigations must be performed to prevent gas and moisture permeation and enhance the mechanical strength of these papers via chemical reactions and introduction of organic/inorganic composites.

• Journal of Information Display
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• v.11 no.1
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• pp.8-11
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• 2010

In this study, a new thin films passivation technique using Zn with high electronegativity and $MgF_2$, a fluorine material with better optical transmittance than the sealing film materials that have thus far been reported was proposed. Targets with various ratios of $MgF_2$ to Zn (5:5, 4:6 and 3:7) were fabricated to control the amount of Zn in the passivation films. The Mg-Zn-F films were deposited onto the substrates and Zn was located in the gap between the lattices of $MgF_2$ without chemical metathesis in the Mg-Zn-F films. The thickness and optical transmittance of the deposited passivation films were approximately 200 nm and 80%, respectively. It was confirmed via electron dispersive spectroscopy (EDS) analysis that the Zn content of the film that was sputtered using a 4:6 ratio target was 9.84 wt%. The Zn contents of the films made from the 5:5 and 3:7 ratio targets were 2.07 and 5.01 wt%, respectively. The water vapor transmission rate (WVTR) was determined to be $38^{\circ}C$, RH 90-100%. The WVTR of the Mg-Zn-F film that was deposited with a 4:6 ratio target nearly reached the limit of the equipment, $1\times10^{-3}\;gm^2{\cdot}day$. As the Zn portion increased, the packing density also increased, and it was found that the passivation films effectively prevented the permeation by either oxygen or water vapor. To measure the characteristics of gas barrier, the film was applied to the emitting device to evaluate their lifetime. The lifetime of the applied device with passivation was increased to 25 times that of the PLED device, which was non-passivated.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.36 no.10
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• pp.1049-1054
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• 2012

Continued advancements in organic materials have led to the development of organic devices that are thin, flexible, and lightweight and that can potentially be used as low-cost energy-conversion devices. While these devices have many advantages, the environmentally induced degradation of the active materials and the low-work-function electrodes remain a valid concern. Hence, many vacuum deposition processes have been applied to develop low-permeation barrier coatings. In this work, we present the results pertaining to the developed thin-film encapsulation. Multilayer encapsulation involves the use of $SiO_x$ or $SiN_x$ with parylene. The effective water vapor transmission rates were investigated using a Ca-corrosion test. The integration of the developed barrier layers was demonstrated by encapsulating pentacene/$C_{60}$ solar cells, and the results are presented.

• Journal of the Korean Society of Manufacturing Process Engineers
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• v.17 no.3
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• pp.51-58
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• 2018

In this paper, the organic material Poly(methyl methacrylate) PMMA is used with inorganic $Al_2O_3$ to fabricate organic-inorganic multilayer barrier thin films. The organic thin films are developed using a roll-to-roll electrohydrodynamic atomization system, whereas the inorganic are grown using a roll-to-roll low-temperature atmospheric pressure atomic layer deposition system. For the first time, these two technologies are used together to develop organic-inorganic multilayer barrier thin films in atmospheric condition. The films are grown under optimized parameters and classified into three classes based on the layer structures, when the total thickness of the barrier is maintained at ~ 160 nm. All classes of barriers show good morphological, optical and chemical properties. The $Al_2O_3$ films with a low average arithmetic roughness of 1.58 nm conceal the non-uniformity and irregularities in PMMA thin films with a roughness of 5.20 nm. All classes of barriers show a notably good optical transmission of ~ 85 %. The hybrid organic-inorganic barriers show water vapor and oxygen permeation in the range of ${\sim}3.2{\times}10^{-2}g/m^2/day$ and $0.015cc/m^2/day$ at $23^{\circ}C$ and 100% relative humidity. It has been confirmed that it can be mass-produced and used as a low-cost barrier thin film in various printing electronic devices.

• Magazine of the Korea Concrete Institute
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• v.7 no.4
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• pp.149-156
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• 1995

The fracture process zone in concrete is a region ahead of a traction-free crack, in which two major mechanisms, microcracking and bridging, play important roles. The toughness due to bridging is dominant compared to toughness induced by microcracking, so that the bridging is dominani: mechanism governing the fracture process of concrete. Fracture mechanics does work for concrete provided that the fracture process zone is being considered, so that the development of model for the fracture process zone is most important to describe fracture phenomena in concrete. In this paper the bridging zone, which is a part of extended rnacrocrack with stresses transmitted by aggregates in concrete, is modelled by a Dugdale-Barenblatt type model with linear tension-softening curve. Two finite element techniques are shown for the analysis of progressive cracking in concrete based on the discrete crack approach: one with crack element, the other without crack element. The advantage of the technique with crack element is that it dees not need to update the mesh topology to follow the progressive cracking. Numerical results by the techniques are demonstrated.

• Journal of the Semiconductor & Display Technology
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• v.21 no.1
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• pp.67-70
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• 2022

In order to prevent water vapor and oxygen permeation in the organic light emitting diodes (OLED), Al₂O₃ thin-film encapsulation (TFE) technology were investigated. Atomic layer deposition (ALD) method was used for making the Al₂O₃ TFE layer because it has superior barrier performance with advantages of excellent uniformity over large scales at relatively low deposition temperatures. In this study, the thickness of the Al₂O₃ layer was varied by controlling the numbers of the unit pulse cycle including Tri Methyl Aluminum(Al(CH₃)₃) injection, Ar purge, and H₂O injection. In this case, several process parameters such as injection pulse times, Ar flow rate, precursor temperature, and substrate temperatures were fixed for analysis of the effect only on the thickness of the Al₂O₃ layer. As results, at least the thickness of 39 nm was required in order to obtain the minimum WVTR of 9.04 mg/m²day per one Al₂O₃ layer and a good transmittance of 90.94 % at 550 nm wavelength.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.251-252
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• 2012

Recently, the growing interest in organic microelectronic devices including OLEDs has led to an increasing amount of research into their many potential applications in the area of flexible electronic devices based on plastic substrates. However, these organic devices require a gas barrier coating to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency OLEDs require an extremely low Water Vapor Transition Rate (WVTR) of $1{\times}10^{-6}g/m^2$/day. The Key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required ($1{\times}10^{-6}g/m^2$/day) is the suppression of defect sites and gas diffusion pathways between grain boundaries. In this study, we developed an $Al_2O_3$ nano-crystal structure single gas barrier layer using a Neutral Beam Assisted Sputtering (NBAS) process. The NBAS system is based on the conventional RF magnetron sputtering and neutral beam source. The neutral beam source consists of an electron cyclotron Resonance (ECR) plasma source and metal reflector. The Ar+ ions in the ECR plasma are accelerated in the plasma sheath between the plasma and reflector, which are then neutralized by Auger neutralization. The neutral beam energies were possible to estimate indirectly through previous experiments and binary collision model. The accelerating potential is the sum of the plasma potential and reflector bias. In previous experiments, while adjusting the reflector bias, changes in the plasma density and the plasma potential were not observed. The neutral beam energy is controlled by the metal reflector bias. The NBAS process can continuously change crystalline structures from an amorphous phase to nano-crystal phase of various grain sizes within a single inorganic thin film. These NBAS process effects can lead to the formation of a nano-crystal structure barrier layer which effectively limits gas diffusion through the pathways between grain boundaries. Our results verify the nano-crystal structure of the NBAS processed $Al_2O_3$ single gas barrier layer through dielectric constant measurement, break down field measurement, and TEM analysis. Finally, the WVTR of $Al_2O_3$ nano-crystal structure single gas barrier layer was measured to be under $5{\times}10^{-6}g/m^2$/day therefore we can confirm that NBAS processed $Al_2O_3$ nano-crystal structure single gas barrier layer is suitable for OLED application.

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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• pp.157-157
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• 2015

Recently, the growing interest in organic microelectronic devices including OLEDs has led to an increasing amount of research into their many potential applications in the area of flexible electronic devices based on plastic substrates. However, these organic devices require a gas barrier coating to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency OLEDs require an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}g/m^2day$. The Key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required ($1{\times}10^{-6}g/m^2day$) is the suppression of defect sites and gas diffusion pathways between grain boundaries. In this study NBAS process was introduced to deposit enhanced film density single gas barrier layer with a low WVTR. Fig. 1. shows a schematic illustration of the NBAS apparatus. The NBAS process was used for the $Al_2O_3$ nano-crystal structure films deposition, as shown in Fig. 1. The NBAS system is based on the conventional RF magnetron sputtering and it has the electron cyclotron resonance (ECR) plasma source and metal reflector. $Ar^+$ ion in the ECR plasma can be accelerated into the plasma sheath between the plasma and metal reflector, which are then neutralized mainly by Auger neutralization. The neutral beam energy is controlled by the metal reflector bias. The controllable neutral beam energy can continuously change crystalline structures from an amorphous phase to nanocrystal phase of various grain sizes. The $Al_2O_3$ films can be high film density by controllable Auger neutral beam energy. we developed $Al_2O_3$ high dense barrier layer using NBAS process. We can verified that NBAS process effect can lead to formation of high density nano-crystal structure barrier layer. As a result, Fig. 2. shows that the NBAS processed $Al_2O_3$ high dense barrier layer shows excellent WVTR property as a under $2{\times}10^{-5}g/m^2day$ in the single barrier layer of 100nm thickness. Therefore, the NBAS processed $Al_2O_3$ high dense barrier layer is very suitable in the high efficiency OLED application.

• 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.

• Polymer(Korea)
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• v.38 no.6
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• pp.687-693
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• 2014

Poly(ether-block-amide) 1657 (PEBAX 1657) blended membranes with molecular weight 400 poly(ethylene glycol) (PEG 400) were prepared and their permeability was tested for the gases $N_2$, $O_2$, $CH_4$, $CO_2$, and $SO_2$ by the time-lag method. The permeation characteristics were investigated in terms of diffusivity and solubility, which are dominant factors for gas transport. With the addition of PEG 400, the permeability of all the gases increased and also the ideal selectivity for several pair gases was enhanced. In particular, selectivity for $CO_2/N_2$ ranged from 53.2 (pristine PEBAX 1657 membrane) to 84.1 (50% PEG 400 added), for $SO_2/CO_2$ from 38.9 to 50.7, and for $CO_2/CH_4$ from 17.7 to 31.4. The increase of both permeability and selectivity is mainly because of the increase of solubility of the gases, especially $CO_2$ and $SO_2$. To obtain durability against water vapor, glutaraldehyde (GA) was added to the PEBAX 1657/PEG 400 blended membranes. As a result, permeability decreased owing to a reduction of the free volume and ether oxide units, which are the main factors in elevating the permeability for the blended membranes, and selectivity decrease however; we believe that the durability of the resulting membranes would be increased.