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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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The Effect of Environmental Factors on the Hydrolysis Characteristics of Lipase (환경인자가 리파제의 가수분해 특성에 미치는 영향)

  • Park, Geon-Gyu;Kim, Eun-Gi;Heo, Byeong-Gi
    • KSBB Journal
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    • v.14 no.4
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    • pp.511-516
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    • 1999
  • The effects of environmental and compositon factors, such as reaction time, metal ions, pH, agitation speed, the weight ratio of water to oil, and the weight of enzyme, on the hydrolysis of oils by Lipase-OF were investigated. In case of oils with low melting point, the optimum temperature of hydrolysis were the enzyme activity was maximum was 37$^{\circ}C$. However, when the melting temperature was higher than 4$0^{\circ}C$, the optimum temperature was around the fusion temperature. The activity of Lipase-OF decreased very rapidly with increase of temperature in the range of higher than 45$^{\circ}C$ and the activity perished above $65^{\circ}C$. The effect of agitation speed was investigated from 150 to 650 rpm. The hydrolysis of oils increased as the agitation speed increased up to 350 rpm, but it did not increase any more above 350 rpm. The weight ratio of water to oil was changed from 1 : 9 to 9 : 1 for the investigation of the effect on the hydrolusis. The weight ratio for maximum hydrolysis was 1 : 1. $Ca^{2+}\;and\;Mg^{2+}$ among various metal ions had some effect on the stimulation of hydrolysis. The optimum concentration of the ions was about 100ppm at which the hydrolysis increased, compared with that of distilled water, by 2 to 3%. The Optimum pH of Lipase-OF was 7. The hydrolysis decreased as the pH decreased as the pH decreased and also decreased as the pH increased. The content of enzyme affected the hydrolysis of oil. The hydrolysis increased with the content of Lipase-OF in the range of less than 0.013 wt% of substrate. However, the increase of hydrolysis with the content of Lipase-OF ceased above 0.013 wt%. The experiments investigating the effect of environmental and composition factors on the hydrolysis of oils showed that the optimum temperature was 37$^{\circ}C$, the pH 7, the concentration of $Ca^{2+}\;or\;Mg^{2+}$ 100 ppm, the agitation speed 350 rpm, the weight ratio of water to oil 1 : 1, and the content of Lipase-OF 0.013 wt% of substrate.

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Effects of Pb and CO2 on Soil Microbial Community Associated with Pinus densiflora-Lab (소나무(Pinus densiflora) 생육토양의 미생물 군집에 미치는 납과 CO2의 영향)

  • Hong, Sun-Hwa;Kim, Sung-Hyun;Kang, Ho-Jeong;Ryu, Hee-Wook;Lee, Sang-Don;Lee, In-Sook;Cho, Kyung-Suk
    • Journal of Ecology and Environment
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    • v.29 no.6
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    • pp.551-558
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    • 2006
  • Effects of Pb and $CO_2$ on soil microbial community associated with Pinus densiflora were investigated using community level physiological profiles (CLPP) and 16S rDNA PCR-denaturing gradient gel electrophoresis (DGGE) methods. Two-years pine trees were planted in Pb-contaminated soils and uncontaminated soils, and cultivated for 3 months in the growth chamber where $CO_2$ concentration was controlled at 380 or 760 ppmv. The structure of microbial community was analyzed in 6 kinds of soil samples (CA-0M : $CO_2$ 380 ppmv + Pb 0 mg/kg + initial, CB-0M : $CO_2$ 380 ppmv + Pb 500 mg/kg + initial, CA-3M : $CO_2$ 380 ppmv + Pb 0 mg/kg + after 3 months, CB-3M : $CO_2$ 380 ppmv + Pb 500 mglkg + after 3 months, EA-3M : $CO_2$ 760 ppmv + Pb 0 mg/kg + after 3 months, EB-3M : $CO_2$ 760 ppmv + Pb 500 mg/kg + after 3 months). After 3 months, the substrate utilization in the uncontaminated soil samples (CA-3M vs EA-3M) was not significantly influenced by $CO_2$ concentrations. However, the substrate utilization in the Pb-contaminated soil samples (CB-3M vs EB-3M) was enhanced by the elevated $CO_2$ concentrations. The results of principal component analysis based on substrate utilization activities showed that the structure of microbial community structure in each soil sample was grouped by Pb-contamination. The similarities of DGGE fingerprints were 56.3 % between the uncontaminated soil samples (CA-3M vs EA-3M), and 71.4% between the Pb-contaminated soil samples (CB-3M vs. EB-3M). The similarities between the soil samples under $CO_2$ 380 ppmv (CA-3M vs CB-3M) and $CO_2$, 760 ppmv (EA-3M vs EB-3M) were 53.3% and 35.8%, respectively. These results suggested that the structure of microbial community associated with Pinus densiflora were sensitively specialized by Pb-contamination rather than $CO_2$ concentration.

Reaction Gas Composition Dependence on the Properties of SnO2 Films on PET Substrate by ECR-MOCVD (반응가스조성이 PET기판위에 ECR 화학증착법에 의해 제조된 SnO2 박막특성에 미치는 영향)

  • Kim, Yun-Seok;Lee, Joong-Kee
    • Journal of the Korean Electrochemical Society
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    • v.8 no.3
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    • pp.139-145
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    • 2005
  • [ $SnO_x$ ] films on the flexible substrate of PET film were prepared at ambient temperature under a $(CH_3)_4Sn(TMT: tetra-methyl tin)-H_2-O_2$ atmosphere in order to obtain transparent conductive polymer by using ECR-MOCVD(Electro Cyclotron Resonance Metal Organic Chemical Yfpor Deposition) system. The prepared $SnO_x$ thin films show generally over $90\%$ of optical transmittance at wavelength range of 380-780nm and about $1\times10^{-2\~3}ohm{\cdot}cm$ of electrical resistivity. In the present study, effects of $O_2/TMT\;and\;H_2/TMT$ mole ratio on the properties of $SnO_x$ films are investigated and the other process parameters such as microwave power, magnetic current power, substrate distance and working pressure are fixed. Based on our experimental results, the $SnO_x$ film composition ratio of Sn and O directly influences on the electrical and optical properties of the films prepared. The $SnO_x$ film with low electric resistivity and high transmittance could be obtained by controlling the process parameters such as $O_2/TMT\;and\;H_2/TMT$ mole ratio, which play an important role to change the composition ratio between Sn and O. An increase of $O_2/TMT$ mole ratio brought on the increases 0 content in the $SnO_x$ film. On the other hand, an increase of $H_2/TMT$ mole ratio lead to decreases the oxygen content in the film. The optimized composition ratio of oxygen : tin Is determined as 2.4: 1 at $O_2/TMT$ of 80 and $H_2/TMT$ of 40 mole ratio, respectively.

Fabrication and Characterization of Hybrid NTC Thermistor Films with Conducting Oxide Particles by an Aerosol-Deposition Process (상온 분사 공정에 의한 산화물전도 입자 복합 하이브리드 NTC 서미스터 필름의 제작 및 특성)

  • Kang, Ju-Eun;Ryu, Jungho;Choi, Jong-Jin;Yoon, Woon-Ha;Kim, Jong-Woo;Ahn, Cheol-Woo;Choi, Joon Hwan;Park, Dong-Soo;Kim, Yang-Do
    • Journal of the Korean Ceramic Society
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    • v.50 no.1
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    • pp.63-69
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    • 2013
  • Negative-temperature coefficient (NTC) thermistors based on nickel manganite spinel ($NiMn_2O_4$) are widely used for many applications, such as sensors and temperature compensators, due to their good thermistor characteristics and stabilities. However, to achieve thermistors with a high NTC B constant, which is an important figure of merit pertaining to the degree of temperature sensitivity, the activation energy should be high such that high resistivity at ambient temperatures results. To obtain a high B constant and low resistivity, Al and Si modified spinel structured $Ni_{0.6}Si_{0.2}Al_{0.6}Mn_{1.6}O_4$ hybrid thick films with the conducting metal oxide of $LaNiO_3$ were fabricated on a glass substrate by aerosol deposition at room temperature (RT). The NTC-$LaNiO_3$ hybrid thick films showed resistivity as low as < $100k{\Omega}\;cm$ at $90^{\circ}C$, which is one or two orders of magnitude lower than that of the monolithic NTC films, while retaining a high B constant of $NiMn_2O_4$ of over 5500 K when 20 wt% $LaNiO_3$ was added without a post-thermal treatment. These phenomena are explained by the percolation threshold mechanism.

A Study on the etching mechanism of $CeO_2$ thin film by high density plasma (고밀도 플라즈마에 의한 $CeO_2$ 박막의 식각 메커니즘 연구)

  • Oh, Chang-Seok;Kim, Chang-Il
    • Journal of the Institute of Electronics Engineers of Korea SD
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    • v.38 no.12
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    • pp.8-13
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    • 2001
  • Cerium oxide ($CeO_2$) thin film has been proposed as a buffer layer between the ferroelectric thin film and the Si substrate in Metal-Ferroelectric-Insulator-Silicon (MFIS) structures for ferroelectric random access memory (FRAM) applications. In this study, $CeO_2$ thin films were etched with $Cl_2$/Ar gas mixture in an inductively coupled plasma (ICP). Etch properties were measured for different gas mixing ratio of $Cl_2$($Cl_2$+Ar) while the other process conditions were fixed at RF power (600 W), dc bias voltage (-200 V), and chamber pressure (15 mTorr). The highest etch rate of $CeO_2$ thin film was 230 ${\AA}$/min and the selectivity of $CeO_2$ to $YMnO_3$ was 1.83 at $Cl_2$($Cl_2$+Ar gas mixing ratio of 0.2. The surface reaction of the etched $CeO_2$ thin films was investigated using x-ray photoelectron spectroscopy (XPS) analysis. There is a Ce-Cl bonding by chemical reaction between Ce and Cl. The results of secondary ion mass spectrometer (SIMS) analysis were compared with the results of XPS analysis and the Ce-Cl bonding was monitored at 176.15 (a.m.u). These results confirm that Ce atoms of $CeO_2$ thin films react with chlorine and a compound such as CeCl remains on the surface of etched $CeO_2$ thin films. These products can be removed by Ar ion bombardment.

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Irradiation enduced In-plane magnetization in Fe/MgO/Fe/Co multilayers

  • Singh, Jitendra Pal;Lim, Weon Cheol;Song, Jonghan;Kim, Jaeyeoul;Asokan, K.;Chae, Keun Hwa
    • Proceedings of the Korean Vacuum Society Conference
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    • 2015.08a
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    • pp.188.1-188.1
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    • 2015
  • For present investigation Fe/MgO/Fe/Co multilayer stack is grown on Si substrate using e-beam evaporation in ultrahigh vacuum. This stack is irradiated perpendicularly by 120 MeV $Ag^{8+}$ at different fluences ranging from $1{\times}10^{11}$ to $1{\times}10^{13}ions/cm^2$ in high vacuum using 15UD Pelletron Accelerator at Inter University Accelerator Centre, New Delhi. Magnetic measurements carried out on pre and post irradiated stacks show significant changes in the shape of perpendicular hysteresis which is relevant with previous observation of re-orientation of magnetic moment along the direction of ion trajectory. However increase in plane squareness may be due to the modification of interface structure of stacks. X-ray reflectivity measurements show onset of interface roughness and interface mixing. X-ray diffraction measurements carried out using synchrotron radiation shows amorphous nature of MgO and Co layer in the stack. Peak corresponding body centered Fe [JCPDS-06-0696] is observed in X-ray diffraction pattern of pre and post irradiated stacks. Peak broadening shows granular nature of Fe layer. Estimated crystallite size is $22{\pm}1nm$ for pre-irradiated stack. Crystallite size first increases with irradiation then decreases. Structural quality of these stacks was further studied using transmission electron microscopic measurements. Thickness from these measurements are 54, 36, 23, 58 and 3 nm respectively for MgO, Fe, MgO, Fe+Co and Au layers in the stack. These measurements envisage poor crystallinity of different layers. Interfaces are not clear which indicate mixing at interface. With increase fluence mixing and diffusion was increased in the stack. X-ray absorption spectroscopic measurements carried out on these stacks show changes of Fe valence state after irradiation along with change of O(2p)-metal (3d) hybridized state. Valence state change predicts oxide formation at interface which causes enhanced in-plane magnetization.

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Surface characteristics and biocompatibility of bioinert nitrides ion plated titanium implant (생불활성 질화물 이온도금된 티타늄 임프란트의 표면특성 및 생체적합성)

  • Chang, Kap-Sung;Kim, Heung-Joong;Park, Joo-Cheol;Kim, Byung-Ock;Han, Kyung-Yoon
    • Journal of Periodontal and Implant Science
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    • v.29 no.1
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    • pp.209-231
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    • 1999
  • Even though titanium(Ti) and its alloys are the most used dental implant materials, there are some problems that Ti wears easily and interferes normal osteogenesis due to the metal ions. Ti coated with bioactive ceramics such as hydroxyapatite has also such problems as the exfoliation or resorption of the coated layer, Recent studies on implant materials have been proceeding to improve physical properties of the implant substrate and biocompatibility of the implant surfaces. The purpose of the present study was to examine the physical property and bone tissue compatibility of bioinert nitrides ion plated Ti, Button type specimens(14mm in diameter, 2.32rrun in height) for the abrasion test and cytotoxicity test and thread type implants(3.75mm in diameter, 6mm in length) for the animal experiments were made from Ti(grade 2) and 316LVM stainless steel. Ti specimens were ion plated with TiN, ZrN by the low temperature arc vapor deposition, and the depth profile of the TiN/Ti, ZrN/Ti ion plated surface was examined by Auger Electron Spectroscopy. Three kind of button type specimens .of TiN/Ti, ZrN/Ti and Ti were used for abrasion test, and HEPAlClC7 cells and CCD cells were cultivated for 4 days with the specimens for cytotoxicity test. Thread type implants of TiN/Ti, ZrN/Ti, Ti, 316LVM were implanted on the femur of 6 adult dogs weighing 10kg-13kg. Two dogs were sacrified for histological examination after 45 days and 90 days, and four dogs were sacrified for the removal torque test of the implant') after 90 days. The removal torque force was measured by Autograph (Shimadzu Co., AGS-1000D series, Japan). Abrasion resistance of TiN/Ti was the highest, and that of ZrN/Ti and Ti were followed. The bioinert nitride ion plated Ti had much better abrasion resistance, compared with Ti, In the cytotoxicity test, the number of both cells were increased in all specimens, and there were no significant difference in cytotoxic reaction among all groups (p>0.1), In histological examination, 316LVM showed the soft tissue engagement in interface between the implant and bone, but the other materials after 45 days noted immature new bone formation in the medullary portion along the implant surface, and those after 90 days showed implant support by new bone formation in both the cortical and the medullary portion, The removal torque force of Tilv/Ti showed significantly higher than that of Ti(p(O,05). The difference in removal torque force between TiN/Ti and ZrN/Ti was not significant(p>0.05), and that of 316LVM was lowest among all groups(p<0.05). These results suggest that bioinert nitrides ion plated Ti can resolve the existing problems of Ti and bioactive ceramics, and it may be clinically applicable to human.

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Purification and Characterization of Collagenase Produced by Staphylococcus aureus JJ-11 Isolated from the Human Skin (피부에서 분리한 Staphylococcus aureus JJ-11이 생산하는 collagenase의 정제 및 특성)

  • Lee Jin-Kyoung;Kim Hae-Nam;Kang Ho-Young;Jun Hong-Ki
    • Journal of Life Science
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    • v.16 no.2 s.75
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    • pp.245-252
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    • 2006
  • A bacterial strain, identified as Staphylococcus aureus JJ-11, producing collagenase was isolated out of 40 persons having skin troubles. S. aureus JJ-11 produced collagenase optimally in the media containing 1.5%(w/v) gelatin, 1%(w/v) yeast extract, 0.4%(w/v) $K_2HPO_4$, 0.005%(w/v) $NiSO_4{\cdot}6H_2O$ at $37^{\circ}C$ for 18 hrs. The collagenase produced by Staphylococcus aureus JJ-11 was purified at 6.66-folds purity through application of chromatography with Amberlite IRA-900 and Sephacryl S-300 HR columns. The molecular weight of the partially purified enzyme was estimated to be 62 kDa by SDS-PAGE. The protein exhibited optimum enzymatic activity at pH 7.0, and showed a stable activity at pH 4-8. The optimum temperature for collagenase was at $37^{\circ}C$, and activity was maintained upto $40^{\circ}C$. The enzyme activity was slightly elevated in the presence of divalents such as, $Fe^{2+},\;Co^{2+}\;and\;Ba^{2+}$ However, the activity was inhibited in the presence of $Sr^{2+}\;or\;Hg^{2+}$. The inhibition of activity by O-phenanthroline and EDTA suggested that the enzyme may contain metal which is required for activity. The enzyme showed the highest activity when insoluble collagen (type I) was, used as a substrate.

Characteristics and Fabrication of Micro Gas Sensor with Single Electrode (단일전극을 가진 마이크로 가스센서의 제작 및 특성)

  • Song, Kap-Duk;Bang, Yeung-Il;Lee, Sang-Mun;Lee, Yun-Su;Choi, Nak-Jin;Joo, Byung-Su;Seo, Moo-Gyo;Huh, Jeung-Soo;Lee, Duk-Dong
    • Journal of Sensor Science and Technology
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    • v.11 no.6
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    • pp.350-357
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    • 2002
  • Micro gas sensor with single electrode was proposed for improving stability and sensitivity. Generally, metal oxide gas sensors have two electrodes for heating and sensing. This fabricated new type sensor have only a single electrode by forming a sensing material onto heating electrode. Pt as a heating and sensing electrode was sputtered on glass substrate and a $SnO_2$ sensing material was thermally evaporated on Pt electrode. $SnO_2$ was patterned by lift-off process and then thermally oxidized in $O_2$ condition for 1 hr., $600^{\circ}C$. The size of fabricated sensor was $1.9{\times}2.1\;mm^2$. As a result of CO gas sensing characteristics, this sensor showed 100 mV change for 1,000 ppm and linearity for wide range($0{\sim}10,000\;ppm$) of gas concentrations. And the sensor shows a good recovery characteristics of 1% deviation compared to initial resistance.