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Effects of Al2O3 Coating on BiVO4 and Mo-doped BiVO4 Film for Solar Water Oxidation

  • Arunachalam, Maheswari;Yun, Gun;Lee, Hyo Seok;Ahn, Kwang-Soon;Heo, Jaeyeong;Kang, Soon Hyung
    • Journal of Electrochemical Science and Technology
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    • v.10 no.4
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    • pp.424-432
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    • 2019
  • Planar BiVO4 and 3 wt% Mo-doped BiVO4 (abbreviated as Mo:BiVO4) film were prepared by the facile spin-coating method on fluorine doped SnO2(FTO) substrate in the same precursor solution including the Mo precursor in Mo:BiVO4 film. After annealing at a high temperature of 450℃ for 30 min to improve crystallinity, the films exhibited the monoclinic crystalline phase and nanoporous architecture. Both films showed no remarkably discrepancy in crystalline or morphological properties. To investigate the effect of surface passivation exploring the Al2O3 layer, the ultra-thin Al2O3 layer with a thickness of approximately 2 nm was deposited on BiVO4 film using the atomic layer deposition (ALD) method. No distinct morphological modification was observed for all prepared BiVO4 and Mo:BiVO4 films. Only slightly reduced nanopores were observed. Although both samples showed some reduction of light absorption in the visible wavelength after coating of Al2O3 layer, the Al2O3 coated BiVO4 (Al2O3/BiVO4) film exhibited enhanced photoelectrochemical performance in 0.5 M Na2SO4 solution (pH 6.5), having higher photocurrent density (0.91 mA/㎠ at 1.23 V vs. reversible hydrogen electrode (RHE), briefly abbreviated as VRHE) than BiVO4 film (0.12 mA/㎠ at 1.23 VRHE). Moreover, Al2O3 coating on the Mo:BiVO4 film exhibited more enhanced photocurrent density (1.5 mA/㎠ at 1.23 VRHE) than the Mo:BiVO4 film (0.86 mA/㎠ at 1.23 VRHE). To examine the reasons, capacitance measurement and Mott-Schottky analysis were conducted, revealing that the significant degradation of capacitance value was observed in both BiVO4 film and Al2O3/Mo:BiVO4 film, probably due to degraded capacitance by surface passivation. Furthermore, the flat-band potential (VFB) was negatively shifted to about 200 mV while the electronic conductivities were enhanced by Al2O3 coating in both samples, contributing to the advancement of PEC performance by ultra-thin Al2O3 layer.

수처리 목적의 대기압플라즈마를 이용한 유사 폴리도파민 필름 증착

  • Mun, Mu-Gyeom;Yeom, Geun-Yeong
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2018.06a
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    • pp.124-124
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    • 2018
  • Polydopamine은 수중 접착력, 친환경 접착제, nanoparticle absorption 등 다양한 특성으로 많이 연구되고 있는 소재이다. 본 연구에서는 dopamine을 이용하여 수중 금속을 흡착시키는 thin film을 제작하였다. 종래의 Polydopamine coating 방법으로 wet coating 이 사용되고 있다. 하지만 wet 방식의 경우 시간이 오래 걸릴 뿐만 아니라 in-line, roll to roll 방식을 적용하는 것이 어렵기 때문에 생산적이지 않다. 이에 본 연구에서는 Atmospheric Pressure Plasma(APP)를 이용 하여 Polydopamine-like film을 coating 하였다. APP의 경우 vacuum system, solution tank가 필요 없고 in-line, roll to roll 방식을 적용 할 수 있기 때문에 더 경제적이고 생산적인 공정이다. 또한 기존의 Plasma polymerization 방법은 Plasma energy가 높기 때문에 source의 분자구조가 바뀌거나 atom 단위로 분해된다. source의 분자구조가 바뀌는 "Atomic polymerization", Neiswender-Rosskamp Mechanism이 적용되면 wet 방식 coating한 film과는 다른 특성을 갖게 된다. 하지만 APP polymerization은 Plasma energy가 vacuum plasma 보다 매우 낮기 때문에 stile polymerization mechanism을 구현 하는데 적합 하다. stile polymerization mechanism은 Plasma 내부에서 polymer source를 분해 성장 시켜서 Polymer film 얻는 것이 아닌 source의 분자구조가 깨지지 않으면서 polymer growing 시키는 방법이다. dopamine source의 분자구조를 최대한 유지하려고 하는 이유는 metal absorption과 같은 특성이 dopamine chemical structure에 영향을 받기 때문이다. 많은 논문들에서 dopamine의 catechol group이 metal absorption, adhesion force에 영향을 주는 주요 인자라고 주장하고 있기 때문이다. 그래서 본 논문에서는 Dopamine source의 형태를 보존하면서 Polymerization 하는 방법으로 APP process를 사용 하여 낮은 전압에서 Polydopamine-like film을 제작 하였다. APP system 의 Plasma 방전부 에 Dopamine source를 유입하기 위하여 본 논문에서는 Piezo Spray 방식을 사용 하였다. Dopamine을 evaporator 하는 것이 어렵고 chemical composition이 유사한 monomer를 사용해서 Plasma Polymerization으로 Dopamine 분자 구조를 재현하는 것도 어렵다. 그래서 본 연구에서는 Dopamine을 water에 immerse 하고 Dopamine solution을 mist 상태로 만들어서 Plasma discharge area에 유입하였다. 이러한 방법으로 만들어진 film은 Polydopamine film은 아니지만 Polydopamine film과 유사한 Chemical composition, chemical structure, metal absorption을 갖는 것을 FT-IR, SEM, XPS을 이용 하여 확인 하였다. Dopamine source의 보존에 대하여 명확하게 확인하기 위하여 FT-IR을 측정 하였다. 전압에 따른 Benzene ring, hydroxyl group의 비율을 확인 하였다. 낮은 전압으로 coating 된 Polydopamine-like film 일수록 hydroxyl group peak($3400{\sim}3000cm^{-1}$)과 비교하여 Benzene ring peak($1600{\sim}1580cm^{-1}$ and $1510{\sim}500cm^{-1}$)이 흡수를 더 많이 하는 것을 확인 할 수 있다. 이것은 Benzene ring이 파괴되지 않고 보존되는 것을 보여준다. Dopamine에서 Benzene ring은 absorption main factor인 catechol에 있는 chemical structure이다. 즉 Benzene ring peak이 높을수록 Catechol이 잘 보존 되었다는 의미 이다. Catechol의 보존은 absorption main factor가 보존 된다는 의미 이다. 이러한 Polydopamine-like film으로 As, Cr, Mg, Cu 200ppm solution에 대한 filtration 능력을 확인 하였다. As, Cr, Cu, Mg 의 제거율이 각각 약25%, 35%, 45%, 65%인 것을 확인 하였다. 이 수치는 시중에 판매되는 제품들과 비교했을 때 300%~500% 향상된 수치 이다.

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MECHANICAL PROPERTIES OF TIN COATED FILM WITH VARIOUS COATING THICKNESS ON TITANIUM ALLOY (타이타늄 합금에 다양한 두께로 코팅된 TiN 피막의 기계적 성질)

  • Lee, Jae-Yun;Oh, Dong-Joon;Kim, Hee-Jung;Chung, Chae-Heon
    • The Journal of Korean Academy of Prosthodontics
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    • v.45 no.5
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    • pp.675-686
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    • 2007
  • Statement of problem: Titanium nitride(TiN) coatings are the most general and popular coating method and used to improve the properties of metallic surface for industrial purposes. When TiN coating applied to the abutment screw, frictional resistance would be reduced, as a results, the greater preload and prevention of the screw loosening could be expected. Purpose: The purpose of this study was to investigate mechanical properties of TiN coated film of various coating thickness on the titanium alloy surface and to evaluate proper coating thickness. Material and method: 95 Titanium alloy (Ti-6Al-4V) discs of 15 mm in diameter and 3 mm in thickness were prepared for TiN coating and divided into 7 groups in this study. Acceding to coating deposition time (CDT) with TiN by using Arc ion plating, were divided into 7 groups : Group A (CDT 30min), Group B (CDT 60min), Group C (CDT 90min), Group D (CDT 120min), Group E (CDT 150min), Group F(CDT 180min) and Group G (no CDT) as a control group. TiN coating surface was observed with Atomic Force Microscope(AFM), field emission scanning electron microscopy(FE-SEM) and examined with scratch tester, wear tester. Result: 1. Coating thickness fir each coated group was increased in proportion to coating deposition time. 2. Surface of all coated groups except Group A was homogeneous and smooth. However, surface of none coated Group G had scratch. 3. Adhesion strength for each coated group was increased in proportion to coating deposition time. 4. Wear resistance for each coated group was increased in proportion to coating deposition time. 5. Surface roughness in Group A, B, C was increased in proportion to coating deposition time. But, surface roughness in Group D, E, F was showed decreased tendency in proportion to coating deposition time. Conclusion: According to coating deposition time, mechanical properties of TiN coated film were changed. It was considered that 120 minutes coating deposition time ($1.32{\mu}m$ in coating thickness) is necessary.

Electrochemical Properties of NiO-YSZ Thin Films on 316 Stainless Steel Bipolar Plates Under a Simulated PEMFC Environment

  • Lee, W.G.;Jang, H.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.4
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    • pp.1177-1182
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    • 2012
  • The corrosion resistance of 316L stainless steel coated with NiO-YSZ (Ni added yttria stabilized zirconia) was examined in a proton exchange membrane fuel cell (PEMFC) environment. The NiO-YSZ coating was carried out using a sol-gel dip coating method, and the corrosion resistance and interfacial contact resistance (ICR) were determined by the composition and morphology of the NiO-YSZ film. The corrosion resistance increased with increasing Ni content in the NiO-YSZ film, but rapid corrosion was observed when the YSZ film contained more than 15 wt % Ni due to surface cracks. The polarization resistance was improved by several orders of magnitude when 316L stainless steel was coated with a 15 wt % NiO-YSZ film compared to bare 316L. The ICR of the NiO-YSZ film was decreased to that of bare 316L when the YSZ film contained 25 wt % NiO, suggesting the possible application of NiO-YSZ coated stainless steel for a bipolar plate.

Novel Methods for Measuring the Surface Hardness of Anodic Oxide Films on Aluminum Alloy (알루미늄 합금 양극산화피막의 표면경도 측정법)

  • Moon, Sungmo
    • Journal of the Korean institute of surface engineering
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    • v.53 no.1
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    • pp.36-42
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    • 2020
  • In this study, two novel methods to measure the surface hardness of anodic oxide films on aluminum alloys are reported. The first method is to impregnate oil-based ink into pores in the anodic oxide film and then to clean the ink on the surface using ethanol, resulting in an impregnation of inks only inside of the pores in anodic oxide film. The second method is to coat the anodic oxide film surface with thin Au layer less than 0.1 ?. Both the ink-impregnating method and Au-coating method provided clear indentation marks on the anodic oxide film surface when it was indented using a pyramidal-diamond penetrator. Thus, Vickers hardness of anodic oxide films on aluminium alloy could be measured successfully and precisely from the anodic film surface. In addition, advantages and disadvantages of the ink-impregnating method and Au-coating method for the measurement of surface hardness of anodic oxide films are discussed.

High-Ic YBCO thick film fabricated by the MOD process (MOD 공정으로 제조된 고임계전류 YBCO 후막)

  • Shin, Geo-Myung;Song, Kyu-Jung;Moon, Seung-Hyun;Yoo, Sang-Im
    • Progress in Superconductivity and Cryogenics
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    • v.10 no.1
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    • pp.6-9
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    • 2008
  • We have investigated the MOD process successfully for the fabrication of the YBCO thick film on the $LaAlO_3$(001) single crystalline substrate. The cracking problem in YBCO thick film, a serious problem in the conventional TFA-MOD method, could be overcome with a careful control of precursor materials. Thus coating solution was prepared for the YBCO thick film by using fluorine-free precursor material. The precursor solutions were coated on the LAO(001) single crystalline substrate using the dip coating method, calcined at the temperature up to $500^{\circ}C$, and fired at various high temperatures for 2 h in a reduced oxygen atmosphere. Optimally processed YBCO thick film exhibited high critical current($I_c$) over 200 A/cm-width at 77K in self-field.

Structural and Dielectrical Properties of PZT(30/70)/PZT(70/30) Heterolayered Thin Film Prepared by Sol-Gel Method (Sol-Gel법으로 제작한 PZT(30/70)/PZT(70/30) 이종층 박막의 구조 및 유전특성)

  • Kim, Gyeong-Gyun;Jeong, Jang-Ho;Lee, Seong-Gap;Lee, Yeong-Hui
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.48 no.7
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    • pp.514-520
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    • 1999
  • Ferroelectric PZT(30/70)/PZT(70/30) heterolayered thin films were fabricated by spin-coating method on the $Pt/Ti/SiO_2Si$ substrate alternately using(30/70) and PZT(70/30) alkoxide solutions prepared by sol-coating method. The coating and heating procedure was repeated six times to form PZT heterolayered films, and thickness of the film obtained by one-times drying/sintering process was about 40-50 nm. All PZT heterolayered films, showed dense and homogeneous structure without the presence of rosette sturctrue. The relative dielectric constant, remanent polarization and leakage current density of PZT heterolayered films were superior to those of single composition PZT(30/70) and PZT(70/30) films, and those values for the PZT-6 film were 975, $21 \muC/cm^2\; and\; 8\times10^{-9}\; A/cm^2$, respectively. And the PZT-6 heterolayered film showed fairly good fatigue characteristics of remanent polarization and coercive field after application of $10^8$ switching cycles.

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Structural and Dielectric Properties of $PbTiO_3$ Ferroelectric Thin Film Prepared by Sol-Gel Processing (Sol-Gel법으로 제조된 $PbTiO_3$ 강유전 박막의 구조적, 유전적 특성)

  • 김준한;백동수;박창엽
    • Journal of the Korean Ceramic Society
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    • v.30 no.9
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    • pp.695-700
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    • 1993
  • In this study, we prepared Pb-Ti stock solution by sol-gel processing and deposited PbTiO3 thin film on a Pt coated SiO2/Si wafer by spin coating using the stock solution. We used lead acetate trihydrate and titanium isopropoxide. The stock solution was partially hydrolized and finally a 0.25M coating solution was prepared. We achieved spin coating at 4000rpm for 30 seconds and heated the thin film at 375$^{\circ}C$ for 5 minutes and at $600^{\circ}C$ for 5 minutes successively, first and second heating state. And the thin film was finally sintered at 90$0^{\circ}C$ for 1 hour in the air. The upper electrode of the thin film was made by gold sputtering and was cricle shape with radius 0.4mm. Measured dielectric constant, dissipation factor and phase transition temperature(Cuire Temp.) were about 275, 0.02 and 521$^{\circ}C$ respectively. To observe ferroelectric characteristics we calculated Pr(remnant polarization) and Ec(coercive field) byhysteresis curve. Ec was 72kV/cm and Pr was 11.46$\mu$C/$\textrm{cm}^2$.

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Preparation of $TiO_2$ Film by the Dip-Coating Method and its Application to Photo electrochemical Electrodes (침액 코오팅 방법에 의한 $TiO_2$ 박막의 제조와 광전기 화학전극의 응용에 관한 연구)

  • Jung, Hyun-Chai;Ahn, Byung-Doo;Kim, Ki-Sun
    • Solar Energy
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    • v.9 no.1
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    • pp.14-21
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    • 1989
  • Preparation of $TiO_2$ Film by the Dip-coating Method and its Application to photo-electrochemical Electrodes. $TiO_2$ film of n-type semiconductor has been of great interest as a material for solar energy conversion. For its practical application, the dip-coating method has been applied to prepare $TiO_2$ (anatase) film on the nesa glass substrate. Films up to about $1.8{\mu}m$ in thickness can be obtained by repeating the operation, dipping $\to$ pulling up $\to$ drying $\to$ heating at $500^{\circ}C$ for 10 minute. Heating temperature at $500^{\circ}C$ was adopted to convert $TiO_2$ gels into $TiO_2$ crystalline films. The $TiO_2$ films showed the maximum photocurrent ($14mA/cm^2$) at the film thickness of about $1.8{\mu}m$. It was also found that the additional heating at $500^{\circ}C$ for about 20 minutes improved remarkably the photo current of the $TiO_2$ films.

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Characterization of Silicon Nitride Coating Films (Si-N 코팅막의 기계적 물성 및 구조 분석)

  • Go, Cheolho;Kim, Bongseob;Yun, Jondo;Kim, Kwangho
    • Journal of the Korean Ceramic Society
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    • v.42 no.5 s.276
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    • pp.359-365
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    • 2005
  • Silicon nitride coating films with various ratios of nitrogen to silicon contents were prepared and characterized. The film was coated on silicon substrate by sputtering method with changing nitrogen gas flow rate in a chamber. The nitrogen to silicon ratio was found to have values in a range from 0 to 1.4. Coated film was characterized with scanning electron microscopy, transmission electron microscopy, electron probe microanalysis, nanoindentation scanning probe microscopy, x-ray photon spectrometry, and Raman spectrometry. Silicon nitride phase in all samples showed amorphous nature regardless of N/Si ratio. When N/Si ratio was 1.25, hardness and elastic modulus of silicon nitride film showed maximum with 22 GPa and 210 GPa, respectively. Those values decreased, when N/Si ratio was higher than 1.25. Raman spectrum showed that no silicon phase exist in the film. XPS result showed that the silicon-nitrogen bond was dominant way for atomic bonding in the film. The structure and property was explained with Random Bonding Model(RBM) which was consistent with the microstructure and chemistry analysis for the coating films.