• Title/Summary/Keyword: Mn-oxide

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Self-formation of Diffusion Barrier at the Interface between Cu-V Alloy and $SiO_2$

  • Mun, Dae-Yong;Park, Jae-Hyeong;Han, Dong-Seok;Gang, Yu-Jin;Seo, Jin-Gyo;Yun, Don-Gyu;Sin, So-Ra;Park, Jong-Wan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.256-256
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    • 2012
  • Cu가 기존 배선물질인 Al을 대체함에 따라 resistance-capacitance delay와 electromigration (EM) 등의 문제들이 어느 정도 해결되었다. 그러나 지속적인 배선 폭의 감소로 배선의 저항 증가, EM 현상 강화 그리고 stability 악화 등의 문제가 지속적으로 야기되고 있다. 이를 해결하기 위한 방법으로 Cu alloy seed layer를 이용한 barrier 자가형성 공정에 대한 연구를 진행하였다. 이 공정은 Cu 합금을 seed layer로 사용하여 도금을 한 후 열처리를 통해 $SiO_2$와의 계면에서 barrier를 자가 형성시키는 공정이다. 이 공정은 매우 균일하고 얇은 barrier를 형성할 수 있고 별도의 barrier와 glue layer를 형성하지 않아 seed layer를 위한 공간을 추가로 확보할 수 있는 장점을 가지고 있다. 또한, via bottom에 barrier가 형성되지 않아 배선 전체 저항을 급격히 낮출 수 있다. 합금 물질로는 초기 Al이나 Mg에 대한 연구가 진행되었으나, 낮은 oxide formation energy로 인해 SiO2에 과도한 손상을 주는 문제점이 제기되었다. 최근 Mn을 합금 물질로 사용한 안정적인 barrier 형성 공정이 보고 되고 있다. 하지만, barrier 형성을 하기 위해 300도 이상의 열처리 온도가 필요하고 열처리 시간 또한 긴 단점이 있다. 본 실험에서는 co-sputtering system을 사용하여 Cu-V 합금을 형성하였고, barrier를 자가 형성을 위해 300도에서 500도까지 열처리 온도를 변화시키며 1시간 동안 열처리를 실시하였다. Cu-V 공정 조건 확립을 위해 AFM, XRD, 4-point probe system을 이용하여 표면 거칠기, 결정성과 비저항을 평가하였다. Cu-V 박막 내 V의 함량은 V target의 plasma power density를 변화시켜 조절 하였으며 XPS를 통해 분석하였다. 열처리 후 시편의 단면을 TEM으로 분석하여 Cu-V 박막과 $SiO_2$ 사이에 interlayer가 형성된 것을 확인 하였으며 EDS를 이용한 element mapping을 통해 Cu-V 내 V의 거동과 interlayer의 성분을 확인하였다. PVD Cu-V 박막은 기판 온도에 큰 영향을 받았고, 200도 이상에서는 Cu의 높은 표면에너지에 의한 agglomeration 현상으로 거친 표면을 가지는 박막이 형성되었다. 7.61 at.%의 V함량을 가지는 Cu-V 박막을 300도에서 1시간 열처리 한 결과 4.5 nm의 V based oxide interlayer가 형성된 것을 확인하였다. 열처리에 의해 Cu-V 박막 내 V은 $SiO_2$와의 계면과 박막 표면으로 확산하며 oxide를 형성했으며 Cu-V 박막 내 V 함량은 줄어들었다. 300, 400, 500도에서 열처리 한 결과 동일 조성과 열처리 온도에서 Cu-Mn에 의해 형성된 interlayer의 두께 보다 두껍게 성장했다. 이는 V의 oxide formation energy가 Mn 보다 작으므로 SiO2와의 계면에서 산화막 형성이 쉽기 때문으로 판단된다. 또한, $V^{+5}$이온 반경이 $Mn^{+2}$이온 반경보다 작아 oxide 내부에서 확산이 용이하며 oxide 박막 내에 여기되는 전기장이 더 큰 산화수를 가지는 V의 경우 더 크기 때문으로 판단된다.

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Synthesis and Properties of La1-xSrxMnO3 System as Air Electrode for Solid Oxide Fuel Cell (고체산화물 연료전지의 공기극으로서 La1-xSrxMnO3 계의 합성 및 특성)

  • Lee, You-Kee;Lee, Young-Ki
    • Korean Journal of Materials Research
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    • v.22 no.9
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    • pp.470-475
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    • 2012
  • $La_{1-x}Sr_xMnO_3$(LSM,$0{\leq}x{\leq}0.5$) powders as the air electrode for solid oxide fuel cell were synthesized by a glycine-nitrate combustion process. The powders were then examined by X-ray diffraction(XRD) and scanning electron microscopy (SEM). The as-formed powders were composed of very fine ash particles linked together in chains. X-ray maps of the LSM powders milled for 1.5 h showed that the metallic elements are homogeneously distributed inside each grain and in the different grains. The powder XRD patterns of the LSM with x < 0.3 showed a rhombohedral phase; the phase changes to the cubic phase at higher compositions($x{\geq}0.3$) calcined in air at $1200^{\circ}C$ for 4 h. Also, the SEM micrographs showed that the average grain size decreases as Sr content increases. Composite air electrodes made of 50/50 vol% of the resulting LSM powders and yttria stabilized zirconia(YSZ) powders were prepared by colloidal deposition technique. The electrodes were studied by ac impedance spectroscopy in order to improve the performance of a solid oxide fuel cell(SOFC). Reproducible impedance spectra were confirmed using the improved cell, which consisted of LSM-YSZ/YSZ. The composite electrode of LSM and YSZ was found to yield a lower cathodic resistivity than that of the non-composite one. Also, the addition of YSZ to the $La_{1-x}Sr_xMnO_3$ ($0.1{\leq}x{\leq}0.2$) electrode led to a pronounced, large decrease in the cathodic resistivity of the LSM-YSZ composite electrodes.

Protective Coatings for Application of Fe-l6Cr Ferritic Alloy as an Interconnector in SOFCs (고체산화물 연료전지용 금속접속자로의 적용을 위한 Fe-16Cr 페라이트 합금의 내산화막 코팅)

  • 이용진;김상우;김긍호;이종호;안진호
    • Journal of the Korean Ceramic Society
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    • v.40 no.2
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    • pp.139-145
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    • 2003
  • We studied oxidation behaviors of anti-oxidative Y-Cr oxide coated sol on ferritic steel for application of the Fe-Cr alloys as interconnectors of planar-type Solid Oxide Fuel Cells(SOFCs). In coated$YCrO_3$on the ferritic steel, the phases of $YCrO_3$,$Cr_2O_3$and $Mn_{1.5}Cr_{1.5}O_4$on the coated surface were detected, but iron base scales were not observed after oxidation at 80$0^{\circ}C$ for 40 h. The Mn-Cr oxide scales were grown with oxidation by diffusing components in the ferritic steel from inner. The Log(ASR/T) value that expresses electrical resistance of coated$YCrO_3$on the ferritic steel was -4.57~$-4.70{omega}cm^2K^{-1}$, lower in comparison with the one of the uncoated ferritic steel,$-3.99{omega}cm^2K^{-1}$. This indicates the applicability of Fe-l6Cr alloy as interconnector materials for SOFCs.

Manganese Oxide Catalyzed Fenton-like Reduction of Chlorinated Compounds (산화망간으로 촉매화된 펜톤유사반응을 적용한 염소계화합물의 환원분해)

  • 김상민;공성호;김용수
    • Journal of Soil and Groundwater Environment
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    • v.7 no.3
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    • pp.95-102
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    • 2002
  • Manganese oxide/ hydrogen peroxide($MnO_2$/${H_2}{O_2}$) reactions were investigated as an alternative to Fenton-like reaction to reduce chlorinated organic compounds in groundwater This system showed high degradation of CT with low ${H_2}{O_2}$concentration($\leq$294mM) at neutral condition, and CT degradation increased with increasing pH values. The rate of CT degradation was not so much dependent on increase in $MnO_2$concentration since increase in production of oxygen during the reaction obstructed reaction of ${H_2}{O_2}$ on the surface of $MnO_2$. These results show that $MnO_2$catalyzed Ponton-like reaction could be a potential alternative method for treating chlorinated organic compounds in groundwater.

Catalytic Oxidation of Toluene over Mn-Ce/${\gamma}-Al_2O_3$ Catalyst Doped with Ce (Ce가 첨가된 Mn-Ce/${\gamma}-Al_2O_3$ 촉매상에서 톨루엔의 촉매 산화 반응)

  • Cheon, Tae-Jin;Kim, Hye-Jin;Choi, Sung-Woo
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.5
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    • pp.513-518
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    • 2005
  • Catalytic oxidation of toluene on the manganese oxide catalysts and manganese-cerium oxide catalysts was investigated. The catalysts were characterised by X-ray diffraction(XRD), thermo gravimetric analyzer(TGA), toluene-temperature program reduction(Toluene-TPR). We found that the optimal manganese content was 18.2 wt.% and the optimal cerium content was 10.0 wt.% at catalytic oxidation of toluene. It is shown that ceria improves the activity of manganese oxide phases. From the XRD results, it was estimated that $MnO_2$ phase was active site in the monometallic and bimetallic catalysts. From the TGA and Toluene-TPR results, it show that ceria improves the mobility of the lattice oxygen, adequate oxidation state of the active phase, reduction ability at low temperature, and re-oxidation of the active site.

MBE growth and magnetic properties of epitaxial FeMn2O4 film on MgO(100)

  • Duong, Van Thiet;Nguyen, Thi Minh Hai;Nguyen, Anh Phuong;Dang, Duc Dung;Duong, Anh Tuan;Nguyen, Van Quang;Cho, Sunglae
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.318.2-318.2
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    • 2016
  • FeM2X4 spinel structures, where M is a transition metal and X is oxygen or sulfur, are candidate materials for spin filters, one of the key devices in spintronics. Both the Fe and M ions can occupy tetrahedral and octahedral sites; therefore, these types of compounds can display various physical and chemical properties [1]. On the other hand, the electronic and magnetic properties of these spinel structures could be modified via the control of cation distribution [2, 3]. Among the spinel oxides, iron manganese oxide is one of promising materials for applications. FeMn2O4 shows inverse spinel structure above 390 K and ferrimagnetic properties below the temperature [4]. In this work, we report on the structural and magnetic properties of epitaxial FeMn2O4 thin film on MgO(100) substrate. The reflection high energy electron diffraction (RHEED) and X-ray diffraction (XRD) results indicated that films were epitaxially grown on MgO(100) without the impurity phases. The valance states of Fe and Mn in the FeMn2O4 film were carried out using x-ray photoelectron spectrometer (XPS). The magnetic properties were measured by vibrating sample magnetometer (VSM), indicating that the samples are ferromagnetic at room temperature. The structural detail and origin of magnetic ordering in FeMn2O4 will be discussed.

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Effects of Oxygen Partial Pressure and Annealing on the Characteristics of Mn-Ni Oxide Thin Films (분위기 산소농도 및 열처리에 따른 Mn-Ni계 산화물 박막의 특성)

  • Choe, Seong-Ho;Kim, Cheol-Su;Lee, Yong-Seong
    • Korean Journal of Materials Research
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    • v.9 no.7
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    • pp.657-662
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    • 1999
  • Mn-Ni oxide thin films for NTC thermistor application were sputtered on alumina substrates at $320^{\circ}C$ Effects of various oxygen partial pressures and annealing temperatures on the microstructure, crystal phase, resistivity and B constant were investigated. In general, microstructure of the films deposited was columnar grain structure. After annealing at $700^{\circ}C$, the microstructure was begun to transform to equiaxed grain structure. Most of the phases were mixture of cubic spinel and $Mn_2$$O_3$. As the oxygen concentration increased, the resistivity and B constant were greatly decreased, and these values become low and stable after annealing between $600^{\circ}C$ and $700^{\circ}C$.

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Effect of Al and Mg Contents on Wettability and Reactivity of Molten Zn-Al-Mg Alloys on Steel Sheets Covered with MnO and SiO2 Layers

  • Huh, Joo-Youl;Hwang, Min-Je;Shim, Seung-Woo;Kim, Tae-Chul;Kim, Jong-Sang
    • Metals and materials international
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    • v.24 no.6
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    • pp.1241-1248
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    • 2018
  • The reactive wetting behaviors of molten Zn-Al-Mg alloys on MnO- and amorphous (a-) $SiO_2$-covered steel sheets were investigated by the sessile drop method, as a function of the Al and Mg contents in the alloys. The sessile drop tests were carried out at $460^{\circ}C$ and the variation in the contact angles (${\theta}_c$) of alloys containing 0.2-2.5 wt% Al and 0-3.0 wt% Mg was monitored for 20 s. For all the alloys, the MnO-covered steel substrate exhibited reactive wetting whereas the $a-SiO_2$-covered steel exhibited nonreactive, nonwetting (${\theta}_c>90^{\circ}$) behavior. The MnO layer was rapidly removed by Al and Mg contained in the alloys. The wetting of the MnO-covered steel sheet significantly improved upon increasing the Mg content but decreased upon increasing the Al content, indicating that the surface tension of the alloy droplet is the main factor controlling its wettability. Although the reactions of Al and Mg in molten alloys with the $a-SiO_2$ layer were found to be sluggish, the wettability of Zn-Al-Mg alloys on the $a-SiO_2$ layer improved upon increasing the Al and Mg contents. These results suggest that the wetting of advanced high-strength steel sheets, the surface oxide layer of which consists of a mixture of MnO and $SiO_2$, with Zn-Al-Mg alloys could be most effectively improved by increasing the Mg content of the alloys.

Varistor Properties and Aging Behavior of V/Mn/Co/ La/Dy Co-doped Zinc Oxide Ceramics Modified with Various Additives

  • Nahm, Choon-Woo
    • Transactions on Electrical and Electronic Materials
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    • v.15 no.5
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    • pp.284-289
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    • 2014
  • The effects of additives (Nb, Bi and Cr) on the microstructure, varistor properties, and aging behavior of V/Mn/Co/ La/Dy co-doped zinc oxide ceramics were systematically investigated. An analysis of the microstructure showed that all of the ceramics that were modified with various additives were composed of zinc oxide grain as the main phase, and secondary phases such as $Zn_3(VO_4)_2$, $ZnV_2O_4$, and $DyVO_4$. The $Bi_2O_3$-modified samples exhibited the lowest density, the $Nb_2O_5$-modified sample exhibited the largest average grain size, and the $Cr_2O_3$-modified samples exhibited the highest breakdown field. All additives improved the non-ohmic coefficient (${\alpha}$) by either a small or a large margin, and in particular an $Nb_2O_5$ additive noticeably increased the non-ohmic coefficient to be as large as 36. The $Bi_2O_3$-modified samples exhibited the highest stability with variation rates for the breakdown field and for the non-ohmic coefficient (${\alpha}$) of -1.2% and -26.3%, respectively, after application of a DC accelerated aging stress of 0.85 EB/$85^{\circ}C$/24 h.

Oxidation Behaviors of Nickel-Base Superalloys in High Temperature Steam Environments (고온 수증기 환경에서 Ni기 초합금의 산화특성)

  • Kim, Donghoon;Koo, Jahyun;Kim, Daejong;Yoo, Young-Sung;Jang, Changheui
    • Transactions of the Korean Society of Pressure Vessels and Piping
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    • v.7 no.2
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    • pp.26-33
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    • 2011
  • To evaluate steam oxidation behaviours of Alloy 617 and Haynes 230, oxidation test were performed at $900^{\circ}C$ in steam and $steam+20\;vol.-%\;H_2$ environments. Oxidation rate in steam condition was similar to that in air for Alloy 617, while it was slightly lower for Haynes 230. When hydrogen was added to steam, oxidation rate was enhanced. Isolated $MnTiO_3$ particle were formed on $Cr_2O_3$ oxide layer and sub layer $Cr_2O_3$ were formed in steam and $steam+20\;vol.-%\;H_2$ for Alloy 617. On the other hands, $MnCr_2O_3$ layer were formed on top of $Cr_2O_3$ oxide layer for Haynes 230. The extensive sub layer $Cr_2O_3$ formation was resulted from the oxygen inward diffusion in such environments. When hydrogen was added, the oxide morphology was changed from polygonal to platelet because of the accelerated diffusion of cations under the oxide layer. In addition, decarburized zone was extended as hydrogen participated into the reactions causing carbide dissolution.