• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.24 no.12
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• pp.962-968
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• 2011

In this study, we investigated the effects of Mn dopant (0.1~3.0 at% $Mn_3O_4$ sintered at 1000$^{\circ}C$ for 1 h in air) on the bulk trap (i.e. defect) and grain boundary properties of ZnO, ZM(0.1~3.0) using admittance spectroscopy (AS), and impedance-modulus spectroscopy (IS & MS). As a result, three kinds of defect were found below the conduction band edge of ZnO as 0.09~0.14 eV (attractive coulombic center), 0.22~25 eV ($Zn^{{\cdot}{\cdot}}_i$), and 0.32~0.33 eV ($V^{\cdot}_o$). The oxygen vacancy increased with Mn doping. In ZM, an electrically single grain boundary as double Schottky barrier was formed with 0.82~1.0 eV of activation energies by IS & MS. We also find out that the barriers of grain boundary of Mn-doped ZnO (${\alpha}$-factor=0.13) were more stabilized and homogenized with temperature compared to pure ZnO.

• Journal of the Korean Ceramic Society
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• v.49 no.5
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• pp.404-411
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• 2012

The reliability of solid oxide fuel cells (SOFCs) particularly depends on the high quality of solid oxide electrolytes. The application of thinner electrolytes and multi electrolyte layers requires a more reliable characterization method. Most of the investigations on thin film solid electrolytes have been made for the parallel transport along the interface, which is not however directly related to the fuel cell performance of those electrolytes. In this work an array of ion-blocking metallic Ti/Au microelectrodes with about a $160{\mu}m$ diameter was applied on top of an ultrathin ($1{\mu}m$) yttria-stabilized-zirconia/gadolinium-doped-ceria (YSZ/GDC) heterolayer solid electrolyte in a micro-SOFC prepared by PLD as well as an 8-${\mu}m$ thick YSZ layer by screen printing, to study the transport characteristics in the perpendicular direction relevant for fuel cell operation. While the capacitance variation in the electrode area supported the working principle of the measurement technique, other local variations could be related to the quality of the electrolyte layers and deposited electrode points. While the small electrode size and low temperature measurements increaseed the electrolyte resistances enough for the reliable estimation, the impedance spectra appeared to consist of only a large electrode polarization. Modulus representation distinguished two high frequency responses with resistance magnitude differing by orders of magnitude, which can be ascribed to the gadolinium-doped ceria buffer electrolyte layer with a 200 nm thickness and yttria-stabilized zirconia layer of about $1{\mu}m$. The major impedance response was attributed to the resistance due to electron hole conduction in GDC due to the ion-blocking top electrodes with activation energy of 0.7 eV. The respective conductivity values were obtained by model analysis using empirical Havriliak-Negami elements and by temperature adjustments with respect to the conductivity of the YSZ layers.

• Corrosion Science and Technology
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• v.8 no.4
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• pp.162-169
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• 2009

Pure titanium and its alloys are drastically used in implant materials due to their excellent mechanical properties, high corrosion resistance and good biocompatibility. However, the widely used Ti-6Al-4V is found to release toxic ions (Al and V) into the body, leading to undesirable long-term effects. Ti-6Al-4V has much higher elastic modulus than cortical bone. Therefore, titanium alloys with low elastic modulus have been developed as biomaterials to minimize stress shielding. For this reason, Ti-30Ta-xZr alloy systems have been studied in this study. The Ti-30Ta containing Zr(5, 10 and 15 wt%) were 10 times melted to improve chemical homogeneity by using a vacuum furnace and then homogenized for 24 hrs at $1000^{\circ}C$. The specimens were cut and polished for corrosion test and Ti coating and then coated with TiN, respectively, by using DC magnetron sputtering method. The analyses of coated surface were carried out by field emission scanning electron microscope(FE-SEM). The electrochemical characteristics were examined using potentiodynamic (- 1500 mV~+ 2000 mV) and AC impedance spectroscopy(100 kHz~10 mHz) in 0.9% NaCl solution at $36.5{\pm}1^{\circ}C$. The equiaxed structure was changed to needle-like structure with increasing Zr content. The surface defects and structures were covered with TiN/Ti coated layer. From the polarization behavior in 0.9% NaCl solution, The corrosion current density of Ti-30Ta-xZr alloys decreased as Zr content increased, whereas, the corrosion potential of Ti-30Ta-xZr alloys increased as Zr content increased. The corrosion resistance of TiN/Ti-coated Ti-30Ta-xZr alloys were higher than that of the TiN-coated Ti-30Ta-xZr alloys. From the AC impedance in 0.9% NaCl solution, polarization resistance($R_p$) value of TiN/Ti coated Ti-30Ta-xZr alloys showed higher than that of TiN-coated Ti-30Ta-xZr alloys.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.23 no.12
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• pp.942-948
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• 2010

In this study we aims to examine the effects of 0.5 mol% $Cr_2O_3$ addition on the reaction, microstructure development, resultant electrical properties, and especially the bulk trap and interface state levels of ZnO-$Bi_2O_3-Sb_2O_3$ (Sb/Bi=0.5, 1.0, and 2.0) systems (ZBS). The samples were prepared by conventional ceramic process, and characterized by XRD, density, SEM, I-V, impedance and modulus spectroscopy (IS & MS) measurement. The sintering and electrical properties of Cr-doped ZBS (ZBSCr) systems were controlled by Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$) was decomposed more than $100^{\circ}C$ lowered on heating in ZBS (Sb/Bi=1.0) by Cr doping. The densification of ZBSCr (Sb/Bi=0.5) system was retarded to $800^{\circ}C$ by unknown Bi-rich phase produced at $700^{\circ}C$. Pyrochlore on cooling was reproduced in all systems. And $Zn_7Sb_2O_{12}$ spinel ($\alpha$-polymorph) and $\delta-Bi_2O_3$ phase were formed by Cr doping. In ZBSCr, the varistor characteristics were not improved drastically (non-linear coefficient $\alpha$ = 7~12) and independent on microstructure according to Sb/Bi ratio. Doping of $Cr_2O_3$ to ZBS seemed to form $Zn_i^{..}$(0.16 eV) and $V^{\bullet}_o$ (0.33 eV) as dominant defects. From IS & MS, especially the grain boundaries of Sb/Bi=0.5 systems were divided into two types, i.e. sensitive to oxygen and thus electrically active one (1.1 eV) and electrically inactive intergranular one (0.95 eV) with temperature.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.06a
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• pp.16-16
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• 2009

ZnO($Zn_{1+x}O$)는 n-type 반도성 세라믹스로 우수한 전기적, 광학적, 화학적 특성을 갖고 있어 바리스터, 투명 전도막, 화학 및 바이오 센서, UV light emitter 등 다양한 용도로 사용되고 있다. 또한 ZnO에 각종 천이 금속 산화물을 일정량 첨가함에 따라 발생하는 결함준위와 입계 특성의 변화에 대한 연구가 활발히 진행되고 있다. 다양한 천이 금속 산화물의 첨가에 따른 전기적 광학적 특성의 변화에 대한 결과들이 많이 보고되고 있지만 서로 상충되거나 해석상 다소 어려운 것으로 알려져 있다. 따라서 본 연구에서는 ZnO에 $Cr_2O_3$를 2.0 at% 첨가하여 Cr 첨가에 따른 ZnO의 결함준위와 입계 특성 변화에 대하여 각종 유전함수($Z^*$, $Y^*$, $M^*$, $\varepsilon^*$, and $tan{\delta}$)를 이용하여 고찰하였다 ZnO에 Cr을 첨가할 경우 결함 중 장범위 쿨롱 인력에 의한 결함(0.13~0.18 eV)이 ~100K 영역에서 나타났으며, ZnO 내 결함 중 대표적인 $Zn_j$와 $V_o$는 서로 겹쳐서 나타났다. 이들 중첩된 결함에 대하여 각종 유전함수를 이용할 경우 서로 분리해 낼 수 있는 강점이 있음을 논하였다. 또한 각 결함준위가 강는 정전용랑(C)과 저항(R)을 impedance-modulus spectroscopy를 이용하여 구한 결과, 소결온도가 높아질수록 정전용량은 증가하였으며, 측정온도가 놓아질수록 높아지는 경향을 나타내었다. 입계의 정전용량은 소결온도가 높아질수록 높아 지지만 측정온도가 높아질수록 낮아지는 경향을 나타내었다. 각 저항값은 소결온도 및 측정온도가 높아질수록 지수적으로 감소하였다. 또한 분포함수를 이용하여 입계 안정성에 대하여 고찰하였다.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.25 no.11
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• pp.878-885
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• 2012

In this study we aims to examine the co-doping effects of 1/3 mol% $Mn_3O_4+Co_3O_4$ (1:1) on the reaction, microstructure, and electrical properties such as the bulk defects and grain boundary properties of $ZnO-Bi_2O_3-Sb_2O_3$ (ZBS; Sb/Bi=0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Mn,Co-doped ZBS, ZBS(MCo) varistors were controlled by Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$) was decomposed and promoted densification at lower temperature on heating in Sb/Bi=1.0 by Mn rather than Co. Pyrochlore on cooling was reproduced in all systems however, spinel (${\alpha}$- or ${\beta}$-polymorph) did not formed in Sb/Bi=0.5. More homogeneous microstructure was obtained in $Sb/Bi{\geq}1.0$ In ZBS(MCo), the varistor characteristics were improved drastically (non-linear coefficient, ${\alpha}$=30~49), and seemed to form $Zn_i^{..}$(0.17 eV) and $V_o^{\bullet}$(0.33 eV) as dominant defects. From impedance and modulus spectroscopy (IS & MS), the grain boundaries have divided into two types, i.e. the one is tentatively assign to $ZnO/Bi_2O_3(Mn,Co)/ZnO$ (0.47 eV) and the other ZnO/ZnO (0.80~0.89 eV) homojunctions.

• Korean Journal of Materials Research
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• v.22 no.12
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• pp.682-688
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• 2012

In this study we aimed to examine the co-doping effects of 1/6 mol% $Co_3O_4$ and 1/4 mol% $Cr_2O_3$ (Co:Cr = 1:1) on the reaction, microstructure, and electrical properties, such as the bulk defects and the grain boundary properties, of ZnO-$Bi_2O_3-Sb_2O_3$ (ZBS; Sb/Bi = 0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Co,Cr-doped ZBS, ZBS(CoCr) varistors were controlled using the Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$), ${\alpha}$-spinel ($Zn_7Sb_2O_{12}$), and ${\delta}-Bi_2O_3$ were formed in all systems. Pyrochlore was decomposed and promoted densification at lower temperature on heating in Sb/Bi = 1.0 by Cr rather than Co. A more homogeneous microstructure was obtained in all systems affected by ${\alpha}$-spinel. In ZBS(CoCr), the varistor characteristics were improved (non-linear coefficient, ${\alpha}$ = 20~63), and seemed to form ${Zn_i}^{{\cdot}{\cdot}}$(0.20 eV) and ${V_o}^{\cdot}$(0.33 eV) as dominant defects. From impedance and modulus spectroscopy, the grain boundaries were found to be composed of an electrically single barrier (0.94~1.1 eV) that is, however, somewhat sensitive to ambient oxygen with temperature. The phase development, densification, and microstructure were controlled by Cr rather than by Co but the electrical and grain boundary properties were controlled by Co rather than by Cr.

• Korean Journal of Materials Research
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• v.22 no.12
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• pp.675-681
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• 2012

We aimed to examine the co-doping effects of 1/6 mol% $Mn_3O_4$ and 1/4 mol% $Cr_2O_3$ (Mn:Cr = 1:1) on the reaction, microstructure, and electrical properties, such as the bulk defects and grain boundary properties, of ZnO-$Bi_2O_3-Sb_2O_3$ (ZBS; Sb/Bi = 0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Mn,Cr-doped ZBS, ZBS(MnCr) varistors were controlled using the Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$), ${\alpha}$-spinel ($Zn_7Sb_2O_{12}$), and ${\delta}-Bi_2O_3$ (also ${\beta}-Bi_2O_3$ at Sb/Bi ${\leq}$ 1.0) were detected for all of the systems. Mn and Cr are involved in the development of each phase. Pyrochlore was decomposed and promoted densification at lower temperature on heating in Sb/Bi = 1.0 system by Mn rather than Cr doping. A more homogeneous microstructure was obtained in all systems affected by ${\alpha}$-spinel. In ZBS(MnCr), the varistor characteristics were improved dramatically (non-linear coefficient, ${\alpha}$ = 40~78), and seemed to form ${V_o}^{\cdot}$(0.33 eV) as a dominant defect. From impedance and modulus spectroscopy, the grain boundaries can be seen to have divided into two types, i.e. one is tentatively assigned to ZnO/$Bi_2O_3$ (Mn,Cr)/ZnO (0.64~1.1 eV) and the other is assigned to the ZnO/ZnO (1.0~1.3 eV) homojunction.

• Korean Journal of Materials Research
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• v.22 no.12
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• pp.689-695
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• 2012

We have examined the co-doping effects of 1/2 mol% NiO and 1/4 mol% $Cr_2O_3$ (Ni:Cr = 1:1) on the reaction, microstructure, and electrical properties, such as the bulk defects and the grain boundary properties, of ZnO-$Bi_2O_3-Sb_2O_3$ (ZBS; Sb/Bi = 0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Ni,Cr-doped ZBS, ZBS(NiCr) varistors were controlled using the Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$), ${\alpha}$-spinel ($Zn_7Sb_2O_{12}$), and ${\delta}-Bi_2O_3$ were detected for all of compositions. For the sample with Sb/Bi = 1.0, the Pyrochlore was decomposed and promoted densification at lower temperature by Ni rather than by Cr. A homogeneous microstructure was obtained for all of the samples affected by ${\alpha}$-spinel. The varistor characteristics were not dramatically improved (non-linear coefficient, ${\alpha}$ = 5~24), and seemed to form ${Zn_i}^{{\cdot}{\cdot}}$(0.17 eV) and ${V_o}^{\cdot}$(0.33 eV) as dominant defects. From impedance and modulus spectroscopy, the grain boundaries were found to have been divided into two types, i.e., one is tentatively assigned to ZnO/$Bi_2O_3$ (Ni,Cr)/ZnO (0.98 eV) and the other is assigned to a ZnO/ZnO (~1.5 eV) homojunction.