• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.451-454
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• 2011

The traditional BCS superconductors $AOs_2O_6$ (A=K, Rb, and Cs) were investigated to find the relationship between their structures and superconducting transition temperatures. The $T_c$ decreases with increasing the unit cell parameter of $AOs_2O_6$. This is in contrast to the case of conventional BCS superconductivity in a single bond model, where $T_c$ may increase with increasing the the unit cell parameter since the DOS at Fermi level increases as the unit cell parameter increases. Instead, the $T_c$ of a $\beta$-pyrochlore oxide is proportional to the lattice softness of the compound.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.22 no.11
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• pp.941-948
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• 2009

The present study aims at the examination of the effects of 1 mol% NiO 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 density, XRD, SEM, I-V, impedance and modulus spectroscopy (IS & MS) measurement. The sintering and electrical properties of Ni-doped ZBS (ZBSN) systems were controlled by Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$) was decomposed more than $100^{\circ}C$ lowered in ZBS (Sb/Bi=1.0) by Ni doping. The reproduction of pyrochlore was suppressed by the addition of Ni in ZBS. Between two polymorphs of $Zn_7Sb_2O_{12}$ spinel ($\alpha$ and $\beta$), microstructure of ZBSN (Sb/Bi=0.5) composed of a-spinel was more homogeneous than $Sb/Bi{\geq}1.0$ composed of $\beta$-spinel phase. In ZBSN, the varistor characteristics were not improved drastically (non-linear coefficient $\alpha\;=\;6{\sim}11$) and independent on microstructure according to Sb/Bi ratio. Doping of Ni to ZBS seemed to form ${V_0}^{\cdot}$ (0.33 eV) as dominant bulk defect. 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 and electrically inactive intergranular one with temperature.

• 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.

• 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.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.21 no.8
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• pp.738-748
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• 2008

In this study, it has been investigated on the changing behavior of electrical properties in $ZnO-Bi_2O_3-Sb_2O_3$ (Sb/Bi=2.0, 1.0 and 0.5) ceramics. The samples were prepared by conventional ceramic process, and then characterized by I-V, C-V curve plots, impedance and modulus spectroscopy (IS & MS) measurement. The electrical properties of ZBS systems were strongly dependent on Sb/Bi. In ZBS systems, the varistor characteristics were deteriorated noticeably with increasing Sb/Bi and the donor density and interface state density were increased with increasing Sb/Bi. On the other hand, we observed that the grain boundary reacted actively with the ambient oxygen according to Sb/Bi ratio. 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 and electrically inactive intergranular one with temperature. Besides, the increased pyrochlore and $\beta$-spinel phase with Sb/Bi ratio caused the distributional inhomogeneity in the grain boundary barrier height and the temperature instability. To the contrary, the grain boundary layer was relatively homogeneous and more stable to temperature change and kept the system highly nonlinear at high Bi-rich phase contents.