• 한국재료학회지
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• 제22권12호
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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.

• 한국세라믹학회지
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• 제26권4호
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• pp.505-513
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• 1989

The sintering behavior and grain growth of ZnO in 99.0mol% ZnO-1.0mol% Bi2O3 which are the basic compositions of ZnO varistor were studied. The microstructrual observation confirmed that the final sintered density was mainly determined at the initial stage of sintering, i.e. grain rearrangement and grain growth which were induced by the penetration of eutectic melts formed at eutectic temperature(74$0^{\circ}C$). But when the liquid penetration was terminated, the grain growth did not promote further densification. Activation energy of the grain growth of ZnO in the system of 99.0mol% ZnO-1.0mol% Bi2O3 was 44.8$\pm$1.8Kcal/mol.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2007년도 추계학술대회 논문집
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• pp.284-284
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• 2007

In this study, the microwave dielectric property variations of (1-x)$BiNbO_4-(x)ZnNb_2O_6$ composites (x=0.3, 0.5 and 0.7) with 10wt% zinc borosilicate(ZBS) glass was investigated as a function of the substitution of $ZnNb_2O_6$ with a view to applying thes system to LTCC technology. The all composition addition of 10wt% ZBS glass ensured a successful sintering below $900^{\circ}C$. In addition, a small amount of $Bi_2SiO_5$ as the secondary phase was observed in the all composition. The substitution of $ZnNb_2O_6$ on the $BiNbO_4$ composites increased the $Q{\times}f$ values, but it decreased the sinterability and dielectric constant due to the high sintering temperature and low dielectric constant of $ZnNb_2O_6\;than\;BiNbO_4$ ceramics. The increasing of $ZnNb_2O_6$ content from 0.3 to 0.7 in the (1-x)$BiNbO_4-(x)ZnNb_2O_6$ composites with 10wt% ZBS glass sintered at $900^{\circ}C$ demonstrated 28.1~15.6 in the dielectric constant$({\varepsilon}_r)$, 5,500~8,700GHz in the $Q{\times}f$ value.

• 한국재료학회지
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• 제2권1호
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• pp.12-18
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• 1992

등온용량과도분광법(Isothermal Capacitance Transient spectroscopy)을 이용하여 ZnO 바리스터의 포획준위를 결정하였다. 여기서 등온용량과도분광기는 YHP 4192A 임피던스 Analyzer와 데이터해석을 위한 개인용 컴퓨터로 구성된다. 이 실험에서 우리는 $ZnO-Bi_2O_3$에 MnO 및 CoO를 첨가한계에서 $-40^{\circ}C~60^{\circ}C$ 온도범위에서 0.28, 0.48, 0.50, 0.94eV 등의 입계포획준위가 존재함을 볼 수 있었다. 또한, $ZnO-Bi_2O_3$계는 CoO를 첨가하면 hole에 의한 emission특성을 나타내고, MnO를 첨가하면 전자에 의한 emission특성을 나타냄을 알 수 있었다. 그리고 비 직선저항계수 $\alpha$는 도너농도의 감소에 직접적으로 비례하였으나, 포획준위의 밀도와는 별다른 비례관계를 발견할 수 없었다. 결론적으로 $ZnO-Bi_2O_3-MnO$계에 CoO를 첨가함에 따라 $\alpha$값이 증가하는 한편, 포획준위밀도는 CoO의 첨가로 감소함을 알 수 있었다.

• 한국재료학회지
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• 제21권10호
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• pp.563-567
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• 2011

We report the structural characterization of $Bi_xZn_{1-x}O$ thin films grown on c-plane sapphire substrates by plasma-assisted molecular beam epitaxy. By increasing the Bi flux during the growth process, $Bi_xZn_{1-x}O$ thin films with various Bi contents (x = 0~13.17 atomic %) were prepared. X-ray diffraction (XRD) measurements revealed the formation of Bi-oxide phase in (Bi)ZnO after increasing the Bi content. However, it was impossible to determine whether the formed Bi-oxide phase was the monoclinic structure ${\alpha}-Bi_2O_3$ or the tetragonal structure ${\beta}-Bi_2O_3$ by means of XRD ${\theta}-2{\theta}$ measurements, as the observed diffraction peaks of the $2{\theta}$ value at ~28 were very close to reflection of the (012) plane for the monoclinic structure ${\alpha}-Bi_2O_3$ at 28.064 and the reflection of the (201) plane for the tetragonal structure ${\beta}-Bi_2O_3$ at 27.946. By means of transmission electron microscopy (TEM) using a diffraction pattern analysis and a high-resolution lattice image, it was finally determined as the monoclinic structure ${\alpha}-Bi_2O_3$ phase. To investigate the distribution of the Bi and Bi-oxide phases in BiZnO films, elemental mapping using energy dispersive spectroscopy equipped with TEM was performed. Considering both the XRD and the elemental mapping results, it was concluded that hexagonal-structure wurtzite $Bi_xZn_{1-x}O$ thin films were grown at a low Bi content (x = ~2.37 atomic %) without the formation of ${\alpha}-Bi_2O_3$. However, the increased Bi content (x = 4.63~13.17 atomic %) resulted in the formation of the ${\alpha}-Bi_2O_3$ phase in the wurtzite (Bi)ZnO matrix.

• 한국재료학회지
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• 제22권12호
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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.

• 한국세라믹학회지
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• 제35권5호
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• pp.499-504
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• 1998

Pechini 방법으로 98.0 mol% ZnO, 1.0mol% $Bi_2O_3$, 0.5mol% CaO, 그리고 0.5mol% $MnO_2$ 조성의 ZnO 바리스터를 제조하여 소결거동과 전기적 특성을 관찰하였다. Pechini 방법으로 제조된 ZnO 바리스터 분말은 평균 입자크기가 $1.5\mu$m 정도이며 좁은 입도 분포를 보였다. $1100^{\circ}C$의 소결온도에서 전형적인 액상소결 과정에서 나타나는 입자성장 거동을 보였으며, 균일한 입자크기와 입계를 따라 Bi가 풍부한 액상이 고르게 분포된ZnO 바리스터를 제조할 수 있었다. 본 실험에서 비직선계수는 40~60 정도의 비교적 높은 값을 보였으며, 항복전압의 역수는 입자크기에 거의 비례하였다. 이것은 Pechini 방법으로 제조한 ZnO 바리스터가 균일한 입자크기와 균일한 액상의 분포를 갖는 바람직한 미세구조를 갖는 것을 보여 주는 것으로, Pechini 방법을 이용함으로서 ZnO 바리스터의 미세구조를 효과적으로 조절할 수 있으므로, 그 전기적 특성의 제어가 가능할 것으로 사료된다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2008년도 추계학술대회 논문집 Vol.21
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• pp.178-178
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• 2008

ZnO 바리스터는 인가되는 전압에 따라 저항이 변하는 전압 의존형 저항체이며 각종 전기 전자 정보통신용 제품에 정전기(ESD) 대책용 소자로 폭 넓게 사용되는 전자 세라믹스 부품이다. 특별히 Bi-based ZnO 바리스터는 다양한 상(phase)으로 구성되어 있으며 그 입계의 전기적 특성은 소량 첨가되는 dopant의 종류에 따라 다양하게 변하는 것으로 알려져 있다. 본 연구에서는 Bi-based ZnO 바리스터 (ZnO-$Bi_2O_3$, ZnO-$Bi_2O_3-Mn_3O_4$)에서 각종 유전함수$(Z^*,M^*,\varepsilon^*,Y^*,tan{\delta})$를 이용하여 입계의 주파수-온도에 대한 특성을 살펴 보았다. 일반적인 ZnO 바리스터 제조법으로 시편을 제작하여 78K~800K 온도 범위에서 각종 유전함수를 이용하여 복소 평면도(complex plane plot)와 주파수 응답도(frequency explicit plot)의 방법으로 defect level과 입계 특성(활성화 에너지, 정전용량, 저항, 입계 안정성 등)에 대하여 고찰하였다. ZnO-$Bi_2O_3$(ZB)계와 ZnO-$Bi_2O_3-Mn_3O_4$(ZBM)계 모두 상온 이하의 온도에서 $Zn_i$와 $V_o$의 결함이 나타났으며, 이들의 결함 준위는 각 유전함수에 따라 다소 차이가 났다. 입계 특성으로 ZB계는 이상구간(560~660K)을 전후로 1.15 eV $\rightarrow$ 1.49 eV의 활성화 에너지의 변화가 나타났지만, ZBM계는 이러한 현상이 나타나지 않았다. 또한 입계 전위 장벽의 온도 안정성에 대해서는 Cole-Cole model을 적용하여 분포 파라미터 (distribution parameter; $\alpha$)를 구하여 고찰하였다. ZB계의 입계 안정성은 온도에 따라 불안정해 졌지만, ZBM계는 안정하였다.

• 한국전기전자재료학회논문지
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• 제25권11호
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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 Chemical Engineering
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• 제35권12호
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• pp.2442-2451
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• 2018

Novel highly active visible-light photocatalysts in the form of zinc bismuth oxide ($ZnBi_2O_4$) and graphite hybrid composites were prepared by coupling via a co-precipitation method followed by calcination at $450^{\circ}C$. The asprepared $ZnBi_2O_4$-graphite hybrid composites were tested for the degradation of rhodamine B (RhB) solutions under visible-light irradiation. The existence of strong electronic coupling between the two components within the $ZnBi_2O_4$-graphite heterostructure suppressed the photogenerated recombination of electrons and holes to a remarkable extent. The prepared composite exhibited excellent photocatalytic activity, leading to more than 93% of RhB degradation at an initial concentration of $50mg{\cdot}L^{-1}$ with 1.0 g catalyst per liter in 150 min. The excellent visible-light photocatalytic mineralization of $ZnBi_2O_4-1.0graphite$ in comparison with pristine $ZnBi_2O_4$ could be attributed to synergetic effects, charge transfer between $ZnBi_2O_4$ and graphite, and the separation efficiency of the photogenerated electrons and holes. The photo-induced $h^+$ and the superoxide anion were the major active species responsible for the photodegradation process. The results demonstrate the feasibility of $ZnBi_2O_4-1.0graphite$ as a potential heterogeneous photocatalyst for environmental remediation.