• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.32 no.4
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• pp.276-280
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• 2019

In this study, we investigated the crystal defects and grain boundary properties in a ZZCCC ($ZnO-Zn_2BiVO_6-Co_3O_4-Cr_2O_3-CaCO_3$) varistor, with the liquid-phase sintering aid $Zn_2BiVO_6$ developed by our laboratory. The ZZCCC varistor sintered at $1,200^{\circ}C$ exhibited excellent nonlinear current-voltage characteristics (${\alpha}=63$), with oxygen vacancy ($V_o^*$ ; 0.35 eV) as a main defect, and an apparent activation energy of 1.1 eV with an electrically single grain boundary. Therefore, among the various additives to improve the electrical properties of ZnO varistors, if $Zn_2BiVO_6$ is used as a liquid phase sintering aid, it will be ideal to use Co for the oxygen vacancy and Ca for the electrically single grain boundary. This will allow the good properties of ZnO varistors to be maintained up to high sintering temperatures.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.30 no.2
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• pp.74-80
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• 2017

This study focuses on the effects of doping $Zn_2BiVO_6$ and $Co_3O_4$ on the sintering and electrical properties of ZnO; where, ZZ consists of 0.5 mol% $Zn_2BiVO_6$ in ZnO, and ZZCo consists of 1/3 mol% $Co_3O_4$ in ZZ. As ZnO was sintered at about $800^{\circ}C$, the liquid phases, which are composed of $Zn_2BiVO_6$ and $Zn_2BiVO_6$-rich phases, were found to be segregated at the grain boundaries of sintered ZZ and ZZCo, respectively, which demonstrates that $V_o^{\cdot}$(0.33~0.36 eV) are formed as dominant defects according to the analysis of admittance spectroscopy. As $Co_3O_4$ is doped to ZZ, the resistivity of ZnO decreases to ~38%, while donor density ($N_d$), interface state density ($N_t$), and barrier height (${\Phi}_b$) increase twice higher than those of ZZ, according to C-V characteristics. This result harbingers that ZZCo and its derivative compositions will open the gate for ZnO to be applied as more progressive varistors in the future, as well as the advantageous opportunity of manufacturing ZnO chip varistors at lower sintering temperatures below $900^{\circ}C$.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.31 no.5
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• pp.313-319
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• 2018

This study introduces a new investigation report on the microstructural and electrical property changes of $ZnO-Zn_2BiVO_6-Mn_3O_4$ (ZZMn), where 0.33 mol% of $Mn_3O_4$ and 0.5 mol% of $Zn_2BiVO_6$ were added to ZnO (99.17 mol%) as liquid phase sintering aids. $Zn_2BiVO_6$ contributes to the decrease of sintering temperatures by up to $800^{\circ}C$, and segregates its particles at the grain boundary, while $Mn_3O_4$ enhances ${\alpha}$, the nonlinear coefficient, of varistor properties up to ${\alpha}=62$. In comparison, when the sintering temperature is increased from $800^{\circ}C$ to $1,000^{\circ}C$, the resistivity of ZnO grains decreases from $0.34{\Omega}cm$ to $0.16{\Omega}cm$, and the varistor property degrades. Oxygen vacancy ($V_o^{\bullet}$) (P1, 0.33~0.36 eV) is formed as a dominant defect. Two different kinds of grain boundary activation energies of P2 (0.51~0.70 eV) and P3 (0.70~0.93 eV) are formed according to different sintering temperatures, which are tentatively attributed to be $ZnO/Zn_2BiVO_6$-rich interface and ZnO/ZnO interface, respectively. Accordingly, this study introduces a progressive method of manufacturing ZnO chip varistors by way of sintering ZZMn-based varistor under $900^{\circ}C$. However, to procure a higher reliability, an in-depth study on the multi-component varistors with double-layer grain boundaries should be executed.

• Journal of Sensor Science and Technology
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• v.25 no.6
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• pp.440-446
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• 2016

This study introduces the characteristics of current-voltage (I-V) and impedance variance for $ZnO-Zn_2BiVO_6-Co_3O_4$ (ZZCo), which is sintered at $900^{\circ}C$, according to temperature changes. ZZCo varistor demonstrates dramatic improvement of non-linear coefficient, ${\alpha}=66$, with lower leakage current and higher insulating resistivity than those of ZZ ($ZnO-Zn_2BiVO_6$) from the aspect of I-V curves. While both systems are thermally stable up to $125^{\circ}C$, ZZCo represents a higher grain boundary activation energy with 1.05 eV and 0.94 eV of J-E-T and from IS & MS, respectively, than that of ZZ with 0.73 eV and 0.82 eV of J-E-T and from IS & MS, respectively, in the region above $180^{\circ}C$. It could be attributed to the formation of $V^*_o$(0.41~0.47 eV) as dominant defect in two systems, as well as the defect-induced capacitance increase from 781 pF to 1 nF in accordance with increasing temperature. On the other hand, both the grain boundary capacitances of ZZ and ZZCo are shown to decrease to 357 pF and 349 pF, respectively, while the resistances systems decreased exponentially, in accordance with increasing temperature. So, this paper suggests that the application of newly formed liquid phases as sintering additives in both $Zn_2BiVO_6$ and the ZZCo-based varistors would be helpful in developing commercialized devices such as chips, disk-type ZnO varistors in the future.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.11a
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• pp.321-324
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• 2003

The effects of various sintering additives such as $Bi_2O_3+V_2O_5$, $BiVO_4$, $B_2O_3$, and $CuO+V_2O_5$ on the low-temperature sintering and microwave dielectric properties of $(ZnMg)TiO_3$ system were studied. Sintering was enhanced by the sintering additives and highly dense samples were obtained for $(Zn_{0.8}Mg_{0.2})TiO_3$ at the sintering temperature of $910^{\circ}C$. $(Zn_{0.8}Mg_{0.2})TiO_3$ with 6.19 mol.%$B_2O_3$ was found to show the best sintering and microwave dielectric properties.

• Transactions on Electrical and Electronic Materials
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• v.14 no.4
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• pp.193-198
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• 2013

The effects of additives (Cr, Nb, Dy, and Bi) on microstructure, electrical properties, dielectric characteristics, and aging behavior of $ZnO-V_2O_5-MnO_2-Co_3O_4-La_2O_3$ (ZVMCL) ceramics were systematically investigated. The phase formed in common for all ZVMCL ceramics modified with various additives consisted of ZnO grain as a main phase, and $Zn_3(VO_4)_2$ and $ZnV_2O_4$ as the secondary phases. The sintered density and average grain size were in the range of $5.4-5.54g/cm^3$ and $3.7-5.1{\mu}m$, respectively. The ZVMCL ceramics modified with Cr exhibited the highest breakdown field (6,386 V/cm) and the ZVMCL ceramics modified with Nb exhibited the lowest breakdown field (3,517 V/cm). All additives enhanced the nonlinear coefficient (${\alpha}$), by a small or large margin, in particular, additives such as Bi and Nb noticeably increased the nonlinear coefficient, with ${\alpha}=25.5$ and ${\alpha}=23$, respectively. However, on the whole, all additives did not improve the stability against a DC stress, compared with ZVMCL ceramics.