Recently, as power and electronic devices have increased in frequency and capacity, it has become a major concern to protect electronic circuits and electronic components used in these devices from abnormal voltages such as various surges and pulse noise. To respond to variously rated voltages applied to power electronic devices, the rated voltages of various varistors can be obtained by controlling the size of internal particles of the varistor or controlling the number of layers of the varistor. During bonding, the problem of unbalanced thermal runaway occurring between the electrode and the varistor interface causes degradation of the varistor and shortens its life of the varistor. In this study, to solve the problem of unbalanced heat distribution of stacked varistors to adjust the operating voltage, the contents of the ZnO-based varistor composition were 96 wt% ZnO, 1 mol% Sb₂O₃, 1 mol% Bi₂O₃, 0.5 mol% CoO, 0.5 mol% MnO, and 1 mol% TiO₂. A multi-layered ZnO varistor was modeled by bonding a single varistor with a composition in three layers according to the operating voltage. The thermal distribution of the triple-layered ZnO varistor was analyzed for the thermal runaway phenomenon that occurred during varistor operation using the finite element method according to Comsol 5.2.

Since the ZnO varistor is a semiconductor device, the internal thermal distribution during the varistor operation is recognized as an important factor in the performance and deterioration of the varistor. For an optimal varistor structure design, the thermal runaway phenomenon during the varistor operation was interpreted using the Comsol 5.2 analysis program by a finite element analysis. The maximum temperature of the center measured in the cross section of the ZnO varistor was confirmed to increase as the temperature moved from the lower electrode to the center towards the upper electrode up to 572.6 K. The electrodes are thinned so that the influence of the Schottky barrier is not great. The heat gradient balance is determined to be improved when the electrode of the hybrid form is introduced. The thickness, density, pore distribution, impurity uniformity, and particle size of the ZnO varistor are required, and it is determined that the pyrolysis gradient will be improved regardless of the electrode thickness. When these results are applied to design the ZnO varistor, the optimal structure of the ZnO varistor can be obtained.

In this study, we investigated the crystal defects and grain boundary properties in a ZZCCC (ZnO-Zn₂BiVO₆-Co₃O₄-Cr₂O₃-CaCO₃) varistor, with the liquid-phase sintering aid Zn₂BiVO₆ developed by our laboratory. The ZZCCC varistor sintered at 1,200℃ exhibited excellent nonlinear current-voltage characteristics (α=63), with oxygen vacancy (V₀^·; 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 Zn₂BiVO₆ 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.

This work presents the response characteristics of a ZnO varistor to conductive EMP. An E1 pulse, standardized to MIL-STD-188-125-1, was applied to the varistors wherein the residual current and response times were measured with the applied E1 pulse current. Additionally, the response time was measured according to the length of the connection path. Consequently, the amplitude of the residual voltage through the ZnO varistors was increased with increasing amplitude of the applied E1 pulse current. As the length of the connection path increased, the operating response time and residual peak voltage also increased. These results indicate that the response characteristics of ZnO varistors can be applied to basic data to support the use of varistors as a protective measure against conductive EMP.

Liquid phases in ZnO varistors cause more complex phase development and microstructure, which makes the control of electrical properties and reliability more difficult. Therefore, we have investigated 2 mol% CaCO₃ doped ZnO-Co₃O₄-Cr₂O₃-La₂O₃ (ZCCLCa) bulk ceramics as one of the compositions without liquid phase sintering additive. The results were as follows: when CaCO₃ is added to ZCCLCa (644 Ωcm) acting as a simple ohmic resistor, CaO does not form a secondary phase with ZnO but is mostly distributed in the grain boundary and has excellent varistor characteristics (high nonlinear coefficient α＝78, low leakage current of 0.06 μA/㎠, and high insulation resistance of 1×10¹¹ Ωcm). The main defects Zn_i^·· (AS: 0.16 eV, IS & MS: 0.20 eV) and V˙_o (AS: 0.29 eV, IS & MS: 0.37 eV) were found, and the grain boundaries had 1.1 eV with electrically single grain boundary. The resistance of each defect and grain boundary decreases exponentially with increasing the measurement temperature. However, the capacitance (0.2 nF) of the grain boundary was ~1/10 lower than that of the two defects (~3.8 nF, ~2.2 nF) and showed a tendency to decrease as the measurement temperature increased. Therefore, ZCCLCa varistors have high sintering temperature of 1,200℃ due to lack of liquid phase additives, but excellent varistor characteristics are exhibited, which means ZCCLCa is a good candidate for realizing chip type or disc type commercial varistor products with excellent performance.

This study introduces a new investigation report on the microstructural and electrical property changes of ZnO-Zn₂BiVO₆-Mn₃O₄ (ZZMn), where 0.33 mol% of Mn₃O₄ and 0.5 mol% of Zn₂BiVO₆ were added to ZnO (99.17 mol%) as liquid phase sintering aids. Zn₂BiVO₆ contributes to the decrease of sintering temperatures by up to 800℃, and segregates its particles at the grain boundary, while Mn₃O₄ enhances α, the nonlinear coefficient, of varistor properties up to α＝62. In comparison, when the sintering temperature is increased from 800℃ to 1,000℃, the resistivity of ZnO grains decreases from 0.34 Ωcm to 0.16 Ωcm, and the varistor property degrades. Oxygen vacancy (V_o^·) (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/Zn₂BiVO₆-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℃. However, to procure a higher reliability, an in-depth study on the multi-component varistors with double-layer grain boundaries should be executed.

As a ZnO varistor is subjected to electrical and environmental stresses, it degrades gradually, which may result in power interruption by short circuit. This study investigates changes in the electrical characteristics of ZnO varistors due to deterioration owing to energy absorption, and determines the optimal parameters for on-line diagnosis of the varistor. Two types of varistors were used for an accelerated aging experiment involving the application of the 8/20 μs standard lightning impulse current. The electrical characteristics in terms of the reference voltage, total leakage current, resistive leakage current, and third-harmonic component of the total leakage current were measured, and their change rates were analyzed. The results revealed that the total leakage current increased slightly with an increase in the varistor absorbed energy, while the resistive leakage current and the third-harmonic component increased apparently. Therefore, the third-harmonic component of the total leakage current was proposed as the optimal parameter for on-line monitoring of ZnO varistor conditions.

In this study we aims to examine the effects of Co3O4 and NiO doping on the defects and electrical properties in ZnO-Bi2O3-Sb2O3 (Sb/Bi=0.5) varistors. It seemed to form □(0.20 eV) and □(0.33 eV) as dominant defects in Co and Ni co-doped ZBS system, however only □appeared in Co- or Ni-doped ZBS. Even though the same defects it was different in capacitance (1.5∼4.5 nF) and resistance (0.3∼9.5 kΩ). The varistor characteristics were improved with Co and Co+Ni doping (non-linear coefficient, α= 36 and 29, relatively) in ZBS. The various parameters (Nd= 1.43∼2.33×1017 cm-3, Nt=1.40∼ 2.28×1012 cm-2, Φb= 1.76∼2.37 V, W= 98∼118 nm) calculated from the C-V characteristics in our systems did not depend greatly on the type of dopant, which were in the range of a typical ZnO varistors. It should be derived a improved C-V equation carefully for more reliable parameters because the variation of the varistor capacitance as a function of the applied dc voltage is depend on the defect, frequency, and temperature.

In this study, we have investigated the effects of Mn and Co co-doping on defects, J-E curves and grain boundary characteristics of ZnO-Bi2O3 (ZB) varistor. Admittance spectra and dielectric functions show two bulk defects of Zn ·· (0.17∼0.18 eV) and V· (0.30∼0.33 eV). From J-E characteristics the nonlinear coefficient (α) and resistivity (ρgb) of pre-breakdown region decreased as 30 to 24 and 5.1 to 0.08 GΩcm with sintering temperature, respectively. The double Schottky barrier of grain boundaries in ZB(MCo) (ZnO-Bi2O3-Mn3O4-Co3O4) could be electrochemically single type. However, its thermal stability was slightly disturbed by ambient oxygen because the apparent activation energy of grain boundaries was changed from 0.64 eV at lower temperature to 1.06 eV at higher temperature. It was revealed that a co-doping of Mn and Co in ZB reduced the heterogeneity of the barrier in grain boundaries and stabilized the barrier against an ambient temperature (α-factor= 0.136).

In this study we aims to examine the co-doping effects of 1/3 mol% Mn3O4+Co3O4 (1:1) on the reaction, microstructure, and electrical properties such as the bulk defects and grain boundary properties of ZnO-Bi2O3-Sb2O3 (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 (Zn2Bi3Sb3O14) 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 (α- or β-polymorph) did not formed in Sb/Bi=0.5. More homogeneous microstructure was obtained in Sb/Bi≥1.0. In ZBS(MCo), the varistor characteristics were improved drastically (non-linear coefficient, α=30∼49), and seemed to form (0.17 eV) and (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/Bi2O3(Mn,Co)/ZnO (0.47 eV) and the other ZnO/ZnO (0.80∼0.89 eV) homojunctions.

In this study we aims to evaluate the effects of 1/3 mol% Co3O4 addition on the reaction, microstructure development, resultant electrical properties, and especially the bulk trap and grain boundary properties of ZnO-Bi2O3-Sb2O3 (Sb/Bi=2.0, 1.0, and 0.5) system (ZBS). The samples were prepared by conventional ceramic process, and characterized by XRD, density, SEM, I-V, impedance and modulus spectroscopy (IS & MS) measurement. In addition of Co3O4 in ZnO-Bi2O3-Sb2O3 (ZBSCo), the phase development, density, and microstructure were controlled by Sb/Bi ratio. Pyrochlore on cooling was reproduced in all systems. The more homogeneous microstructure was obtained in ZBSCo (Sb/Bi=1.0) system. In ZBSCo, the varistor characteristics were improved drastically (non-linear coefficient α=23∼50) compared to ZBS. Doping of Co3O4 to ZBS seemed to form V*o (0.33 eV) as dominant defect. From IS & MS, especially the grain boundary of Sb/Bi=0.5 system is composed of electrically single barrier (0.93 eV) and somewhat sensitive to ambient oxygen with temperature.

In this study we aims to examine the effects of 0.5 mol% Cr2O3 addition on the reaction, microstructure development, resultant electrical properties, and especially the bulk trap and interface state levels of ZnO-Bi2O3-Sb2O3 (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 (Zn2Bi3Sb3O14) was decomposed more than 100℃ 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℃ by unknown Bi-rich phase produced at 700℃. Pyrochlore on cooling was reproduced in all systems. And Zn7Sb2O12 spinel (α-polymorph) and δ-Bi(2)O(3) phase were formed by Cr doping. In ZBSCr, the varistor characteristics were not improved drastically (non-linear coefficient α=7~12) and independent on microstructure according to Sb/Bi ratio. Doping of Cr2O3 to ZBS seemed to form Zn(i) (0.16 eV) and Vo (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.