Electrical properties of new tin dioxide varistor ceramics at high currents

New dense SnO₂-based varistor ceramics with high nonlinear current–voltage characteristics (nonlinearity coefficients are of approximately 50) in a system of SnO₂–CoO–Nb₂O₅–Cr₂O₃–Y₂O₃–SrO–MgO are reported. The current–voltage behaviour at high currents is studied by using exponential voltage pulses. The obtained SnO₂ varistor ceramics exhibit low grain resistivity values of 0.23–0.64 ohm cm. To date, such values are the lowest known for SnO₂ varistors, and are closely approaching the grain resistivity of the ZnO varistor. The current–voltage characteristics of the obtained SnO₂-based varistor materials are reproducible in a wide current range from 10^?11 to approximately 10⁴ A cm^?2. The minimum current density and the minimum electric field necessary to cause the irreversible electrical breakdown are measured. It is established that a decrease in the grain resistivity leads to an increase in the minimum current density necessary for irreversible electrical breakdown to occur.     

水基流延片式ZnO压敏电阻器低温共烧工艺及其性能

用环境扫描电子显微镜（ESEM）、X射线衍射（XRD）和X射线能谱（EDXS）等研究了水基流延片式ZnO压敏电阻器的低温共烧工艺及其对微观结构和电学性能的影响规律。ESEM分析结果表明：当等静压压力为60 MPa时,Ag电极与流延膜生坯界面结合紧密,Ag电极分布连续,900℃共烧时,未出现开裂、分层,两者收缩率接近。EDXS和XRD分析结果表明：900℃共烧时,Ag在片式压敏电阻器中以单质形式存在,流延膜与Ag电极化学兼容性良好,且在共烧界面处未发现有明显的Ag离子扩散。该流延膜可以与Ag电极在900℃时实现低温共烧,用此制备的片式ZnO压敏电阻器具有良好的压敏性能：压敏电压V1mA=6.1 V,非线性系数α=28.1,漏电流IL=0.15μA。     

Electrical Nonuniformity of Grain Boundaries within ZnO Varistors

ZnO varistors with and without ZnO crystalline seeds have been prepared through conventional ceramic processing. Their electrical nonuniformity has been carefully examined using microcontact measurements of single grain boundaries, current-voltage ( I-V ) characteristics, and dielectric temperature spectra of bulk samples. Three types of grain boundaries with barrier heights of 0.2, 0.5, and 0.6 eV are identified in a ZnO varistor with the seeds, while only one with 0.4 eV barrier height has been found in a varistor without the seeds. Using a computerized electric circuit simulation, the influence of boundary thickness and grain size on I-V characteristics of varistor is investigated extensively. The simulated results show that currents passing across various grain boundaries are quite different. For a model varistor (1 × 1 × 1 mm³) with different grain size, a good agreement between measured data and simulated curves can be achieved.     

Design and fabrication of flexible poly(vinyl chloride) dielectric composite reinforced with ZnO microvaristors

Flexible poly(vinyl chloride)/varistor composites were fabricated by solution casting method. High‐field ZnO varistor particles processed from micron‐sized Zn dust is explored as multifunctional filler for PVC composites. Mechanical blending of Zn dust with La₂O₃‐CeO₂ rare earths and varistor forming minor additives followed by sintering at 1250 °C resulted in fine‐grained ZnO varistors. Bulk varistor was subsequently milled to obtain ZnO microvaristor grains. The effect of microvaristor on the UV stability, dielectric, and mechanical properties of the PVC composite was analyzed. The varistor filler in PVC enhanced the microhardness and retained the tensile properties without any significant loss. After UV irradiation PVC/varistor composite shows remarkable mechanical stability retention (95%) compared to pure PVC (75%). Also, microvaristor reinforcement resulted in dielectric constant tunability (? = 2–37) without any drastic change in the dielectric loss (0.02–0.05). Thus, Zn dust‐derived ZnO varistors could be potentially exploited to design functional PVC composites for electronic applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46031.     

Conducting polymer based hybrid nano-composites for enhanced corrosion protective coatings

Hybrid composite coatings containing zinc oxide (ZnO) and polyaniline (PANI) as nano-additives dispersions were prepared with poly(vinyl acetate) (PVAc) as the major matrix. The steel plates dip-coated with these formulations were tested for corrosion protection by immersion in saline water over long periods. The Tafel plots for the determination of open circuit potential (OCP) and corrosion current (I_corr) were recorded. The coatings containing both ZnO and PANI showed improved corrosion resistance as compared to the single component coating. The I_corr values of PVAc–ZnO–PANI are found to be two-order magnitude lower than that of PVAc and PVAc–ZnO coatings. The results are explained on the basis of enhancement in barrier properties due to nano-particulate additives in PVAc–ZnO–PANI film together with the redox behaviour of PANI and protective oxide layer formation near the substrate.     

Combustion synthesis of doped nanocrystalline ZnO powders for varistors applications

Doped nanocrystalline ZnO powders in the size range between 15 and 250 nm were synthesized by chemical combustion method. The powders were characterized for their physical, structural and chemical properties by BET, X-ray diffraction, FESEM, TEM and XPS. These powders were consolidated into dense varistors discs by compaction, sintering and evaluated for their I-V characteristics. Post-calcinations of these powders were found to have great influence on the green density and sinterability. The formations of phases after sintering were confirmed by XRD analysis and EDX. The varistor properties have been studied for different calcination temperatures and compositions. Breakdown voltage as high as 9.5 kV/cm and coefficient of nonlinearity 134 were obtained. Leakage current density was found to be ∼1.29 μA/cm² for a specific composition and condition. These studies demonstrate the feasibility of one step synthesis of doped ZnO nanopowder and their consolidation into ZnO fine grain varistor exhibiting improved performance.     

Simultaneously improving the electrical properties and long-term stability of ZnO varistor ceramics by reversely manipulating intrinsic point defects

Excellent electrical properties and the improved long-term stability of ZnO varistor ceramics were simultaneously achieved by doping NiO. The microstructural features were investigated using X-ray diffractometer, scanning electron microscopy, and energy dispersive spectroscopy, while the intrinsic point defects were characterized using frequency domain dielectric spectroscopy and verified by photoluminescence and Raman spectra. The results indicated that in the ZnO varistor ceramics, a reverse manipulation of donor point defects, i.e., suppressing mobile zinc interstitial but increasing stable oxygen vacancy, was achieved. The long-term stability of NiO-doped ZnO ceramics was improved via a decrease in zinc interstitial density, with a degradation rate of 0.064 μA cm^?2 h^?0.5. Meanwhile, due to an increase in oxygen vacancy density, the excellent nonlinear current–voltage performance, i.e., a high nonlinear coefficient (72.9), low leakage current density (0.08 μA cm^?2), and low grain resistivity (13.43 × 10^?3 Ω m), was maintained. The findings of this study provide a possible method for developing high-performance ZnO varistor ceramics by manipulating point defects.     

ZnO掺杂量与烧结温度对SnO2–Ta2O5–ZnO压敏变阻材料性能的影响

以SnO2、Ta2O5和ZnO粉为原料,通过传统陶瓷固相反应烧结法制备了压敏变阻材料,实验中ZnO含量为0～2.00%(摩尔分数),烧结温度控制在1 300～1500℃并保温2 h。研究了ZnO掺杂量和烧结温度对材料的组成、微观结构和电学性能的影响。结果表明:在温度一定条件下,随着ZnO掺杂量的增加,材料的非线性系数、压敏电压先增大后减小;在ZnO含量一定时,随着烧结温度从1 300℃升至1 450℃,材料的非线性系数、压敏电压先增大后减小。ZnO掺杂量为0.50%时,在1450℃烧结得到的样品的非线性系数最高(6.2),漏电流最小(262μA/cm2),压敏电压较高(83V/mm)。     

High Nonlinearity and High Voltage Gradient ZnO Varistor Ceramics Tailored by Combining Ga2O3, Al2O3, and Y2O3 Dopants

This paper deals with the electrical characteristics of rare‐earth‐doped ZnO varistor ceramics. Multiple donor dopants (Al³⁺, Ga³⁺, and Y³⁺) were employed to improve the comprehensive performance of ZnO varistor ceramics. The leakage current of rare‐earth‐doped ZnO varistor ceramics decreased noticeably with Ga₂O₃ dopants. The Ga³⁺ dopant occupies the defect sites of grain boundaries and increases the barrier potential of ZnO varistor ceramics, so the leakage current is effectively inhibited. Y₂O₃ is primarily located around the grains, which restrains ZnO grain growth, increasing the voltage gradient. The Al³⁺ goes into the lattices of ZnO grains, decreasing the grain resistance; thus, the residual voltage ratio can be controlled at low levels under a high impulse current. With the combined incorporation of Al³⁺, Ga³⁺, and Y³, excellent electrical properties of ZnO varistor ceramics can be acquired with a nonlinearity coefficient of 87, voltage gradient of 517 V/mm, leakage current of 0.96 μA/cm², and residual voltage ratio of 1.60. These rare multiple donor dopants can aid in engineering high‐quality ZnO varistors.     

Investigation of schottky barriers at Pd-ZnO junctions in varistors

This is the first comprehensive study of the electrical behaviour, namely the I–V characteristics, of electrode-grain junctions in Pr-based ZnO varistor ceramics with Pd electrodes. These junctions have been investigated by a micro 4-point probe setup on the microstructural scale. A mean Schottky barrier height of 0.47 ± 0.03 eV was found. The reverse current through the junctions could be described by a model based on an interfacial layer. Furthermore, crystal orientations and polarities of grains with respect to the electrode layers were determined by electron back scatter diffraction and analysing etching patterns to check a possible influence on the barrier height. But within the set of experiments no correlation between grain orientation and barrier height could be found.     

A Novel Test Method for Ultrafast Pulse Response Characteristics of ZnO Varistor Ceramics

A ZnO varistors in series connected with a semi‐insulating GaAs photoconductive switches (SI‐GaAs PCSS's), a test method for ultrafast pulse response characteristics of ZnO varistor ceramics with DC bias was presented for the first time. The DC voltage distribution of the PCSS's and the varistors was measured in a dark state and the pulse response characteristics of the ZnO varistor ceramics was examined by a nanosecond laser pulse illuminating the PCSS's. The results indicate that the electric pulse output from the varistors includes capacitive current and conduction current and there is a time delay between their peaks. It is revealed that ZnO varistors has a nonlinear conductivity for the nanosecond electric impulse excitation and the barrier capacitance decay constant of the ceramics sample is 105 ns, which is explained through the analysis of examining the material structure and the conductive mechanisms.     

Microstructure–Property Relationships for Low-Voltage Varistors

The low-voltage varistors with various layer thickness are prepared by laminating thin ZnO-based ceramic layers and AgPd electrodes together. The breakdown voltage dose not exhibit linear relationship with layer thickness. It is due to that the presence of the AgPd electrodes enhances the growth of ZnO grains. As some ZnO grains are large enough to touch the upper and lower electrodes, the breakdown voltage of the varistor is only 3.7 V. The nonlinear coefficient of the low-voltage varistor is 33. Such nonlinear current–voltage behavior is mainly contributed by the interface between the AgPd electrode and ZnO grains.     

氧化锌压敏电阻的烧结行为

为了研究ZnO压敏电阻组成中非化学配比氧化物对ZnO压敏电阻导电性能的影响,采用在不同氧分压条件下烧结样品以研究其烧结行为。结果表明：ZnO晶粒的电导率对数与氧分压对数成线性关系;斜率为-1/4;间隙Zn原子以一价电离Zni形式存在。由于CoO,MnO和NiO阳离子空位氧化物多偏析于晶界,晶界处氧的增加有利于降低压敏电阻漏电流,烧结时间从2h延长到8h,漏电流从5μA/cm^2降到3.6μA/cm^2。波谱分析表明：掺杂氧化物在晶界处都有偏析,ZnO晶粒中掺杂原子混溶比例不完全与掺杂阳离子半径相关。     

High-current measurement of the grain resistivity in zinc oxide varistor ceramics

A new pulse technique for grain resistivity measurement in varistor ceramics is suggested. Such technique allows obtaining more precise value of the grain resistivity due to the use of the concept of differential electrical resistance. This technique can be used in the current density range where the overheating of varistor sample is insignificant. The technique was verified using commercial ZnO varistors. Grain resistivities of 0.60±0.02 Ω cm at 293 K and of 3.40±0.13 Ω cm at 77 K were obtained. This result indicates the negative temperature coefficient of grain resistance in ZnO varistor in the range (77–293) K. The contribution of the grain boundaries to the current–voltage characteristic of ZnO varistor is estimated on the basis of the measured grain resistivity and the current–voltage data. It is shown that the electrical conduction in ZnO varistor is controlled by grains if the current density exceeds approximately 1000 А сm⁻².     

Influence of sintering on microstructure and electrical properties of ZnO-based multilayer varistor (MLV)

The effect of sintering on microstructure, dielectric property and varistor property of ZnO-based multilayer varistor (MLV) were investigated. The results show that an optimum microstructure of ZnO-based MLV can be obtained when sintering at 950 °C/1.5 h. The reaction between ZnO and Sb₂O₃ is noted. Also, the segregation of Bi₂O₃ to the inner electrode and thus the reaction of Bi₂O₃ with Pd are observed. The V_B and α value of ZnO-based MLV can be controlled in a straightforward manner through the control of grain size. The decrease in V_B directly relates to the grain growth of ZnO grains when increasing the sintering temperatures from 900 to 1050 °C. Moreover, the increase of capacitance with sintering temperature may mainly result from the coalescence of ZnO matrix grains. The energy absorption capabilities in terms of electro-static discharge (ESD) and peak current (PC) measurements of ZnO-based MLV are reported. The optimum varistor properties of ZnO-based MLV can be obtained when sintering at 950 °C.     

Microstructure and electrical properties of ZnO–ZrO2–Bi2O3–M3O4 (MCo,Mn) varistors

Phase evolution, microstructure and the electrical properties of ZrO₂-added pyrochlore-free ZnO–Bi₂O₃–M₃O₄ (MCo, Mn) varistors have been studied as functions of ZrO₂ content up to 10 vol% and the sintering temperature between 900 and 1300 °C. Zirconia remained as intergranular second phase particles up to 1100 °C, which retarded densification and inhibited the grain growth of ZnO. At higher temperatures, on the contrary, ZrO₂ particles began to be entrapped in ZnO grains and irreversibly transform from monoclinic to stable cubic phase dissolving transition metal ions. The grain size of ZnO decreased with increasing ZrO₂ content, and increased with the increase of the sintering temperature. Accordingly breakdown voltage changed with both ZrO₂ content and the sintering temperature as was expected. Nonlinear coefficient (α) depended primarily on the sintering temperature: it increased to >40 up to 1000 °C, and significantly decreased to <30 at higher temperatures probably due to the volatilization of Bi₂O₃. While the specimens sintered at 1200 °C or above had relatively high leakage current (I_L) and large clamping ratio (C_R), those with ZrO₂ content of 0.5–5.0 vol% and sintered below 1200 °C revealed low I_L of ⩽20 μA/cm² and C_R well below 2.0. In spite that varistor characteristics of ZrO₂-added system could not match those of commercial ZnO varistors, its low temperature sinterability and ease of breakdown voltage control via ZrO₂ content without a serious loss of its figures of merit are worth noticing, particularly for multi-layered chip varistor (MLV) application.     

Improvement of surge current performances of ZnO varistor ceramics via C3N4-doping

ZnO-Bi₂O₃ based varistor ceramics doped with C₃N₄ were fabricated via solid state method. Experimental results show that C₃N₄ additive acts as an inhibitor in ZnO grain growth, and the average grain size decreases from 10.2–7.1 μm. The varistor breakdown voltage gradient increases from 222.3–282.3 V/mm, and the nonlinear coefficient increases from 51.9–58.2 with the increase of C₃N₄ content from 0 to 3.0 wt%. The C₃N₄-added samples exhibited smaller residual voltage ratio and better surge current withstanding capability. It is proposed that the C₃N₄-doping leads to substitution of nitrogen for oxygen in the grain boundary region, forming acceptor type defects. The acceptor type defects act as electron traps, increasing the barrier height from 1.31 to 1.50 eV and the depletion layer width from 54.9–61.8 nm, which increases the nonlinearity, and the surge current performances of the C₃N₄ doped ZnO varistor ceramics are improved.     

共沉淀法制备ZnO基纳米复合粉体及高压ZnO压敏电阻的电性能

以金属离子盐为原料,氨水、乙醇胺为沉淀剂,十二烷基苯磺酸钠、聚乙二醇2000为表面改性剂,采用共沉淀法制备ZnO基纳米复合粉体。以共沉淀法最佳工艺所得粉体制备高压ZnO压敏电阻。采用热重–差示扫描量热分析、X射线衍射、扫描电子显微镜、激光粒径分析对ZnO基复合前驱体及ZnO基纳米复合粉体进行表征,探讨了沉淀剂种类、溶液pH值、Zn2＋起始浓度和表面改性剂对粉体粒度的影响。结果表明：以氨水为沉淀剂、溶液体系pH值为6.0、Zn2＋浓度为1.0mol/L、聚乙二醇2000为表面改性剂时可制备出粒径分布窄、平均粒径为89nm的ZnO基复合粉体。用该粉体制备的高压ZnO压敏电阻的平均电位梯度为543V/mm,非线性系数为29.3,漏电流为49μA。通过共沉淀工艺,可制备出电性能优良的高压ZnO压敏电阻。     

Segregation and properties at curved vs straight (000) inversion boundaries in piezotronic ZnO bicrystals

TEM and SEM investigations of ZnO bicrystal interfaces were undertaken with an aim to study the correlation of local grain-boundary structure, segregation, and electrical transport perpendicular to the interface. To this end, varistor-like ZnO bicrystals with piezotronic characteristics were chosen with (000)║(000) tail-to-tail orientation with respect to the c-axis. In order to contrast different local grain-boundary structures with different coherency and segregation of bismuth, but identical macroscopic polarization state, two complementary processing techniques were applied. A diffusion-bonded bicrystal with an intermediate thin film containing Zn–Bi–Co–O provided a straight interface as reference. In contrast, a ZnO bicrystal prepared by epitaxial solid-state transformation was manufactured by bonding two ZnO single crystals with a 100 µm thick polycrystalline ZnO varistor material with a typical dopant composition including bismuth and cobalt. This structure was annealed to the point that a bicrystal was formed with the varistor concentration at the boundary, which was strongly curved due to the polycrystalline microstructure still providing a shadow image at the interface. The results highlight a distinct correlation between local interfacial morphology, degree of segregation of bismuth, and degree of nonlinearity of the electrical transport across the interface.     

Effect of Nb2O5 on ZnBiMnO varistor ceramic prepared by solid-state sintering at 850°C

Nb₂O₅ is a commonly used donor dopant for ZnO-based varistor ceramics, but its effect, especially on the low-temperature sintered ZnO varistor ceramics, is not fully understood. To provide a possible answer to this problem, ZnO–Bi₂O₃–MnCO₃ (ZnBiMnO) based varistor ceramics with 0.05%–0.3% (in mole ratio) Nb₂O₅ were fabricated by solid-state sintering at 850 °C for 3 h. Their microstructure and nonlinear electrical properties were studied by XRD, SEM and the standard current-voltage (I–V) tests to reveal the effect of Nb₂O₅. With the increase of Nb₂O₅ from 0.05 mol% to 0.3 mol%, more solid Bi₅Nb₃O₁₅ inter-granular particles form within the ceramic during sintering, thereby decreasing the Bi-rich liquid phase. As a result, the average size of ZnO grain decreases from 4.35 μm to 1.67 μm. This microstructural change leads to the increase of the breakdown voltage in the range of 821 V/mm to 1851 V/mm. The ZnBiMnO varistor ceramic with 0.1 mol% Nb₂O₅ shows the best nonlinear properties. The optimum nonlinear coefficient is 35.81, the breakdown voltage is 907.51 V/mm, and the leakage current is 7.72 μA/cm². The result of this study provides a promising candidate material for manufacturing the multilayered low-voltage varistor that may use Ag, Ni or even Cu as the inner electrodes.