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.     

Influence of the preparation process on the electrical properties of high-field co-doped zinc oxide varistors

High-field ZnO/Bi₂O₃ varistors co-doped with Mn and Co were synthesized using a two-step co-precipitating process. A Zn²⁺ solution containing the Mn and Co doping elements was first precipitated into hydroxides, further converted into oxalates and finally calcined to create the doped ZnO phase. Bi³⁺ precipitated at the grain boundaries thanks to an HNO₃ treatment of the ZnO grains. The influence of the precursor type (nitrates or chlorides) and the calcination temperature on the properties of the powders and ceramics were investigated. ICP-AES, microstructural analysis and non-linear voltage measurements were used to characterize the samples. The type of precursor solution was found to have a strong influence on the electrical properties. Furthermore, the calcination temperature modified the microstructure of the powder and consequently also that of the varistor.     

Electrical properties and AC degradation characteristics of low voltage ZnO varistors doped with Nd2O3

The electrical properties and degradation characteristics of low voltage ZnO varistors were investigated as a function of Nd₂O₃ content. The varistor ceramics with 0.03 mol% Nd₂O₃ sintered at 1250 °C were far more densified than those with 0.06, 0.09 and 0.12 mol% Nd₂O₃. The addition of Nd₂O₃ to the low voltage ZnO varistors greatly improved the current–voltage characteristics; the nonlinear coefficient of varistors increase from 12.2 to 34.6 with increasing Nd₂O₃ content. The samples with 0.03 mol% Nd₂O₃ showed excellent stability due to high density and relatively good V–I characteristics, with the nonlinear coefficient of 22.5 and the leakage current of 9.6 μA. Their variation rate of varistor voltage and nonlinear coefficient and leakage current were −4.7%, −5.4%, 18.3%, respectively, under AC degradation stress (1.0 V_1 mA/125 °C/24 h).     

Microstructural, crystal structure and electrical characteristics of shock-consolidated Ga2O3 doped ZnO bulk

Ga₂O₃ (5 wt.%) doped zinc oxide (ZnO, 95 wt.%) bulk was fabricated by underwater shock compaction technique. The microstructural, crystal structure and electrical properties of shock-consolidated samples were investigated and compared to a commercially available sintered Ga₂O₃ (5 wt.%) doped ZnO (95 wt.%). The relative density of shock-consolidated sample was about 97% of the theoretical density, and no grain growth and lattice defects were confirmed. The grain boundary resistance was remarkably higher than that of commercial sintered Ga₂O₃ doped ZnO and nonlinear current-voltage (I-V) characteristics of shock-consolidated ZnO and Ga₂O₃ doped ZnO were very lower than that of commercial ZnO varistor.     

Co-doping effects of (Al,Ti, Mg) on the microstructure and electrical behavior of ZnO-based ceramics

Co-doped ZnO-based ceramics using Al, Ti, and Mg ions in different ratios were synthesized with the objective to investigate the doping effects on the crystalline features, microstructure and the electrical behavior. For Al and Ti doping, a coexistence of crystalline phases was shown with a major wurtzite ZnO structure and secondary spinel phases (ZnAl₂O₄, Zn₂TiO₄, or Zn_aTi_bAl_cO_d), while Mg doping did not alter significantly the structural features of the wurtzite ZnO phase. The electrical behavior induced by Al, Ti, and Mg co-doping in different ratios was investigated using Raman, electron paramagnetic resonance (EPR) and ²⁷Al and ⁶⁷Zn solid-state nuclear magnetic resonance (NMR). Al doping induces a high electrical conductivity compared to other doping elements. In particular, shallow donors from Zn_i-Al_Zn defect structures are inferred from the characteristic NMR signal at about 185 ppm; that is, quite far from the usual oxygen coordinated Al. The Knight shift effect emanating from a highly conducting Al-doped ZnO ceramics was considered as the origin of this observation. Oppositely, as Ti doping leads to the formation of secondary spinel phases, EPR analysis shows a high concentration of Ti³⁺ ions which limit the electrical conductivity. The correlation between the structural features at the local order, the involved defects and the electrical behavior as function of the doping process are discussed.     

Effects of Sb2O3 on the microstructure and electrical properties of ZnO–Bi2O3-based varistor ceramics fabricated by two-step solid-state reaction route

In this work, the ZnO–Bi₂O₃–Cr₂O₃–Co₂O₃–MnO₂ varistors doped with different content of Sb₂O₃ were prepared by two-step solid-state reaction route, including a pre-calcining of the mixtures of nanosized ZnO and the other additives at an optimized temperature, followed by a consequent sintering process at different temperatures. Meanwhile, the effects of Sb₂O₃ on the sintering temperature, microstructure and electrical properties of the objective varistors were investigated. It was found the densification temperature went up in a proper range and the content of pyrochlore phase, spinel phase and β-Bi₂O₃ phase increased with the increasing content of Sb₂O₃, while the grain size of ZnO–Bi₂O₃-based varistor reduced. The results demonstrated that at the same sintering temperature, the second particles increased with the increasing amount of Sb₂O₃, which was helpful to control the grain growth, leading to a higher breakdown voltage. However, the decrease of α-Bi₂O₃ phase (melting point of α-Bi₂O₃ phase is 825 °C), which is the main component of the liquid Bi₂O₃ phase in the sample during sintering process, leads to the increase of the sintering temperature of the green pallet. As a result, the ZnO varistor doped with 3.0 mol% Sb₂O₃ sintered at 1000 °C exhibited the highest breakdown voltage of 1863.3 V/mm. By contrast, the ZnO varistor without Sb₂O₃ doping sintered at 900 °C had the optimum nonlinear coefficient of 59.8.     

Effect of Ta2O5 in (Ca,Si, Ta)-doped TiO2 ceramic varistors

TiO₂ varistors doped with 0.2 mol% Ca, 0.4 mol% Si and different concentrations of Ta were obtained by ceramic sintering processing at 1350 °C. The effect of Ta on the microstructures, nonlinear electrical behavior and dielectric properties of the (Ca, Si, Ta)-doped TiO₂ ceramics were investigated. The ceramics have nonlinear coefficients of α = 3.0–5.0 and ultrahigh relative dielectric constants which is up to 10⁴. Experimental evidence shows that small quantities of Ta₂O₅ improve the nonlinear properties of the samples significantly. It was found that an optimal doping composition of 0.8 mol% Ta₂O₅ leads to a low breakdown voltage of 14.7 V/mm, a high nonlinear constant of 4.8 and an ultrahigh electrical permittivity of 5.0 × 10⁴ and tg δ = 0.66 (measured at 1 kHz), which is consistent with the highest and narrowest grain boundary barriers of the ceramics. In view of these electrical characteristics, the TiO₂–0.8 mol% Ta₂O₅ ceramic is a viable candidate for capacitor–varistor functional devices. The characteristics of the ceramics can be explained by the effect and the maximum of the substitution of Ta⁵⁺ for Ti⁴⁺.     

Er2O3 Doping Effect on Varistor Properties and Multiimpulse Stress Behavior of ZnO–PrO1.83–CoO–Cr2O3–Dy2O3 Ceramics

The Er₂O₃ doping effects on varistor properties and impulse aging behavior of the ZnO–PrO_1.83–CoO–Cr₂O₃–Dy₂O₃ ceramics were investigated in the range of 0–2.0 mol%. The nonlinear coefficient increased from 42 to 56 with an increase in the amount of Er₂O₃. The clamp voltage ratio (K) decreased with an increase in the amount of Er₂O₃. The varistors doped with 2.0 mol% in the amount of Er₂O₃ exhibited the best clamping characteristics, with K = 1.43–1.83 at an impulse current of 1–50 A. The varistors doped with 0.25 mol% in the amount of Er₂O₃ exhibited the strongest electrical stability, with the variation rate of the breakdown field of ?0.5%, the variation rate of the nonlinear coefficient of ?5.5%, and the variation rate of the leakage current of ?1.5% after applying 400 times at an impulse current of 400 A     

Electrical properties of Pr6O11-doped WO3 capacitor–varistor ceramics

The microstructure and electrical properties of Pr₆O₁₁-doped WO₃ ceramics were investigated. Results showed that the breakdown voltage of doped samples was lower than that of the undoped. The dielectric constant of doped samples was higher than that of the undoped, and the high dielectric constant made Pr₆O₁₁-doped WO₃ ceramics to be applicable as a kind of capacitor–varistor materials. A small content of Pr₆O₁₁ could significantly improve nonlinear properties of the samples. The WO₃–0.03 mol% Pr₆O₁₁ obtained a large nonlinear coefficient of 3.8, a low breakdown voltage of 8.8 V/mm, and a high dielectric constant of 7.69 × 10⁴ at 1 kHz. The defects theory was introduced to explain the nonlinear electrical behavior of Pr₆O₁₁-doped WO₃ ceramics.     

Effect of donor dopants cerium and tungsten on the dielectric and electrical properties of high Curie point ferroelectric strontium niobate

The perovskite-like layered structure (PLS) A₂B₂O₇ compound Sr₂Nb₂O₇ was doped with donor dopants CeO₂ and WO₃ to explore their doping effect on its A and B site, respectively. The doped ceramics were prepared by Spark Plasma Sintering. For Ce doping on the A site, single phase was maintained up to 5 mol% Ce (x=0.05 in (Sr_1−xCe_x)₂Nb₂O₇). For W doping on the B site, single phase was maintained at 2.5 mol% W (x=0.025 in Sr₂(W_xNb_1−x)₂O₇). The cerium and tungsten doping both inhibited grain growth and changed the grain morphology, leading to less anisotropic grains. The Curie point T_c was obtained by measuring the temperature dependence of the dielectric constant and it was found to reduce for both Ce and W doped SNO. The W doped ceramics showed a diffuse ferroelectric phase transition at the Curie point. The DC resistivity of tungsten and cerium doped SNO increased compared to undoped SNO at temperatures below 700 °C. These results showed that both Ce and W had a strong influence on the dielectric and electrical properties of the Sr₂Nb₂O₇ ceramics.     

Effects of the nature of the doping salt and of the thermal pre-treatment and sintering temperature on Spark Plasma Sintering of transparent alumina

A slurry of α-Al₂O₃ was doped with Mg, Zr and La nitrates or chlorides, in various amounts in the range 150-500 wt ppm and then freeze-dried to produce nanosized doped powder (∼150 nm). The powder was sintered by SPS to yield transparent polycrystalline alpha alumina. The influence of the nature of the doping element and the starting salt, the thermal treatment before sintering and the sintering temperature on the transparency of the ceramics were investigated. The transparency of the ceramics of nanosized Al₂O₃ was shown to depend mainly on the way the powder was prepared, the nature of the doping salt also had an effect. Finally, a high real inline transmittance, reaching 48.1% was achieved after optimization.     

Microstructure and electrical properties of rare earth doped ZnO-based varistor ceramics

ZnO-based varistor ceramics doped with Nd₂O₃ and Y₂O₃ have been prepared by the conventional ceramics method. The phase composition, microstructure and electrical properties of the ceramics have been investigated by XRD, SEM and a V–I source/measure unit. The XRD and EDS analyses show the presence of ZnO, Bi₂O₃, Zn₇Sb₂O₁₂, Y₂O₃, Nd-rich phase and Y-containing Bi-rich phase. The electrical properties analyzed show that the nonlinear coefficient of the varistor ceramics is in the range of 4.4–70.2, the threshold voltage is in the range of 247.1–1288.8 V/mm, and the leakage current is in the range of 1.51–214.6 μA/cm². The 0.25 mol% Nd₂O₃ added varistor ceramics with 0.10 mol%Y₂O₃ sintered at 1050 °C exhibits excellent electrical properties with the high threshold voltage of 556.4 V/mm, the nonlinear coefficient of 61 and the leakage current of 1.55 μA/cm². The results illustrate that doping Nd₂O₃ and Y₂O₃ in ZnO-based varistor ceramics may be a very promising route for the production of the higher threshold voltage and the nonlinear coefficient of ZnO-based varistor ceramics.     

Influence of Bi2O3/TiO2, Sb2O3 and Cr2O3 doping on low-voltage varistor ceramics

The influence of the amount of Bi₂O₃ and TiO₂ additions at a TiO₂/Bi₂O₃ ratio of 1, as well as Sb₂O₃ and/or Cr₂O₃ doping, on the microstructural development and electrical properties of varistor ceramics in the ZnO–Bi₂O₃–TiO₂–Co₃O₄–Mn₂O₃ system was investigated. In samples with a low level of Bi₂O₃ and TiO₂ (0·3 mol%) and therefore small amount of liquid phase, exaggerated growth of the ZnO grains results in high microstructural inhomogeneity. Co-doping with Sb₂O₃ significantly changes the phase composition of TiO₂ doped low-voltage varistor ceramics. The Bi₃Zn₂Sb₃O₁₁ type pyrochlore phase forms at the expense of the γ-Bi₂O₃ and Bi₄Ti₃O₁₂ phases and decreases the amount of liquid phase in the early stages of sintering. Already small amounts of Sb₂O₃ and/or Cr₂O₃ added to a TiO₂ doped low-voltage varistor ceramics limit ZnO grain growth and increase the threshold voltage V_T of the samples.     

Densification and grain growth of CuO-doped Pr6O11 varistors

The effect of CuO doping on the microstructure and electrical properties of Pr₆O₁₁ varistors was investigated. Samples were prepared by conventional ceramic techniques, and were sintered at 1150 °C in air for 2 h. The microstructure was investigated by scanning electron microscopy (SEM). The phases and chemical composition were analyzed by X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). The results indicated that CuO can promote the densification of the Pr₆O₁₁-based varistors to 95.8% of the theoretical density. CuO forms a solid solution with Pr₆O₁₁ up to 0.5 mol%, above which Pr₂CuO₄ precipitates in the grain boundary. From the I–V measurements, minor CuO doping can improve the nonlinear electrical properties. A further increase in CuO content induces a reduction in the nonlinear electrical properties due to the consumption of absorbed oxygen on the grain surfaces.     

Effect of In, Ce and Bi dopings on sintering and dielectric properties of Ba(Zn1/3Nb2/3)O3 ceramics

In, Ce and Bi doped Ba(Zn_1/3Nb_2/3)O₃ (BZN) ceramics were prepared by conventional mixed oxide technique. In doping between 0.2 and 4.0 mol% increased the density of BZN at 1300 °C, Ce doping caused a decrease in density at 1250 °C. Levels of Bi₂O₃ up to 1.0 mol% had negative effect on densification, while high level doping could significantly improve the densification of the specimens. XRD of the samples indicated that In, Ce and Bi doping resulted in single phase formation at all concentrations, except 0.5 mol% Bi. SEM of Bi doped BZN indicated only single phase structure and Ce doping even at 0.2 mol% gave some secondary phases. In and Ce doping increased the dielectric constant from 41 to around 66 at 1 MHz. Bi doping decreased the dielectric constant to about 37 at 0.2 mol%, and then higher doping led to dielectric constant to increase to about 63.     

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.     

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.     

Electrical characterization of ZnO multilayer varistors on the nanometre scale with conductive atomic force microscopy

The conductivity of ZnO–varistor ceramics has been analyzed with conductive atomic force microscopy (C-AFM) under atmospheric conditions by measuring the current at different voltages and positions in zinc oxide-based multilayer varistors (MLVs). It is possible to detect individual ZnO grains on the polished sample surface in the AFM topography mode as well as in the two-dimensional current images. Additionally local current–voltage (IV) curves revealed details of the electrical behaviour of the material. To correlate the laterally resolved current image with grain orientations, electron backscattering diffraction (EBSD) has been performed. Beside the well-known varistor behaviour specific influence of the local microstructure has been found.     

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.     

Shock-sintering of low-voltage ZnO-based varistor ceramics with Bi4Ti3O12 additions

Microstructure development in ZnO ceramics with Bi₄Ti₃O₁₂ (BIT) additions was studied in dependence of sintering temperature, inversion boundary (IBs) nucleation, heating rate and doping with transition metal oxides (NiO, MnO₂ and Co₃O₄). We demonstrated that one of the essential conditions for homogeneous microstructure development in this system is rapid release and efficient distribution of TiO₂, necessary for the formation of Ti-rich (tail-to-tail) IBs in ZnO grains. This can be achieved via the so-called shock-sintering procedure described in this article. Immediate decomposition of BIT to TiO₂-rich Bi₂O₃ liquid phase above 1200 °C leads to nucleation of ZnO grains with IBs. Exploiting the growth of ZnO grains with IBs, microstructure development can be easily controlled via the IB-induced grain growth mechanism, previously described in SnO₂-doped and Sb₂O₃-doped ZnO. In contrast to conventional sintering, where erratic nucleation of IBs leads to bimodal grain size distribution, shock-sintering sintering regime produces microstructures with uniform coarse-grain sizes, required for low-voltage varistor ceramics.