Electrical Behavior of Ceria-Stabilized Zirconia with Rare-Earth Oxide Additives

The electrical properties of rare-earth oxide doped CeO₂-ZrO₂ ceramics are evaluated by impedance spectroscopy. Doping of the trivalent metal oxide decreases both the grain and grain-boundary resistivities of the CeO₂-ZrO₂ system. The grain and grain-boundary resistivities as well as the activation energy for conduction increase with the dopant cation radius. The grain conductivity is fairly constant for 2 mol% YO_1.5-10 mol% CeO₂-88 mol% ZrO₂ samples sintered under different conditions, while lower grain-boundary resistivity is obtained for samples sintered at higher temperature for longer times. Possible mechanisms for the electrical behavior of the rare-earth oxide doped CeO₂-ZrO₂ ceramics are proposed and discussed.     

Influence of Ba/Ti Ratio on the Positive Temperature Coefficient of Resistivity Characteristics of Ca-Doped Semiconducting BaTiO3 Fired in Reducing Atmosphere and Reoxidized in Air

The positive temperature coefficient of resistivity (PTCR) characteristics of donor-doped BaTiO₃ fired in a reducing atmosphere and reoxidized in air are investigated. The result reveals that conventional semiconducting BaTiO₃ ceramics fired in a reducing atmosphere and reoxidized at a low temperature of 800°C in air show minimal PTCR characteristics, as reported earlier; however, Ca-doped BaTiO₃ with compositions in the range of 1.005≤(Ba+Ca+La)/Ti≤1.010 exhibit pronounced PTCR characteristics, even when reoxidized at such a low temperature. The semiconducting BaTiO₃ ceramics with {(Ba+Ca+La)/Ti}=1.005 and Ca-doped to 20 mol% exhibit remarkable PTCR characteristics with a resistivity jump of two orders of magnitude when they have been reoxidized at 800°C after firing in a reducing atmosphere.     

Evolution of Microstructure and V-Shaped Positive Temperature Coefficient of Resistivity of (Pb0.6Sr0.4)TiO3 Materials

The effects of various liquid-phase sintering aids on (Pb_0.6SrO_0.4)TiO₃ ceramics have been investigated. The relationships between electrical properties and microstructures have been scrutinized. It has been found that, among the sintering aids studied, only SiO₂ exhibits a significant effect on the grain growth of (Pb_0.6SrO₄)TiO₃. The optimum firing profiles for sound microstructure and good electrical properties of (Pb_0.6SrO_0.4)TiO₃+ 5.0 mol% SiO₂ have been established. The V-shaped electrical behavior is prominent, and a PTCR jump of about 10^2.9 is observed. The formation of cation vacancies may increase the resistivity of the over-fired specimens. Various milling methods to pulverize the calcined powder and the optimum amount of packing protection powder during sintering are also discussed.     

Synthesis of Y-Doped BaTiO3–(Bi1/2K1/2)TiO3 Lead-Free Positive Temperature Coefficient of Resistivity Ceramics and Their PTC Effects

As a lead-free positive temperature coefficient of resistivity (PTCR) material, (1– x mol%) BaTiO₃– x mol% (Bi_1/2K_1/2) TiO₃– y mol% Y₂O₃–0.5 mol% TiO₂ (BT– x BKT–2 y Y–0.5TiO₂) systems were prepared by the conventional solid-state reaction method. All samples containing <2 mol% BKT sintered in air possessed relatively low room-temperature resistivity (ρ₂₅) and high positive temperature coefficient (PTC) effect. However, when the BKT content exceeded 2 mol%, the sample was not semiconductive after sintering in air. The effects of sintering schedule on the properties of PTCR ceramics were discussed. The results showed that the optimum composition of BT–1BKT–0.2Y–0.5TiO₂, sintered at 1330°C for not-soaking and then fast quenched in air, achieved rather low ρ₂₅ of 28 Ω·cm and a high jump of resistivity (maximum resistivity [ρ_max]/minimum resistivity [ρ_min]) of 4.0 orders of magnitude with T _c about 155°C. The ρ₂₅ of the as-sintered sample could be further reduced to about 10 Ω·cm by annealing in N₂ at 450°C for 30 min, accompanied decrease on the PTC effect.     

Semiconducting–Insulating Transition for Highly Donor-Dopod Barium Titanate Ceramics

BaTiO₃ ceramics doped with La (0.01–0.84 at.%) were prepared only with the addition of La and stoichiometric TiO₂. As a result, even when BaTiO₃ was doped with 0.53 at.% La, it could be converted to a semiconductor by sintering at 1540°C for 2 h in air and cooled slowly in the furnace. Differential thermal analysis data clearly demonstrated that the Curie point in the materials shifted toward lower temperatures with increased content of La substituted at the Ba site up to a critical concentration that varied with the sintering temperature. The obtained results suggest that the semiconducting–insulating transition for highly donor-doped BaTiO₃ was closely related to the incorporation of donor into the grains and to the resultant grain size, which were significantly affected by the sinterability of the BaTiO₃ starting powders and sintering conditions used.     

Lanthanum-Magnesium and Lanthanum-Manganese Donor-Acceptor-Codoped Semiconducting Barium Titanate

BaTiO₃ powder doped with La donor and codoped with Mn or Mg acceptor was sintered at 1350°C/1 h in air. For Ladoped BaTiO₃, the room-temperature resistivity decreased to a minimum at [La³⁺] ∼ 0.15 mol%. For La-Mn-codoped BaTiO₃, the minimum resistivity occurred at [La³⁺] - 2[Mn²⁺] ∼ 0.15 mol%. When the ceramic was changed to a fine-grained insulator by high donor doping ([La³⁺] >0.15 mol%), its semiconductivity was restored, and the relatively homogeneous, coarse-grained microstructure recurred by codoping with either Mg or Mn acceptor, with the transition at [La³⁺] - 2[Mg²⁺] = 0.15 mol% or [La³⁺] - 2[Mn²⁺] = 0.15 mol%. The analogy of a compensation effect between La-Mn- and La-Mg-codoped BaTiO₃ suggested that Mn acceptor added to BaTiO₃ exists as Mn²⁺ ion in the bulk grain region; its influence on the positive temperature coefficient of resistivity behavior is then discussed.     

Shift of the Curie Point of Barium Titanate Ceramics with Sintering Temperature

Definite increases in the Curie point (T_C) of undoped and lanthanum- (La-) doped (<0.5 at.%) barium titanate (BaTiO₃) ceramics sintered at elevated temperatures in the range of 1300°-1450°C were observed. Both undoped and 0.3 at.% La-doped BaTiO₃ (chosen as a typical doping concentration to yield semiconducting materials) ceramics showed almost the same T_C behavior; their T_C values increased by ∼3.5°C as the sintering temperature was increased from 1300° to 1450°C. Semiconducting 0.3 at.% La-doped materials increased in room-temperature bulk resistivity and TC with increased sintering temperature. The bulk resistivity of the La-doped materials, which was obtained from complex impedance analysis, increased from ∼2 omega cm for the material sintered at 1350°C to ∼6 ω cm at 1450°C. The phenomenon of bulk resistivity increase with sintering temperature was observed in the materials with a doping concentration of ≥ 0.2 at.% La, but was not observed in those doped with <0.2 at.% La. The mechanisms of TC and the bulk resistivity increase observed in the present materials with increased sintering temperature are discussed based on various models found in the literature, particularly in terms of the defect chemistry in semiconducting BaTiO₃ ceramics and the influence of liquid phases present during sintering.     

Effect of Sintering Aids on Microstructures and PTCR Characteristics of (Sr0.2Ba0.8)TiO3 Ceramics

The effects of liquid-phase sintering aids on the microstructures and PTCR characteristics of (Sr_0.2Ba_0.8)TiO₃ materials have been studied. The grain size of sintered materials monotonically decreases with increasing content of Al₂O₃–SiO₂–TiO₂ (AST). The ultimate PTCR properties with ρ_ht/ρ_rt as great as 10^5.61 are obtained for fine-grain (10-μm) samples, which contain 12.5 mol% AST and were sintered at 1350°C for 1.5 h. The quantity of liquid phase formed due to eutectic reaction between AST and (Sr,Ba)TiO₃ is presumably the prime factor in determining the grain size of samples. The grains grow rapidly at the sintering temperature in the first stage until the liquid phase residing at the grain boundaries reaches certain critical thickness such that the liquid–solid interfacial energy dominates the mechanism of grain growth.     

Proposed Phenomenological PTCR Model and Accompanying Phenomenological PTCR Chart

The positive temperature coefficient of resistivity (PTCR) behavior of semiconductive BaTiO₃ is well explained by the Heywang model, which predicts the resistivity behavior above the Curie point based on the acceptor state density at the grain boundaries, the charge carrier density, and the energy gap, E _s, between the conduction band and the acceptor levels. However, the relationship between these parameters and the production parameters (sintering time, composition, and cooling rate) is not well understood. Recently, the present authors have found that E _s can be increased by thorough oxidation. This increase is attributed to a change in the oxidation state of the acceptor. Based on this finding and results from the literature, a phenomenological PTCR model and an accompanying PTCR chart for acceptor–donor-codoped BaTiO₃ are proposed to clarify this relationship. The PTCR chart clarifies that acceptor dopant concentrations, oxidation time, and oxygen partial pressure during oxidation or cooling can be optimized simultaneously to obtain optical PTCR properties.     

Determination of Inversion Temperature of Sb2O3-Doped BaTiO3 Positive Temperature Coefficient of Resistivity (PTCR) Ceramics by the Finite Difference Method

The effect of the cooling rate on the PTCR (positive temperature coefficient of resistivity) characteristics of 0.1 mol% Sb₂O₃-doped BaTiO₃ ceramics has been investigated. Resistances both below and above the Curie temperature were increased by slow cooling, which indicated that the resistive layer width at the grain boundary increased as the cooling rate decreased. Concentration profiles of the Ba vacancies as a function of distance from the grain boundary have been simulated by the finite difference method. The inversion temperature of the 0.1 mol% Sb₂O₃-doped BaTiO₃ system was determined to be 1160°C from the measured electrical properties and computed concentration profiles.     

Influence of Stoichiometry on the Microstructure and Positive Temperature Coefficient of Resistivity of Semiconducting Barium Titanate Ceramics

The influence of stoichiometry, i.e., Ba/Ti ratio, on the microstructure and positive temperature coefficient of resistivity (PTCR) characteristics of BaTiO₃ was investigated. Fine-grain microstructures are obtained for Ba-rich, stoichiometric, low-temperature-sintered, Ti-rich materials. The room-temperature resistivities ( ρRT ) of the fine-grain Ti-rich samples are large (>10⁸Ω·cm). Excess Ba²⁺ ions can decrease the ρRT , by more than 2 orders of magnitude, because of the compensation of barium vacancies near the grain-boundary regions. Rapid cooling after sintering can also decrease ρRT (⋍100×) and is ascribed to the suppression of reoxidation. Large-grain microstructures and low ρRT , on the other hand, are generally observed for Ti-rich and Al₂O₃-SiO₂-TiO₂-added samples after sintering at a temperature higher than the corresponding eutectic point.     

The Influence of ZnF2 Doping on the Electrical Properties and Microstructure in Bi2O3–ZnO-Based Varistors

ZnO varistors with different amounts of ZnF₂ from 0.00 to 0.80 mol% were prepared using a solid-state reaction technique, to explore the potential application of ZnO. The F-doping effects on the microstructure and electrical properties of ZnO-based varistors were investigated. The average grain size of ZnO increased from 4.93 to 6.48 μm as the ZnF₂ content increased. Experimental results showed that as the ZnF₂ content increased, the breakdown voltage decreased from 617 to 367 V/mm, and the nonlinear coefficient did not change much. However, a slight increase was observed in the leakage current. Besides, when the ZnF₂ content increased, the donor concentration increased from 0.669 × 10¹⁸ to 8.720 × 10¹⁸ cm⁻³. The study indicated that ZnF₂ played a similar role as sintering aids to promote grain growth and the substitutional F atoms in the bulk served as a donor to increase the donor concentration.     

Preparation of PTCR ceramics in the BaO–Nb2O5–TiO2 system

The PTCR effect was investigated in the ferroelectric BaNb₂O₆ phase doped with TiO₂. Composite ceramics formed after sintering in a reducing atmosphere and subsequent reoxidation show the PTCR effect at around 70 and 300°C, respectively. Both PTCR anomalies are associated with the formation of high resistivity grain boundaries after controlled oxidation of reduced constituent phases.     

High-K Dielectric Ceramics from Donor/Acceptor-Codoped (Ba1−xCax)(Ti1-yZry)O3 (BCTZ)

(Ba_{1− x} Ca _x )(Ti_{1− y} Zr _y )O₃ ceramics doped with various donors and acceptors were sintered in a reducing atmosphere and then annealed at different oxygen partial pressures. The dielectric maxima at the Curie point increased up to ∼30000 after reoxidation, depending on the grain size, the type of acceptor, and the annealing conditions. The increase of the dielectric maxima seems to be correlated with oxidation of the grain boundaries. The dielectric properties show relaxation effects with increased frequency.     

Compensating Defects in Highly Donor-Doped BaTiO3

Nb-doped BaTiO₃ has been prepared with various Ba/(Ti + Nb) ratios such that single-phase products will be obtained if the charged donor center is assumed to be compensated in turn by Ba vacancies, Ti vacancies, equal concentrations of the two cation vacancies, oxygen interstitials, or electrons. For air-Fired samples, examination by transmission electron microscopy showed that only the composition adjusted for compensation by titanium vacancies was single phase. The other compositions contained a Ti-rich second phase in order to achieve a matrix with the appropriate concentration of titanium vacancies. When sintered in a reducing atmosphere, compensation was by electrons, and a Ba-rich second phase was present hi the composition adjusted to give compensation by titanium vacancies. The results indicate that for donor concentrations greater than ∼0.5 mol% in BaTiO₃, charge compensation is achieved by Ti vacancies under oxidizing conditions, and by electrons (as is well-known) under reducing conditions.' The effect of compensating defects on grain growth is also discussed.     

Effect of Li2O and PbO Additions on Abnormal Grain Growth in the Pb(Mg1/3Nb2/3)O3–35 mol% PbTiO3 System

Abnormal grain growth in Pb(Mg_1/3Nb_2/3)O₃–35 mol% PbTiO₃ (PMN-35PT) ceramics doped with Li₂O and PbO has been investigated. Replacing the PbO dopant with up to 2 mol% Li₂O caused an increase in the number of abnormal grains. For the composition containing 2 mol% Li₂O and 6 mol% PbO, the amount of abnormal grain growth decreased with increasing sintering temperature. Single crystals of ∼6 mm × 6 mm × 2 mm thickness were grown from the 2 mol% Li₂O, 6 mol% PbO-containing composition via the templated grain growth method. Grain growth behavior with temperature is explained in terms of the effect of Li₂O on interface-reaction-controlled grain growth and the critical driving force.     

Positive Temperature Coefficient of Resistivity in Ba1-xSrxPb1+yO3-8 Ceramics

The positive temperature coefficient of resistivity (PTCR) effect in Ba_1-xSr_xPb_1+yO_3-s ceramics is systematically studied. The influence of the preparation conditions on the PTCR properties is experimentally tested. The PTCR effect in metallic-conducting BaPb_1+yO₃ is confirmed around 700°C. The temperature where the PTCR effect starts can be shifted to a higher temperature range by substituting strontium for the A-site barium. By the enhancement of the sintering, the magnitude of the PTCR effect was increased and the resisitivity was reduced. In addition to Pb(IV) in the perovskite structure, Pb(II) is detected at the grain boundary in the sintered body.     

PTCR behaviour of highly donor doped BaTiO3

The electrical properties of donor doped BaTiO₃ samples with a donor concentration >0·3 mol% were studied. Samples were sintered at a low partial pressure of oxygen in order to facilitate the anomalous grain growth and donor incorporation. In order to optimise the PTCR anomaly the samples were annealed in an oxidising atmosphere. The samples were characterised using impedance spectroscopy and SEM. Results show that by the use of a specific sintering profile PTCR ceramics containing a higher amount of donor dopant can be prepared.     

Core-Shell Structure Formation in Nb2O5-Doped SrTiO3 by Oxygen Partial Pressure Change

A core-shell structure was observed in SrTiO₃ doped with 1.2 mol% of Nb₂O₅, after sintering in a reducing atmosphere (5H₂-95N₂) and then in an oxidizing atmosphere (air). In undoped and Al₂O₃-doped SrTiO₃ specimens, no core-shell structure formed after the same sintering treatments as those for SrTiO₃ doped with 1.2 mol% of Nb₂O₅. The measured chemical compositions of the core and shell regions of 1.2-mol%-Nb₂O₅-doped SrTiO₃ grains showed that the Sr/(Ti + Nb) ratio of the shell regions grown in air was ~1% less than that of core regions grown in 5H₂-95N₂, which was in good agreement with a value predicted by available defect equations. Therefore, the observed core-shell structure is thought to result from the formation of strontium vacancies in an oxidizing atmosphere.     

Influence of Potassium on Preparation and Performance of PTC Resistors

Different amounts of K₂CO₃ were added to (Ba,Sr)TiO₃-based PTCR (positive temperature coefficient of resistance) ceramics to investigate their influence on the microstructural and electrical properties. Experimental results showed that the incorporation of K acted as an A-site acceptor-type dopant. In addition to enhancing discontinuous grain growth, the increase of K₂CO₃ was found to raise the room-temperature resistivity which was dominated by grain-boundary resistance rather than grain resistance. By adjusting to a suitable amount of donor dopant, the inherent contamination of K in raw material can be compensated to achieve a high-quality PTC resistor.