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For a high capacitance and high lifetime reliability of multilayer ceramic capacitors for automotive applications, the activation energy on thermal activation process can typically be calculated by using Arrhenius based Prokopowicz–Vaskas equation as a method for lifetime prediction. In this study, it is clearly observed that the activation energy shows to be constant in the range of ~ 1.5 eV for the prototype MLCCs, higher than the activation energy values of ~ 1.0 eV related to the motion or diffusion of oxygen vacancies reported in the previous literature. The activation energy value of ~ 1.5 eV for three prototype MLCCs is close to a half the energy band gap (Eg/2 ≈ 1.6 eV) of BaTiO3 obtained from specific environment, where oxygen vacancies are stabilized by external containment such as the effect of rare earth oxide additives. Due to an obvious difference in activation energy values, it difficult to explain the conduction mechanism for failure by only oxygen vacancy migration. Therefore, the concepts of electronic processes and oxygen vacancy should be considered together to understand conduction mechanism for failure of BaTiO3-based MLCCs in thermal activation processes. It can be useful as an indicator for future MLCC development with high lifetime reliability. [ABSTRACT FROM AUTHOR]

The effect of excess Ba concentration on the dielectric nonlinearity was investigated in Mn and V-doped BaTiO3 multi layer ceramic capacitors (MLCC) under the same grain size condition, which was described by the Preisach model utilizing the first order reversal curve (FORC) distribution. The high-field dielectric constant and its ac field dependence dramatically changed increasing to a maximum and then decreasing with the increase of Ba concentration. The saturation polarization which scales to the magnitude of spontaneous polarization also showed similar behavior. These results indicate that the dependence of the dielectric constant on the Ba concentration is associated with the variation of both domain wall contribution and the magnitude of the spontaneous polarization, which could be correlated with the same dependence on the Ba concentration of the reversible FORC distribution at zero bias and the irreversible FORC distribution near origin. In the corresponding bulk specimens of the dielectrics of MLCC, almost the same amount of the Ba2TiSi2O8 second phases were detected irrespective of Ba concentration, which shows that the excess Ba incorporate into BaTiO3. Thus, low and high Ba concentration corresponds to Ba-deficient and Ba-rich or Ti-deficient BaTiO3, respectively, which results in a small spontaneous polarization and low domain wall density. The intermediate Ba concentration for the maximum dielectric constant is supposed to be near stoichiometric condition in the ABO3 structure corresponding to large spontaneous polarization and high domain wall density. The excess Ba concentration and its resultant A/B stoichiometry is a crucial factor controlling dielectric properties. [ABSTRACT FROM AUTHOR]

Abstract: The influence of temperature on the variation in dielectric nonlinearity and domain structures was investigated for the (Ba0.95Ca0.05)(Ti0.83Zr0.17)O3 (BCTZ)‐based multilayer ceramic capacitor that shows a diffuse phase transition. Whereas the dielectric constant (εr) vs temperature shows a broadened maximum peak at low ac driving field, such a peaked behavior disappears at high ac driving field due to an abrupt increase in dielectric constants at low temperatures. Such low temperature effect can be associated with an enhanced spontaneous polarization (PS) and a significant increase in irreversible domain wall contribution to polarization representing normal ferroelectric behavior based on the Preisach analysis. No ferroelectric domain contrasts were observed at room temperature through transmission electron microscopy. However, they appeared and became more and more distinct with the decrease in temperature, and the crystal structure also changed from cubic to rhombohedral with increased lattice constants. It demonstrates that the dramatic increase in the dielectric nonlinearity with decreasing temperatures originates from the corresponding changes in domain and crystal structure, where the polar‐micro‐regions of BCTZ at room temperature change to normal ferroelectric domains at low temperatures. [ABSTRACT FROM AUTHOR]

The effect of Dy-doping on the dielectric nonlinearity was investigated in Mn and V-doped BaTiO3 multilayer ceramic capacitors under the same grain size condition, which was described by the Preisach model utilizing the first order reversal curve (FORC) distribution. The dielectric constants in both low and high field region could be enhanced by the Dy-doping, and it was associated with the increase of both reversible and irreversible FORC distributions near zero bias, whereas there was little variation in the saturation polarization that scales to the magnitude of spontaneous polarization. These results demonstrate that both reversible and irreversible domain wall motions are enhanced by Dy-donor incorporation in BaTiO3 resulting in softening of the dielectrics and increase of dielectric constants, which is supposed to be caused by the decrease of the pinning sources such as defect dipoles formed by the oxygen vacancies and their interaction with the domain walls. [ABSTRACT FROM PUBLISHER]

Dielectric aging of Dy and Mn-codoped BaTiO3 multilayer ceramic capacitors was investigated. The increase of Dy concentration significantly decreased the aging rate and caused a disappearance of the thermally stimulated depolarization current peak associated with the defect dipole of Mn such as ${\rm{Mn}}_{{\rm{Ti}}}^{\prime \prime } {\rm{ - V}}_{\rm{O}}^{\cdot\cdot}$ or ${\rm{Mn}}_{{\rm{Ti}}}^\prime {\rm{ - V}}_{\rm{O}}^{\cdot\cdot}$, which was observed in low Dy-concentration specimens. These results experimentally demonstrate that the rare earth element, Dy, decreases the concentration of the defect dipoles and thereby controls dielectric aging. [ABSTRACT FROM PUBLISHER]

Resistance degradation of zirconium (Zr)-doped barium titanate (BaTiO3) was investigated. A series of Ba(Ti1−yZry)O3 powders and coarse-grained ceramics ranging y from 0 to 0.1 were prepared. The increase of Zr concentration systematically increased the time to as well as electric field to degradation. Such behaviors directly corresponded to those of ionic conduction contribution as evaluated by the Warburg impedance. The magnitude of Warburg impedance decreased with the increase of Zr concentration, which demonstrates that the Zr incorporation inhibits the ionic conduction caused by oxygen vacancies. The prototype multilayer ceramic capacitor (MLCC) samples were also prepared by applying these Ba(Ti1−yZry)O3 base powders and formulated X5R additives of commercial application. In this case, however, such distinct difference in degradation behavior with the variation of Zr concentration did not appear. It is supposed that the influence of additives far outweighs the effect of relative difference in the ionic conduction of Ba(Ti1−yZry)O3 under the MLCC test condition where the applied electric field strength is much higher than those for the coarse-grained bulk ceramics. Resistance degradation of MLCC under such high field might not be explained by only oxygen vacancy-related behavior alone. [ABSTRACT FROM AUTHOR]

I (Current)-V (voltage) characteristics of Mn-doped BaTiO3 multilayer ceramic capacitor were investigated. The increase of Mn concentration reduced the slope of current increase with increasing dc field and enhanced the dc field to the abrupt increase of current and thereby breakdown. Ohmic, Schottky, and Poole-Frenkel type conduction was successively observed with the increase of dc field in all specimens. The region of Child's law did not appear before breakdown, which suggests space charge limited (SCL) conduction with field enhanced trap barrier lowering. A peak of thermally stimulated depolarization current (TSDC) beyond 300 °C associated with trapped space charges appeared, which increased by the increase of Mn concentration. In addition, the peak intensity increased to a maximum value and then decreased again with increasing polarization dc field in TSDC measurement. Its activation energies were around 1.9 eV for all specimens, which is very close to the energy level for the ionization of Mn3+/Mn2+. These results experimentally demonstrate the role of the variable valence acceptor Mn as trapping center for injected charges, and the occurrence of field enhanced trap charge release, and therefore, the conduction mechanism can be described by the SCL model incorporating the Poole-Frenkel effect. [ABSTRACT FROM AUTHOR]

Dielectric aging of Mn and V-codoped BaTiO3 was investigated. The increase of V concentration had little influence on aging, whereas that of Mn increased it. Thermally stimulated depolarization current (TSDC) of low Mn concentration specimen showed one peak, whereas Mn-increased specimen showed two peaks. The first and second peak is supposed to be caused by the phase transition of the undoped core region and the defect dipole of Mn such as MnTi″-VO•• or MnTi′-VO••, respectively. High TSDC associated with the defect dipole of Mn and significant aging rate experimentally demonstrates that the dielectric aging is controlled by the defect dipole. [ABSTRACT FROM AUTHOR]