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Dielectrics with high permittivity and temperature stability are important for the development of high-temperature multilayer ceramic capacitors (MLCCs). In this study, Ca1−xNaxTi1−xNbxSiO5 (abbreviated as CTS−xNN) ceramics were prepared by solid-phase reaction method. The introduction of NN weakens the long-range ordered displacement of Ti, leading to a significant increase in the dielectric temperature stability. The CTS−2%NN samples exhibit high permittivity (53) and TCC ≤±170 ppm/∘C in the range of −55∘C to 300∘C. The CTS-based ceramics behave high dielectric temperature stability. In addition, the bandgap of the CTS-based ceramics increased significantly, which is favorable for improving the breakdown strength of the material. For x=4% samples, the breakdown strength reaches 621kV/cm. Thus, the designed CTS-based dielectrics are promising for high-temperature capacitors.