With the increasing demand for the miniaturization, high capacitance and high reliability of the Multilayer Ceramic Capacitor (MLCC), the thickness of single dielectric layer is less than 1 μm and the original partical size of the powder has reached the scale less than 300 nm. In this paper, BaTiO3 powder of various partical sizes (150–500 nm) was modified with Dy and Ho through a chemical coating method. The dense and uniform ceramics in accordance with EIA X7R-type temperature stability were sintered under low oxygen partial pressure and good dielectric properties of dielectric constant >2000 and dielectric loss <1% were obtained. The grain size effect on the dielectric properties under various dc-bias field were systematically investigated. It is found that the fine-grain ceramic exhibits a lower absolute change of the dielectric constant and a higher dc-bias stability. Furthermore, the modified 150 nm BaTiO3 powders was made into 1210-type MLCCs, and the dielectric behavior of the MLCCs with different dc-fields and ac-fields were study over −55 °C–125 °C. It is found that the ac electric field had a greater influence on the dielectric properties at room temperature and below, and the dielectric constant variation under a dc-bias field was also greatly advanced for the modified fine-grain MLCCs. The results provide a reference for the design of the next generation of BME-MLCCs.
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