Investigation into the crystal structure–dielectric property correlation in barium titanate nanocrystals of different sizes

For high capacitance multilayer ceramic capacitors, high dielectric constant and lead-free ceramic nanoparticles are highly desired. However, as the particle size decreases to a few tens of nanometers, their dielectric constant significantly decreases, and the underlying mechanism has yet to be fully elucidated. Herein, we report a systematic investigation into the crystal structure-dielectric property relationship of combustion-made BaTiO₃ (BTO) nanocrystals. When the nanocrystal size was 100 nm and below, a metastable paraelectric cubic phase was found in the as-received BTO (denoted as arBTO) nanocrystals based on an X-ray diffraction (XRD) study. A stable ferroelectric tetragonal phase was present when the nanocrystal size was above 200 nm. Notably, the cubic arBTO (particle size ≤100 nm) exhibited tetragonal fluctuations as revealed by Raman spectroscopy, whereas the tetragonal arBTO (particle size ≥200 nm) contained ∼10% cubic fraction according to the Rietveld fitting of the XRD profiles. Thermal annealing of the multi-grain tetragonal arBTO at 950 °C yielded single crystals of annealed BTO (denoted as anBTO), whose dielectric constants were higher than those of arBTO. However, the single crystalline anBTO prevented the formation of 90° domains; therefore, they exhibited a low dielectric constant of ∼300. Although X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy could not identify the exact structural defects, our study revealed that surface and bulk defects formed during synthesis affect the final crystal structures and thus the dielectric properties of BTO nanocrystals with different sizes. The understanding obtained from this study will help us design high dielectric constant perovskite nanocrystals for next-generation multilayer ceramic capacitor applications.