Modification of BCZT piezoelectric ceramics by modulating oxygen vacancies in different sintering atmospheres

In this work, we regulated the oxygen vacancy concentration by sintering BCZT + 0.1 mol % Y + 0.1 mol % Nb [BCZT-0.1 mol % (Y + Nb)] ceramics under air, oxygen, argon, and vacuum atmospheres and examined the effect of oxygen vacancy concentration on phase composition, crystal structure, microstructure, and electrical properties. X-ray photoelectron spectrometry and X-ray diffraction Rietveld refinement showed that the air- and oxygen-sintered ceramic samples had lower oxygen vacancy concentrations, and the oxygen octahedral lattice distortion in the samples was stable when the R-O-T phases coexisted, forming a multiphase coexistence structure with more spontaneous polarization directions. The oxygen-sintering atmosphere is important in oxygen compensation, which promotes the formation of dense microstructure, thereby increasing the Curie temperature (TC). Oxygen vacancy formation energy was low in the argon and vacuum atmospheres, and some oxygen vacancies increased the mass transfer effect and grain growth. Nevertheless, excess oxygen vacancies increased the leakage current during polarization resulting in poor polarity, which prevents directional deflection of domains and degrades performance. The vacuum-sintered sample was calcined in 1000 °C air for oxygen supplementation sintering, and as the sintering time increased, the oxygen vacancy concentration decreased, the grains grew further, the density increased, and the piezoelectric properties improved. The oxygen-sintered BCZT-0.1 mol % (Y + Nb) samples had good comprehensive electrical properties (d33 = 547 pC/N, kp = 55%, εr = 5355, Pr = 10.63 µC/cm2, EC = 1.89 kV/cm, tan δ = 0.02, and TC = 102 °C).