Phase transition behavior and electrical properties of lead-free (Ba1−xCax)(Zr0.1Ti0.9)O3 piezoelectric ceramics

Lead-free (Ba1−xCax)(Zr0.1Ti0.9)O3(BCZT) ceramics were synthesized by conventional solid-state sintering process. The Ca ion substitutions on phase transition behavior, microstructure, ferroelectric and piezoelectric properties of BCZT ceramics were systemically investigated. The diffuse phase transition (DPT) behavior was suppressed, while the orthorhombic → tetragonal (O→T) and rhombohedral → orthorhombic (R→O) phase transitions were observed when the Ca content is at x = 0.05. Further increasing the Ca content, the DPT behavior gradually enhanced, and both the O→T and R→O phase transitions gradually evolved into R→T phase transition when the Ca content increases up to 0.15 at 25 °C. This behavior was related with phase structure and morphology, which significantly impacted the ferroelectric and piezoelectric properties near the R→T phase boundary. As a result, the sample with Ca contents of 0.15 shows the outstanding piezoelectric properties (with d33 = 572 pC/N, kp = 57%, Qm = 125, εr = 4821, and tan δ = 0.015) while negligible change for the ferroelectric properties. The abnormal ferroelectric behavior and potential factor contributing to large piezoelectric response also were discussed.