Next-generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)-free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi-phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead-free piezoelectric materials (1-
x)Ba
0.95Ca
0.05Ti
0.95Zr
0.05O
3-(
x)Ba
0.95Ca
0.05Ti
0.95Sn
0.05O
3, are reported, which are represented as (1-
x)BCZT-(
x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1-
x)BCZT-(
x)BCST materials are synthesized by high-temperature solid-state ceramic reaction method by varying
x in the full range (
x = 0.00–1.00). In-depth exploration research is performed on the structural, dielectric, ferroelectric, and electro-mechanical properties of (1-
x)BCZT-(
x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X-ray diffraction (XRD) analyses, which also reveals that the Ca
2+, Zr
4+, and Sn
4+ are well dispersed within the BaTiO
3 lattice. For all (1-
x)BCZT-(
x)BCST ceramics, thorough investigation of phase formation and phase-stability using XRD, Rietveld refinement, Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), and temperature-dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (
Amm2 +
P4mm) phases at room temperature. The steady transition of
Amm2 crystal symmetry to
P4mm crystal symmetry with increasing
x content is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral-orthorhombic (T
R-O), orthorhombic- tetragonal (T
O-T), and tetragonal-cubic (T
C), gradually shift toward lower temperature with increasing
x content. For (1-
x)BCZT-(
x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constant
εr ≈ 1900–3300 (near room temperature),
εr ≈ 8800–12 900 (near Curie temperature), dielectric loss, tan
δ ≈ 0.01–0.02, remanent polarization
Pr ≈ 9.4–14 µC cm
−2, coercive electric field
Ec ≈ 2.5–3.6 kV cm
−1. Further, high electric field-induced strain
S ≈ 0.12–0.175%, piezoelectric charge coefficient
d33 ≈ 296–360 pC N
−1, converse piezoelectric coefficient
≈ 240–340 pm V
−1, planar electromechanical coupling coefficient
kp ≈ 0.34–0.45, and electrostrictive coefficient (
Q33)
avg ≈ 0.026–0.038 m
4 C
−2 are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT-(0.4)BCST composition (
x = 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead-free piezoelectric (1-
x)BCZT-(
x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1-
x)BCZT-(
x)BCST ceramics as a potentially strong contender within the family of Pb-free piezoelectric materials for future electronics and energy harvesting device technologies.
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