Seed-Free Solid-State Growth of Large Lead-Free Piezoelectric Single Crystals: (Na_1/2K_1/2)NbO₃

Large Na_0.5K_0.5NbO₃ (NKN) piezoelectric single crystals were obtained by seed-free solid-state crystal growth method, which is a traditional sintering grain growth process, with LiBiO₃ used as a sintering aid. The largest dimension of the single crystals obtained was 11 mm × 9 mm × 3 mm. In addition to the LiBiO₃ doping content, temperature, and time effect of the crystal growth process was systematically investigated and considered from the kinetics point of view. With the assistance of Avrami analysis, parameters relevant to the crystal growth process were determined. Laue diffraction and transmission electron microscopy suggested an orthorhombic symmetry for the single crystalline structure. Dielectric-frequency-temperature measurements revealed an orthorhombic-tetragonal and tetragonal-cubic phase transition at 155C and 405C, respectively, both of which are typical of first-order transitions, and have a well-defined thermal hysteresis. Rayleigh analysis was performed regarding to the extrinsic reversible and nonreversible piezoelectric properties, and the result suggested a dominant intrinsic reversible piezoelectric contribution of 91.5% under E₀ = 1 kV/cm AC amplitude. Such a single crystal growth process route is low cost and a relative simple preparation process.