Realization of Negative Thermal Expansion in Lead-Free Bi_0.5K_0.5VO₃ by the Suppression of Tetragonality

Bi_1/2K_1/2VO₃ is a lead-free PbTiO₃-type compound with a tetragonality (c/a = 1.054) comparable to that of typical ferroelectric PbTiO₃ (c/a = 1.064) with negative thermal expansion (NTE) during the tetragonal-to-cubic phase transition; therefore, Bi_1/2K_1/2VO₃ is a potential lead-free NTE material if its metastable perovskite structure can be maintained at high temperatures. In the present experiment, electron doping in Bi_1/2K_1/2VO₃ was conducted through substituting K⁺ with La³⁺ to suppress the tetragonality and achieve NTE. La substitution successfully suppressed the tetragonality of Bi_1/2K_1/2VO₃ and also improved its thermal stability. Moreover, both composition- and temperature-induced tetragonal-to-cubic phase transitions occurred. In particular, a large volume shrinkage with a large negative thermal coefficient of expansion (CTE) was obtained for Bi_0.5K_0.46La_0.04VO₃ during the tetragonal-to-cubic phase transition (ΔV = −0.66%). Hence, this study extends the NTE family and also sheds light on the exploration of lead-free piezoelectric materials with controllable thermal expansion.