Insights into the Early Size Effects of Lead‐Free Piezoelectric Ba0.85Ca0.15Zr0.1Ti0.9O3

Abstract Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) stands out among lead‐free ferroelectric oxides under consideration to replace state‐of‐the‐art high‐sensitivity piezoelectric Pb(Zr,Ti)O3, for a range of energy conversion ceramic technologies. However, the best performances have been reported for very coarse‐grained materials, and attempts to refine microstructure below 10 µm grain size consistently result in significant property degradation. Here a comprehensive study of the grain size effects on the properties of BCZT across the micron scale is reported, down to the verge of the submicron one. Results show a distinctive early evolution of properties for grain sizes between 1 and 5 µm. For the larger sizes in this range, an opposite effect is found for the piezoelectric charge coefficient and electric field‐induced strain with respect to the very coarse‐grained material, while very good overall performance is maintained. For the lower sizes, relaxor features appear, yet materials can still be poled indicating their ferroelectric nature. This strongly resembles size effects in the Pb(Mg1/3Nb2/3)O3‐PbTiO3 system, driven by the slowing down of the relaxor to ferroelectric transition with size reduction, though kinetics seem to slow down across much larger grain sizes for BCZT. Concomitant changes in the polymorphic phase coexistence are described and discussed by synchrotron X‐ray diffraction.