Synthesis and physical properties of Ca- and Ta-modified (K,Na)NbO3 lead-free piezoelectric ceramics

Polycrystalline samples of lead-free Ca and Ta co-substituted potassium sodium niobate (K0.5Na0.5NbO3, KNN) ceramics have been prepared by solid state reaction technique. X-ray diffraction showed formation of a single-phase perovskite structure with orthorhombic symmetry. Substitution inhibits the grain growth, improves densification and decreases the ferro-paraelectric phase transition temperature. Temperature dependent dielectric permittivity studies demonstrate significant decrease in peak-permittivity values in the substituted samples. Bulk longitudinal piezoelectric coefficient is significantly enhanced, up to approximate to 155 pC/N for (K0.48Na0.48Ca0.02)(Nb0.85Ta0.15O3) as compared to 95 pC/N for pristine KNN ceramic. Local piezoelectric properties have been observed by piezoresponse force microscopy (PFM) technique. Distinct piezocontrast was studied in both vertical and in-plane modes of PFM for all samples. The samples exhibit self-polarization effect in the unpoled state and effective local vertical piezoelectric coefficient was the largest in Ca and Ta co-substituted sample whereas the in-plane piezoelectric coefficient was maximum for Ca-substituted KNN sample. These studies are important for using substituted lead free KNN materials in various piezoelectric applications.Authors (IC and NP) would like to thank the Portuguese foundation FCT for financial support through projects SFRH/BPD/81032/2011 and SFRH/BPD/71289/2010, respectively. Financial sup- port from FCT through projects PTDC/FIS/108025/2008 and PTDC/CTM-CER/115085/2009 is also acknowledged. Financial support by Spanish MICINN project MAT2011-23709 is also acknowledged