Piezoelectric nonlinearity and frequency dispersion of the direct piezoelectric response of BiFeO3 ceramics

We report on the frequency and stress dependence of the direct piezoelectric d33 coefficient in BiFeO3 ceramics. The measurements reveal considerable piezoelectric nonlinearity, i.e., dependence of d33 on the amplitude of the dynamic stress. The nonlinear response suggests a large irreversible contribution of non-180 domain walls to the piezoelectric response of the ferrite, which, at present measurement conditions, reached a maximum of 38% of the total measured d33. In agreement with this interpretation, both types of non-180 domain walls, characteristic for the rhombohedral BiFeO3, i.e., 71 and 109, were identified in the poled ceramics using transmission electron microscopy. In support to the link between nonlinearity and non-180 domain-wall contribution, we found a correlation between nonlinearity and processes leading to depinning of domain walls from defects, such as quenching from above the Curie temperature and high-temperature sintering. In addition, the nonlinear piezoelectric response of BiFeO3 showed a frequency dependence that is qualitatively different from that measured in other nonlinear ferroelectric ceramics, such as “soft” (donor-doped) Pb(Zr,Ti)O3 (PZT), i.e., in the case of the BiFeO3 large nonlinearities were observed only at low field frequencies (