Epitaxial PbZrxTi1-xO3 Ferroelectric Bilayers with Giant Electromechanical Properties

Giant electromechanical response viaferroelastic domain switching is achieved in epitaxial (001) ferroelectric tetragonal (T) PbZr0.3Ti0.7O3/rhombohedral (R) PbZr0.55Ti0.45O3 bilayers, grown on La0.67Sr0.33MnO3 buffered SrTiO3 substrates. X-ray diffraction and transmission electron microscopy show that the domain structure of the T films is tuned as a function of its thickness, from a fully a1/a2-domains (30 nm thick T layer) to a three domain stress-free c/a1/c/a2 polytwin state (100 nm thick T layer). A large switchable polarization is found up to 65 μC cm-2. Quantitative piezoelectric force microscopy reveals enhanced piezoelectric coefficients, with d33 coefficients ranging from 250 to 350 pm V-1, which is up to seven times higher than the nominal PbZrxTi1-xO3 thin film values. These are attributed to the motion of nanoscale ferroelastic domains. Fatigue testing proves that these domains are reversible and repeatable up to 107 cycles. In-situ X-ray synchrotron measurements reveal that the ferroelastic domain switching is promoted by a pulsating strain effect imposed by the R layer. The study reports a fundamental understanding of the origin of giant piezoelectric coefficients in epitaxial ferroelectric bilayers.