Dielectric evidence of persistence of polar nanoregions within the ferroelectric phases of (1-x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 relaxor ferroelectric system

Piezoelectric materials, which convert mechanical to electrical energy (and vice versa), are crucial in medical imaging, telecommunication and ultrasonic devices. A new generation of single-crystal materials, such as Pb(Zn1/3Nb2/3)O3-PbTiO3 (PZN-PT) and Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT), exhibit a piezoelectric effect that is ten times larger than conventional ceramics, and may revolutionize these applications. However, the mechanism underlying the ultrahigh performance of these new materials-and consequently the possibilities for further improvements-are not at present clear. Here we report a first-principles study of the ferroelectric perovskite, BaTiO3, which is similar to single-crystal PZN-PT but is a simpler system to analyse. We show that a large piezoelectric response can be driven by polarization rotation induced by an external electric field. Our computations suggest how to design materials with better performance, and may stimulate further interest in the fundamental theory of dielectric systems in finite electric fields.

The direct conversion of electrical energy to mechanical work by a material is relevant to a number of applications. This is illustrated by ferroelectric 'relaxors' such as Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PMN-PT; refs 5, 6): these materials exhibit a giant electromechanical (piezoelectric) response that is finding use in ultrasonic and medical applications, as well as in telecommunications. The origins of this effect are, however, still unclear. Here we show that the giant electromechanical response in PMN-PT (and potentially other ferroelectric relaxors) is the manifestation of critical points that define a line in the phase diagram of this system. Specifically, in the electric-field-temperature-composition phase diagram of PMN-PT (the composition being varied by changing the PT concentration), a first-order paraelectric-ferroelectric phase transition terminates in a line of critical points where the piezoelectric coefficient is maximum. Above this line, supercritical evolution is observed. On approaching the critical point, both the energy cost and the electric field necessary to induce ferroelectric polarization rotations decrease significantly, thus explaining the giant electromechanical response of these relaxors.