Unusual thermodynamic properties and nonergodicity in ferroelectric superlattices

The properties of [Pb(Zr1-x1Tix1)O-3](n)/[Pb(Zr1-x2Tix2)O-3](n) superlattices, with a 2n period, are simulated using an ab initio based approach. The x(1) and x(2) compositions are chosen to be located across the morphotropic phase boundary of the corresponding disordered alloys, while the (x(1)+x(2))/2 average composition lies inside this boundary. These superlattices exhibit an unusual thermodynamic phase transition sequence, including a triclinic ground state. They also have the kind of peculiar free-energy landscape yielding nonergodicity. The effects responsible for these anomalies are discussed.