Microscopic interpretation of sign reversal in the electrocaloric effect in a ferroelectric PbMg1/3Nb2/3O3-30PbTiO3 single crystal

With increasing temperature, PbMg1/3Nb2/3O3-30PbTiO3 (PMN-30PT) crystals change from pseudo-rhombohedral to tetragonal to cubic phases. In addition to the usual positive electrocaloric effect (ECE), a negative ECE, whose origin is uncertain, is observed. Here, these two types of the ECE contributions in PbMg1/3Nb2/3O3-30PbTiO3 crystals are modelled theoretically using a one dimensional statistical mechanical lattice model, which is solved by an exact matrix method. The quasi one-dimensional model reproduces the trends in the experimental behaviour and attributes the electrocaloric sign reversal to free energy changes induced by the electric field.