Ferroelectrics are attractive candidate materials for environmentally friendly solid state refrigeration free of greenhouse gases. Their thermal response upon variations of external electric fields is largest in the vicinity of their phase transition
s, which may occur near room temperature. The magnitude of the effect, however, is too small for useful cooling applications even when they are driven close to dielectric breakdown. Insight from microscopic theory is therefore needed to characterize materials and provide guiding principles to search for new ones with enhanced electrocaloric performance. Here, we derive from well-known microscopic models of ferroelectricity meaningful figures of merit which provide insight into the relation between the strength of the effect and the characteristic interactions of ferroelectrics such as dipole forces. We find that the long range nature of these interactions results in a small effect. A strategy is proposed to make it larger by shortening the correlation lengths of fluctuations of polarization.
We study the free energy landscape of a minimal model for relaxor ferroelectrics. Using a variational method which includes leading correlations beyond the mean-field approximation as well as disorder averaging at the level of a simple replica theory
, we find metastable paraelectric states with a stability region that extends to zero temperature. The free energy of such states exhibits an essential singularity for weak compositional disorder pointing to their necessary occurrence. Ferroelectric states appear as local minima in the free energy at high temperatures and become stable below a coexistence temperature $T_c$. We calculate the phase diagram in the electric field-temperature plane and find a coexistence line of the polar and non-polar phases which ends at a critical point. First-order phase transitions are induced for fields sufficiently large to cross the region of stability of the metastable paraelectric phase. These polar and non-polar states have distinct structure factors from those of conventional ferroelectrics. We use this theoretical framework to compare and to gain physical understanding of various experimental results in typical relaxors.
We study a minimal model for a relaxor ferroelectric including dipolar interactions, and short-range harmonic and anharmonic forces for the critical modes as in the theory of pure ferroelectrics together with quenched disorder coupled linearly to the
critical modes. We present the simplest approximate solution of the model necessary to obtain the principal features of the correlation functions. Specifically, we calculate and compare the structure factor measured by neutron scattering in different characteristic regimes of temperature in the relaxor PbMg$_{1/3}$Nb$_{2/3}$O$_3$.
