Revisiting the Kittel's model of antiferroelectricity: phase diagrams, hysteresis loops and electrocaloric effect.

We revisit the Kittel's model of antiferroelectricity by extending the model to study the phase transitions, hysteresis loop behaviors and electrocaloric effect (ECE) of antiferroelectrics (AFEs). By considering both the first- and second-order AFEs, explicit expressions for the physical and staggered polarizations of AFEs in the stable states are derived. We also obtain the analytical solutions for describing the dielectric susceptibilities of AFEs in the AFE and paraelectric (PE) phases. Coercive fields in AFE are also derived and studied. To verify the usefulness of the Kittel's model of antiferroelectricity, we apply the model to systematically investigate the phase transitions, hysteresis loops and ECEs of PbZrO3(PZO). By adopting appropriate values of the Kittel's parameters for first-order transition, analytical and numerical results are obtained and discussed. Our results show that PZO exhibits a complex temperature (T)-electric field (E) phase diagram, consisting of the AFE, ferroelectrics, ferrielectric, PE and mixed phases. TheT-Ephase diagram is qualitatively agreed with the new AFE model that was derived based on symmetry by Tolédano and Khalyavin (2019Phys. Rev.B99024105). We found that the calculated zero-field dielectric susceptibility is qualitatively and quantitatively agreed with experimental results. We show that the polarizations and dielectric susceptibilities of PZO in heating and cooling deviate from each other, as expected for the first-order materials. Our calculated results also reveal that the ECE in PZO has an electro-heating of ΔT≈ +6.5 °C and an electro-cooling of ΔT≈ -4.0 °C, respectively, which are comparable to the experimental results.

Rich antiferroelectric phase diagram of antiferroelectric-ferroelectric superlattices: internal electric field- and interface induced phase transitions.

We propose a thermodynamic model to the study the antiferroelectric (AFE) phase transitions in antiferroelectric-ferroelectric (AFE-FE) superlattices in which the coupling at the interface between two layers is mediated by local polarizations. Phase diagram of the AFE layer in term of the degree of interfacial effect λ and temperature T involving ferrielectric (FI) and ferroelectric (FE) phases is investigated. These two phases are stabilized by the interfacial effect and internal electric field. AFE thickness L AFE versus T phase diagram is also constructed. Intermediate regions of two-phase coexistence (IM) emerge in the λ-T and L AFE-T phase diagrams, if certain interface properties λ and layer thickness L AFE criteria are met. These IM regions are metastable states, which exist as a transition state between two phases. A tricritical point locates at the boundaries across the FI, IM and FE phases is found in the L AFE-T phase diagram. Competition among the internal electric field due to the electrostatic coupling, the FE ordering arises from the interfacial effect and the antiferroelectric ordering within the AFE layer giving rises to the rich AFE phase diagram.