Insights into improved ferroelectric and electrocaloric performance of Ba0.85Ca0.15Ti0.9Zr0.1O3 thick films grown by the electrophoretic deposition

Abstract

Lead-free Ba0.85Ca0.15Ti0.9Zr0.1O3 (BCZT) bulk ceramics have recently gained attention as one of the attractive candidates for electrocaloric cooling due to their large heat absorption capacity induced by electro-structural phase transition near room temperature. However, adiabatic temperature change (ΔT) at room temperature in ceramics has been limited by their relatively low dielectric breakdown strength. Thick films, in this respect, possess the advantages of ceramics (volume) and thin films (thickness). In this work, a systematic ferroelectric and electrocaloric investigation of BCZT thick films, fabricated by electrophoretic deposition combined with laser annealing, has been carried out. Laser annealing at an optimized energy density of 398 W/cm2 has resulted in densely packed grain morphology with no compositional heterogeneities. Analysis of the scaling behavior of dynamic hysteresis revealed that ferroelectric domain reversal in BCZT/Pt has good stability and low energy consumption in the saturation region. The present thick films exhibited larger breakdown strength of 294 kV/cm and recoverable energy storage density of ∼7.3 J/cm3, at least five-fold enhancement compared to the bulk which is stable up to a 4 mm bending radius. The indirect electrocaloric measurements displayed parameters such as a ΔT and entropy change (ΔS) of 2.94 K and 3.1 J kg−1 K−1 respectively, for 205 kV/cm which are more than two orders increased compared to the bulk. Higher values of ΔT (1.9 K) at 25 °C, refrigerant capacity of 249 J/kg, and responsivity of 0.143 K mm/kV for BCZT/Pt film compared to relevant lead-free ferroelectric thick films elucidate the potential use of these films for solid-state refrigeration applications. The work also presents electrophoretic deposition with laser annealing as an alternative technique to widely studied tape-casting of thick films for electrocaloric studies.