The electrocaloric effect (ECE), known for its environmentally friendly characteristics, holds significant promise for advancing next-generation solid-state refrigeration technologies. Achieving a large ECE along with a wide working temperature range near room temperature remains a key developmental goal. In this study, we successfully obtained a substantial ECE of 1.78 K and an extensive working temperature range of 103 K (ΔT > 1.52 K) near room temperature in CaZrO₃-modified BaTiO₃ lead-free ferroelectric ceramics. Furthermore, this achievement was verified using direct methods. The piezoresponse force microscopy (PFM) results suggest that the broad temperature range is attributed to the formation of ferroelectric microdomains and polar nanoregions (PNRs). Furthermore, X-ray photoelectron spectroscopy (XPS) and ultraviolet‒visible (UV‒Vis) spectroscopy reveal a decrease in the oxygen vacancy concentration and an increase in the bandgap for higher CaZrO₃ doping levels. These changes synergistically enhance the maximum applied electric field, helping to achieve a high-performance ECE near room temperature. This research presents a straightforward and effective approach for achieving high-performance ECEs in BaTiO₃ lead-free ceramics, offering promising prospects for application in next-generation solid-state refrigeration technologies.

The electrocaloric effect (ECE) offers a pathway to environmentally sustainable and easily miniaturized refrigeration technology, positioning it as a front-runner for the next generation of solid-state cooling solutions. This research unveils a remarkable ECE in a finely tuned (Ba_0.86Ca_0.14)_0.98La_0.02Ti_0.92Sn_0.08O₃ ceramic, exhibiting a temperature shift (ΔT) of 1.6 K across more than 85% of the maximum ΔT (ΔT_max) and spanning an exceptionally wide operational range of 92 K. Our investigation on dielectric responses and ferroelectric polarization-electric field (P–E) loops suggests that the broad operational scope results from the fragmentation of extended ferroelectric domains into smaller domains and polar nano-regions (PNRs) supported by PFM analysis. Furthermore, the introduction of La enhances spontaneous polarization by significantly extending the maximum electric field that can be applied, facilitating high-performance ECE at ambient temperature. This study positions BaTiO₃-based lead-free ceramic as a sustainable alternative for addressing the cooling demands of modern electronic components, marking a significant stride toward next-generation solid-state refrigeration.