Thermally Stable Capacitive Energy-Density and Colossal Electrocaloric and Pyroelectric Effects of Sm-Doped Pb(Mg1/3Nb2/3)O3–PbTiO3 Thin Films

Sm-doped Pb(Mg1/3Nb2/3)O3–PbTiO3 (Sm-PMN–PT) bulk materials have revealed outstanding ferroelectric and piezoelectric properties due to enhanced local structural heterogeneity. In this study, we further explore the potential of Sm-PMN–PT by fabricating epitaxial thin films by pulsed laser deposition, revealing that Sm doping significantly improves the capacitive energy-storage, piezoelectric, electrocaloric, and pyroelectric properties of PMN–PT thin films. These Sm-PMN–PT thin films exhibit fatigue-free performance up to 109 charge–discharge cycles and maintain thermal stability across a wide temperature range from −40 to 200 °C. Notably, the films demonstrate a colossal electrocaloric effect with a temperature change of 59.4 K and a remarkable pyroelectric energy density reaching 40 J cm–3. By using scanning transmission electron microscopy and phase-field modeling, we revealed that these exceptional properties arise from the increased local structural heterogeneity and strong local electric fields along spontaneous polarization directions, facilitating the nucleation of polymorphic nanodomains characterized by a slush-like polar structure. These findings highlight the enormous potential of Sm-PMN–PT films in capacitive energy storage and solid-state electrothermal energy interconversion. Furthermore, this approach holds broad potential for other relaxor ferroelectrics by enabling the manipulation of nanodomain structures, paving the way for developing robust multifunctional materials.