Giant photocaloric effects across a vast temperature range in ferroelectric perovskites

Abstract

Solid-state cooling presents an energy-efficient and environmentally friendly alternative to traditional refrigeration technologies that rely on thermodynamic cycles involving greenhouse gases. However, conventional caloric effects face several challenges that impede their practical application in refrigeration devices. Firstly, operational temperature conditions must align closely with zero-field phase transition points; otherwise, the required driving fields become excessively large. But phase transitions occur infrequently near room temperature. Additionally, caloric effects typically exhibit strong temperature dependence and are sizeable only within relatively narrow temperature ranges. In this study, we employ first-principles simulation methods to demonstrate that light-driven phase transitions in polar oxide perovskites have the potential to overcome such limitations. Specifically, for the prototypical ferroelectric KNbO$_{3}$ we illustrate the existence of giant photocaloric effects induced by light absorption ($\Delta S_{\rm PC} \sim 100$~J~K$^{-1}$~kg$^{-1}$ and $\Delta T_{\rm PC} \sim 10$~K) across a vast temperature range of several hundred Kelvin, encompassing room temperature. These findings are expected to be generalizable to other materials exhibiting similar polar behavior.