Thermally Induced Lattice-Defective Oxygen Breathing in Perovskite-Structure Stannates with High-Contrast Reversible Thermochromism.

Inorganic thermochromic materials exhibit a tunable color gamut and a wide chromatic temperature range, indicating their potential for intelligent adaptive applications in thermal warning, temperature indication, thermal regulation, and interactive light-to-thermal energy conversion. However, most metal-oxide-based thermochromic materials show weak chromaticity adaption with the change of temperature, which needs further understanding of the microscopic principle to clarify the potential route to improve the contrast and identifiability for fabricating better thermochromic materials. Using perovskite-structure (AMO3 ) alkaline earth metal stannate (Ba1- x Sr x SnO3 , 0.0 ≤ x ≤ 1.0) as a model system, this paper reports for the first time the mechanism of the properties of thermally induced defect-enhanced charge transfer-type (CTT) thermochromic materials and the strategy for regulating their thermochromic properties by A-site cations. BaSnO3 exhibits continuously reversible thermochromic properties with high contrast from weak light yellow ( b * = 11) to strong bright yellow ( b * = 58) between room temperature and 550 °C. In-situ high-temperature X-ray diffraction (in-situ XRD), in-situ UV-vis absorption spectroscopy (in-situ UV-vis), thermogravimetric (TG), and electron paramagnetic resonance (EPR) spectra indicate that this excellent thermochromic phenomenon is attributed to the weakening of Sn-O bond hybridization at high temperatures, as well as the formation of a large number of oxygen vacancies at the top of the valence band, and the enhanced charge transfer resulting from the generation of impurity levels in the Sn2+ 5s2 intermediate. Replacing Ba2+ by Sr2+ in Ba1- x Sr x SnO3 successfully tuned the thermochromic properties, which is attributed to the Sr2+ doping level-directed oxygen defect concentration and deoxygenation rate. The demonstrated defect-enhanced charge transfer behavior promotes a feasible route for lattice oxygen-mediated thermochromic materials and provides a fundamental relationship between thermally induced defects and colorimetry.