AbstractBroad‐temperature optical thermometry necessitates materials with exceptional sensitivity and stability across varied thermal conditions, presenting challenges for conventional systems. Here, we report a lead‐free, vacancy‐ordered perovskite Cs2TeCl6, that achieves precise temperature sensing through a novel combination of self‐trapped excitons (STEs) photoluminescence (PL) lifetime modulation and unprecedented fifth‐order phonon anharmonicity. The STEs PL lifetime demonstrates a highly temperature‐sensitive response from 200 to 300 K, ideal for low‐to‐intermediate thermal sensing. In contrast, the Eg phonon mode undergoes significant linewidth broadening due to five‐phonon scattering processes, with a distinct nonlinear temperature dependence up to 500 K. This fifth‐order anharmonic effect enhances Raman‐based temperature sensitivity, yielding a specific sensitivity (Sr) of 0.577 % K–1 at 330 K and remaining above 0.5 % K–1 at elevated temperatures. This study presents the first evidence of fifth‐order anharmonic effects enhancing Raman‐based temperature sensitivity, establishing Cs2TeCl6 as a versatile candidate for broad‐temperature optical thermometry and opening new avenues for precise non‐contact temperature sensing in advanced technological applications.
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