Soft Lattice and Dual-Emitter Engineering in Cr ³⁺ -Doped Fluorides: Achieving Highly Sensitive and High-Fidelity Near-Infrared Optical Thermometry

Cr³⁺-activated near-infrared phosphors are a promising optical thermometry platform in biomedicine and industrial applications, yet confront low lifetime sensing sensitivity (<i>S</i>_r < 2% K^-1). Here, Li₃GaF₆:Cr³⁺ is proposed as a high-sensitive, high-fidelity thermometry via a soft structure and dual-emitter modulation. Two Ga sites yield a dual-emitter mechanism: isolated Cr³⁺ ions and spatially confined Cr³⁺-Cr³⁺ pair (<5 Å interatomic distance)─a novel observation in fluorides. Density functional theory, Rietveld refinement, and luminescence behavior confirm that Cr³⁺ evenly occupies both Ga sites. Isolated Cr³⁺ centers exhibit rapid emission intensity and lifetime decay with temperature due to strong electron-phonon coupling and enhanced parity-forbidden transition probability from asymmetric soft lattice expansion. The formation of the Cr³⁺-Cr³⁺ pair suppresses energy migration between Cr³⁺ ions and eliminates spectral crosstalk within the dual-emitter. Isomorphic Li₃AlF₆:Cr³⁺ displays similar phenomena but slower decay, smaller lattice expansion, and better structure stability, highlighting soft lattice's role in thermal quenching. A fabricated Li₃GaF₆:Cr³⁺-based optical fiber thermometric platform achieves minimal temperature uncertainty (<i>∼</i>0.027 K) and a high <i>S</i>_r of 4.08% K^-1 at 423 K. An application demonstration on real-time temperature pointing of stainless-steel vessels validates an accuracy comparable to that of commercial thermometers. This work advances soft lattice design for high-performance optical thermometry and pioneers spatial structural confinement engineering of Cr³⁺-Cr³⁺ pair in fluorides.