From Disorder to Function: Entropy-Engineered Broadband Photonics with Ion-Transport-Stabilized Spectral Fidelity

Abstract

The high-entropy halide-perovskite field has expanded rapidly, yet a key gap remains: configurational entropy is not yet a reliable, designable lever to co-deliver expanded photonic functionality and operational robustness with a composition-transferable mechanistic basis. Here we develop entropy-engineered rare-earth halide double-perovskite single crystals, Cs2Na(Sb, RE)Cl6 (RE3+ = Sc3+, Er3+, Yb3+, Tm3+), that simultaneously expand near-infrared (NIR) functionality and establish a mechanistic stability rule. Near-equiatomic B(III)-site alloying yields a single-phase high-entropy solid solution (Delta_Sconfig about 1.6R). Sb3+ serves as a sensitizer that unifies excitation and cooperatively activates multiple lanthanide channels, transforming the parent single-mode response into a broadband NIR output (~850-1600 nm) with three spectrally orthogonal fingerprint bands at 996, 1220, and 1540 nm. This tri-peak, self-referenced output enables redundancy-based ratiometric solvent identification and quantitative mixture sensing with reduced susceptibility to intensity drift. Accelerated aging under humidity and oxygen shows improved phase and emission stability versus single-component analogues. DFT and molecular dynamics attribute the robustness to strongly suppressed RE${}^{3+}$/Cl${}^{-}$ self-diffusion despite comparable H${}_2$O/O${}_2$ adsorption, kinetically impeding ion-migration-assisted reconstruction and degradation. Integration into a phosphor-converted LED delivers spectrally stable, broadband NIR illumination, establishing entropy engineering as a practical handle to couple expanded photonic functionality with mechanistically accountable durability in metal-halide photonics.