Control of Luminescence by Tuning of Crystal Symmetry and Local Structure in Mn⁴⁺‐Activated Narrow Band Fluoride Phosphors

Abstract

Mn⁴⁺ -doped fluoride phosphors have been widely used in wide-gamut backlighting devices because of their extremely narrow emission band. Solid solutions of Na₂ (Si_x Ge_1-x )F₆ :Mn⁴⁺ and Na₂ (Ge_y Ti_1-y )F₆ :Mn⁴⁺ were successfully synthesized to elucidate the behavior of the zero-phonon line (ZPL) in different structures. The ratio between ZPL and the highest emission intensity υ₆ phonon sideband exhibits a strong relationship with luminescent decay rate. First-principles calculations are conducted to model the variation in the structural and electronic properties of the prepared solid solutions as a function of the composition. To compensate for the limitations of the Rietveld refinement, electron paramagnetic resonance and high-resolution steady-state emission spectra are used to confirm the diverse local environment for Mn⁴⁺ in the structure. Finally, the spectral luminous efficacy of radiation (LER) is used to reveal the important role of ZPL in practical applications.