Highly Luminous N^3--Substituted Li₂MSiO_4-δN_2/3δ:Eu²⁺ (M = Ca, Sr, and Ba) for White NUV Light-Emitting Diodes

The N^3--substituted Li₂MSiO₄:Eu²⁺ (M = Ca, Sr, and Ba) phosphors were systematically prepared and analyzed. Secondary-ion mass spectroscopy measurements revealed that the average N^3- contents are 0.003 for Ca, 0.009 for Sr, and 0.032 for Ba. Furthermore, the N^3- incorporation in the host lattices was corroborated by infrared and X-ray photoelectron spectroscopies. From the photoluminescence spectra of Li₂MSiO₄:Eu²⁺ (M = Ca, Sr, and Ba) phosphors before and after N^3- doping, it was verified that the enhanced emission intensity of the phosphors is most likely due to the N^3- doping. In Li₂MSiO₄:Eu²⁺ (M = Ca, Sr, and Ba) phosphors, the maximum wavelengths of the emission band were red-shifted in the order Ca < Ba < Sr, which is not consistent with the trend of crystal field splitting: Ba < Sr < Ca. This discrepancy was clearly explained by electron-electron repulsions among polyhedra, LiO₄-MO , SiO₄-MO , and MO -M'O associated with structural difference in the host lattices. Therefore, the energy levels associated with the 4f⁶5d energy levels of Eu²⁺ are definitely established in the following order: Li₂CaSiO₄:Eu²⁺ > Li₂BaSiO₄:Eu²⁺ > Li₂SrSiO₄:Eu²⁺. Furthermore, using the Williamson-Hall (W-H) method, the determined structural strains of Li₂MSiO₄:Eu²⁺ (M = Ca, Sr, and Ba) phosphors revealed that the increased compressive strain after N^3- doping induces the enhanced emission intensity of these phosphors. White light-emitting diodes made by three N^3--doped phosphors and a 365 nm emitting InGaN chip showed the (0.333, 0.373) color coordinate and high color-rendering index (R _a = 83). These phosphor materials may provide a platform for development of new efficient phosphors in solid-state lighting field.