Photoluminescence tuning via cation substitution in oxonitridosilicate phosphors: DFT calculations, different site occupations, and luminescence mechanisms

Tuning and optimizing luminescent properties of oxonitridosilicates phosphors are important for white light-emitting diode (WLED) applications. To improve the color rendering index, correlated color temperature and thermal stability of layer-structured MSi₂O₂N₂:Eu (M = Sr, Ba) phosphors, cation substitutions have been used to adjust their luminescent properties. However, the underlying mechanisms are still unclear. In this research, a series of (Sr_1-xBa_x)Si₂O ₂N₂:Eu (0 ≤ x ≤ 1) compounds were prepared by solid-state reaction, after which systematic emission variations were investigated. The crystal structures of (Sr_1-xBa_x)Si ₂O₂N₂:Eu (0 ≤ x ≤ 1) are nominally divided into three sections, namely, Phase 1 (0 ≤ x ≤ 0.65), Phase 2 (0.65 < x < 0.80), and Phase 3 (0.80 ≤ x ≤ 1) based on the X-ray diffraction measurements. These experimental results are further confirmed by optimizing the crystal structure data with first-principle calculations. Continuous luminescence adjustments from green to yellow are observed in Phase 1 with gradual replacement of Sr²⁺ with Ba²⁺, and the abnormal redshift is clarified through extended X-ray absorption fine structure analysis. Sr(Eu)-O/N bond length shrinkage in local structure causes the redshift emission, and the corresponding luminescence mechanism is proposed. Controllable luminescence in Phase 2 (from blue to white) and Phase 3 (from cyan to yellowish green) are observed. Based on the high-resolution transmission electron microscopy and selected area electron diffraction analysis, the two kinds of luminescence tuning are attributed to phase segregation. This study serves as a guide in developing oxonitride luminescent materials with controllable optical properties based on variations in local coordination environments through cation substitutions.