Bi3+ photoluminescence in Y1−xBixCa3(GaO)3(BO3)4 and energy transfer to Eu3+ and Tb3+ in co-doped phosphors

Abstract

Bi³⁺ possesses outer shell lone pair electrons, and, thus the so-involved photoluminescence (PL) is sensitive to the surrounding coordination. Besides, the similarity in the structural chemistry between Bi³⁺ and rare earth (RE) ions inspires us to investigate the Bi³⁺-PL performance in RE³⁺-containing hosts. Herein, Y_1−xBi_xCa₃(GaO)₃(BO₃)₄ (0.01 ≤ x ≤ 0.15) compounds were prepared by a high temperature solid state reaction method. The successful cationic doping and phase purity were confirmed by powder X-ray diffraction analysis. This series of phosphors exhibit the very strong absorption of Bi^{3+ 1}S₀ → ³P₁ at 272 nm along with the intense blue emission with a maximum at 399 nm and a full width at half maximum (FWHM) of 59 nm. They retained 78.86% of the emission intensity at 150 °C, with reference to that at room temperature. Moreover, Bi³⁺ could also behave as a sensitizer to enhance the emission efficiency of RE³⁺ and thus to realize color-tunable phosphors. The energy transfer was proved in the co-doped phosphors Y_0.95−yBi_0.05Eu_yCa₃(GaO)₃(BO₃)₄ (0.05 ≤ y ≤ 0.6) and Y_0.95−zBi_0.05Tb_zCa₃(GaO)₃(BO₃)₄ (0.05 ≤ z ≤ 0.6), and color-tunable emissions from blue to red, or from blue to green were realized in these two series of phosphors.