本工作研究了卤素离子含量对卤磷酸钙固溶体中Bi离子的价态和发光性能的影响.荧光分析表明,卤素磷酸钙中的Bi2+/Bi3+可以通过其F-/Cl-组分变化实现有效调控;当卤素离子全部为Cl-离子时,晶体中Bi2+全部消失.上述现象的主要原因在于,当卤素离子为F或者Cl时,晶体中与其邻近的Ca(2)位点可以被分裂为Ca(2)a或Ca(2)b两种不同的格位,而Ca(2)a位点则有利于实现Bi3+的自还原.上述研究结果可以为Bi离子在晶体中的价态调控提供指导.
Effect of halide ions on valence state and luminescence property of Bi ions in calcium halophosphates was investigated. Bi-activated fluorapatite-chlorapatite solid solutions were synthesized by a solid state reaction. The con-tent ratio between Bi2+ and Bi3+ ions in the crystals could be tuned rationally by the component ratio of F-/Cl-, and the absent emission of Bi2+ ion occur when halide ions are all occupied by Cl-ions. The origin of this change is because the Ca2 site of calcium halophosphate is split into Ca(2)a and Ca(2)b sites for F– and Cl- as the nearest neighbors, and the Ca(2)a is adopted to offer activator site that enables Bi3+ to be self-reduced. The results in this study can provide a sci-entific reference for controlling the valence state of Bi ions in crystals.
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