F/Cl比对卤磷酸钙固溶体Bi离子掺杂位点及价态的调控

doi:10.15541/jim20160471

摘要/Abstract

摘要：

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。

关键词: 卤磷酸钙, Bi, 发光性能, 调控

Abstract:

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 content 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 scientific reference for controlling the valence state of Bi ions in crystals.

Key words: calcium halophosphate, bismuth, luminescence properties, control

中图分类号:

O482

张庆福, 李臣, 宋志国, 李永进, 邱建备, 杨正文. F/Cl比对卤磷酸钙固溶体Bi离子掺杂位点及价态的调控[J]. 无机材料学报, 2017, 32(6): 661-666.

ZHANG Qing-Fu, LI Chen, SONG Zhi-Guo, LI Yong-Jin, QIU Jian-Bei, YANG Zheng-Wen. Tuning Bismuth Activator Valence in Calcium Halophosphate Solid Solution by Controlling Activator Site[J]. Journal of Inorganic Materials, 2017, 32(6): 661-666.

图/表 6

Fig. 1 Two cationic sites and crystal structure of Ca5(PO4)3M

Fig. 2 (a) XRD patterns and (b) A-lattice lattice parameter of the prepared samples varies linearly with the change of F content

Fig. 3 Excitation and emission spectra of (a) Ca4.99(PO4)3Cl and (b) Ca4.99(PO4)3F doped with 1% Bi

Fig. 4 The emission of (a) Bi2+ and (b) Bi3+-doped Ca4.99Bi0.01 (PO4)3 F(1-x)Clx (x =0.4, 0.5, 0.6, 0.7 and 0.8)

Fig. 5 Triangular-planar arrangement of Ca3M in haloapatite along the z-axis of (a) flourapatite, (b) chlorapatite, and (c) haloapatite solid solution. Substitution of Cl- for F- into the triangular arrangement and splitting of the Ca(2) site into Ca(2)a and Ca(2)b

Fig. 6 The emission peak position of Bi2+ ions in samples with different F contents

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