Stabilization of divalent Eu(2+) in fluorosilicate glass-ceramics via lattice site substitution.
Stabilization of divalent Eu(2+) in fluorosilicate glass-ceramics via lattice site substitution.
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DOI：
10.1039/c8ra06843g
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发表时间：
2018-10-04
期刊：
影响因子：
3.9
通讯作者：
Han, Gaorong
中科院分区：
文献类型：
--
作者：
Wang, Chenhao;Chen, Xiaotong;Luo, Xue;Zhao, Junjie;Qiao, Xvsheng;Liu, Yong;Fan, Xianping;Qian, Guodong;Zhang, Xianghua;Han, Gaorong
Fluorosilicate glasses and glass-ceramics with MF2 (M = Ca, Sr, Ba), ZnF2 or LaF3 components were investigated to host divalent Eu2+ for photoluminescence (PL) application. X-ray diffraction phase identification and a series of spectroscopic analyses were performed to reveal the relationship between microstructure and the reduction of Eu3+ → Eu2+. The precursor glasses were believed being constituted by silicate-rich phases and fluoride-rich phases, due to the immiscibility of fluoride-and-silicate mixed glass system. After heat treatment, the fluoride-rich glass phases could transform into fluoride crystalline phase in the glass-ceramics. Europium tended to enrich in the fluoride-rich phases in the glasses or in the precipitated fluoride crystalline phases in the glass-ceramics. Small amounts of Eu3+ were reduced to Eu2+ in the glasses where the electronegativity had a crucial impact. In contrast, large amounts of Eu3+ were reduced to Eu2+ in the glass-ceramics containing MF2 nanocrystals, where the reduction was determined by lattice site substitution. Using ZnAl2O4 containing glass-ceramics as reference, it was evidenced that the similar and a little larger radii between sites and substitution ions are the prerequisite for Eu3+/M2+ substitution. And using LaF3 containing glass-ceramics as reference, it was certified that unbalanced charge at substitution sites induce the Eu3+ → Eu2+ reduction. Both valency and ionic radius determine the Eu3+ → Eu2+ reduction on the substituted lattice sites in glass-ceramics.
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