How to induce red persistent luminescence in biocompatible Ca3(PO4)2
How to induce red persistent luminescence in biocompatible Ca3(PO4)2
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DOI：
10.1039/c2tc00138a
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发表时间：
2013-01-01
影响因子：
6.4
通讯作者：
Viana, Bruno
中科院分区：
文献类型：
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作者：
Bessiere, Aurelie;Lecointre, Aurelie;Viana, Bruno
高度生物相容性的β-磷酸三钙（β-TCP）β-Ca-3（PO 4）（2）被定制为发出适合小动物体内成像的强烈红色持久发光。选择取代八面体Ca 5位点的Mn 2+作为发光掺杂剂，其在类似于660 nm处显示T-4（1）（（4）G）->（6）A（1）（S-6）发射。在Ar-H-2中退火的TCP：Mn ~（2+）样品仅表现出低温热释光（TSL），因此室温下的持续发光（RT）较弱。Ln（3+）（Ln = Tb，Dy）共掺杂增强了Mn ~（2+）的X射线激发发光，同时完全消除了TSL。随后的Ar-H-2退火的（Ln（3+），Mn 2+）共掺杂的TCP恢复强烈的TSL。TSL机制被描述为在Mn 2+的深空穴捕获和在还原产生的缺陷处的浅电子捕获，即最可能的二磷酸盐。Tb ~（3+）共掺杂在室温TSL峰以下促进TSL，Dy ~（3+）共掺杂在320 ~ 450 K诱导强烈的TSL。因此，相对于用于体内成像的硅酸盐参考，在Ar-H-2中退火的TCP：Mn 2+，Dy 3+显示出高度增强的X射线激发的持续发光。
Highly biocompatible beta-TriCalcium Phosphate (beta-TCP) beta-Ca-3(PO4)(2) was tailored to emit intense red persistent luminescence suitable for small animal in vivo imaging. Mn2+ substituting the octahedral Ca5 site was selected as the luminescent dopant showing T-4(1) ((4)G) -> (6)A(1) (S-6) emission at similar to 660 nm. TCP:Mn2+ annealed in Ar-H-2 showed only low temperature thermally stimulated luminescence (TSL) and therefore persistent luminescence at room temperature (RT) was weak. Ln(3+) (Ln = Tb, Dy) co-doping strongly enhanced Mn2+ X-ray excited optical luminescence while totally annihilating TSL. A subsequent Ar-H-2 annealing of (Ln(3+), Mn2+) codoped TCPs restored intense TSL. The TSL mechanism was described in terms of deep hole trapping at Mn2+ and shallow electron trapping at defects created by reduction, i.e. most probably diphosphates. While Tb3+ co-doping promoted below RT TSL peaks, Dy3+ co-doping induced intense TSL between 320 and 450 K. TCP:Mn2+, Dy3+ annealed in Ar-H-2 therefore showed highly enhanced X-ray excited persistent luminescence relative to the silicate reference used for in vivo imaging.