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共掺杂荧光粉的发光性质及能量传递(3)
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摘要:利用Blasse[18]提出的式(3),可以计算出Er3+-Cr3+之间发生能量传递的临界距离. 式中,REr-Cr为Er3+到Cr3+能量传递临界距离,Xc为临界浓度,N为一个晶胞中可以取
利用Blasse[18]提出的式(3),可以计算出Er3+-Cr3+之间发生能量传递的临界距离.
式中,REr-Cr为Er3+到Cr3+能量传递临界距离,Xc为临界浓度,N为一个晶胞中可以取代的格位,V为体积.对于BaAl2Si2O8基质,Xc=0.015,N=2,V=147.5 nm3,计算可得能量传递的临界距离REr-Cr=4.5 nm,远大于0.3~0.4 nm,这表明Er3+和Cr3+通过交换作用发生能量传递的概率很小.因此,Er3+→ Cr3+能量传递主要是通过电多极相互作用.根据Dexter[19]理论,如果能量传输发生在同一类原子之间,那么相互作用的强度可以通过发射光谱的强度来确定.发光强度I与掺杂摩尔分数x之间的关系为
式中,c为常数,n为多极相互作用函数.当n=6、8、10时,分别对应于电偶极-电偶极、电偶极-电四极、电四极-电四极相互作用.在550 nm激发下,测得694 nm的发射强度,做lg(I/x)与lgx的关系图,如图7,得到直线斜率-n/3=-1.99,n≈6,表明BaAl2Si2O8:1%Cr3+,x%Er3+的浓度猝灭机理是电偶极-电偶极相互作用.
图7 BaAl2Si2O8:1%Cr3+,x%Er3+中lg(I/x)与lgx的关系Fig.7 Correlation between lg(I/x) and lgxfor theBa Al2Si2O8:1%Cr3+,x%Er3+samples
3 结论
本文利用高温固相法合成了BaAl2Si2O8:Cr3+, Er3+系列荧光材料,并研究了Cr3+, Er3+单掺及共掺样品的发光性质及其之间的联系.单掺Cr3+和Er3+的BaAl2Si2O8样品分别显示红光和绿光发射.共掺杂时,样品呈现Cr3+较强的特征激发,Er3+激发峰则较弱,并伴随掺入Er3+离子浓度增加,Cr3+的发射和激发明显增强.通过对荧光光谱和荧光寿命的分析以及理论计算得到,Cr3+和Er3+之间存在两种能量传递,一种为辐射能量传递;另一种为共振能量传递,随着Er3+离子掺杂浓度增大时,Cr3+的发射峰强度呈现先逐渐增加后减少的趋势,在掺杂Er3+离子浓度为0.5%时,出现浓度猝灭.另外,当固定Cr3+浓度,逐渐增加Er3+离子掺杂浓度时,Cr3+的荧光寿命逐渐增加;当固定Er3+浓度,逐渐增加Cr3+离子掺杂浓度时,Cr3+的荧光寿命逐渐减少.这些现象确定了BaAl2Si2O8:Cr3+, Er3+荧光材料中存在Er→Cr能量传递,并计算得出是电偶极-电偶极相互作用.
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