单一基质白光荧光粉Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu^(2+),xMn^(2+)的晶胞参数变化和光谱特性  

Lattice Parameters and Luminescent Property of Single-Phase White Light-Emitting Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu^(2+), xMn^(2+)Phosphors

作　　者：王飞[1,2] 田一光 张乔[3] WANG Fei;TIAN Yi-Guang;ZHANG Qiao(Experimental Center of Anhui Sanlian University, Hefei 230601, China;College of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China;College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, China)

机构地区：[1]安徽三联学院实验中心,合肥230601 [2]安徽大学化学化工学院,合肥230601 [3]温州大学化学与材料工程学院,温州325035

出　　处：《无机化学学报》2019年第1期25-33,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.20771086);安徽省教育厅重点项目(No.KJ2016A893);安徽省高校优秀青年人才支持计划项目(No.gxyq2018126);安徽三联学院科研项目(No.KJZD2018004;2015Z001;2013Z001);安徽三联学院质量工程项目(No.15zlgc008;16zlgc060;17zlgc030);国家级大学生创新创业项目(No.201710959055;201810959050)资助

摘　　要：利用高温固相反应制备了Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu^(2+),xMn^(2+)(x=0,0.05,0.10,0.15,0.20,0.25,0.30,0.325,0.35,0.375,0.40,0.425)一系列试样,系统研究了Mn^(2+)取代基质中Ca^(2+)进入晶格中对其晶胞参数和光谱特性影响。Mn^(2+)以类质同相替代Ca^(2+)进入晶体晶格中,形成了连续固溶体,试样均为三斜晶系,P空间群。随着Mn^(2+)掺杂量增加,晶胞参数(a,b,c,γ)和晶胞体积V均呈线性递减,且a轴减幅最大,b轴最小,晶面夹角(α,β)呈线性递增。在357 nm激发下,获得的Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu^(2+),xMn^(2+)发射光谱均有Eu^(2+)的4f→5d跃迁产生的433 nm和Mn^(2+)的~4T_1(~4G)→~6A_1(~6S)跃迁产生的567 nm两个宽带谱组成。在荧光粉Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu^(2+),xMn^(2+)中,Eu^(2+)与Mn^(2+)间存在能量传递,Eu^(2+)→Mn^(2+)间能量传递的临界距离R_(Eu-Mn)=0.947 1 nm,Eu^(2+)→Mn^(2+)能量传递过程为电四极-电四极的多极矩相互作用。通过改变Mn^(2+)掺杂量,在紫外芯片的有效激发下,荧光粉的发射光颜色可从蓝光区(0.158 2,0.086 0)逐渐移至近白光区(0.295 3,0.298 9),可获得一种紫外激发适用于白光LED的单一组分白色荧光粉。A series oF phosphors Ca09550xAl2Si2O8:0.045Eu^2+,xMn^2+(x=0,0.05,0.10, 0.15,0.20,0.25,0.30,0.325, 0.35, 0.375, 0.40, 0.425) were prepared via solid-state reaction. As Mn^2+ was substituted for Ca^2+ into the crystal lattice, the effect on its lattice parameters and spectral properties were discussed. The results show that complete solid solutions were formed in the whole range for x while Mn^2+ enterers CaAl2Si2O8 lattice and substitutes for Ca^2+. The samples belong to triclinic system, and P1 space group. The lattice parameters (a,b,c,γ) and unit cell volume of phosphors Ca09550xAl2Si2O8:0.045Eu^2+, xMn^2+ decreased linearly, and the lattice parameters (a,β) increased linearly as Mn^2+ content increased in the phosphors. When Mn^2+ substitutes for Ca^2+ the most obvious change is in cell parameter a, the second is c, and the minimum is b. When excited by 357 nm, the Ca0955-xAl2Si2O8:0.045Eu^2+Mn ^2+ phosphors exhibited two emission peaks centered at 433 and 567 n m , which are ascribed to 5 d-4f and ^4T1^(4G)→^6A1(^6S) transition of Eu^2+ and Mn ^2+, respectively. The results show that the existence of efficient energy transfer between Eu^2+ and Mn ^2+ in phosphors Ca0.955J!Al2Si2O8:0-045Eu^2+XMn^2+, the critical distance is calculated to be 0.947 1nm . The energy transfer between Eu^2+ and Mn^2+ was due to the electric dipole-dipole interaction of the resonance transfer. Under the effective excitation of the ultraviolet chip, by changing the amount of Mn^2+ doping, the color of the emitted light of the phosphors can be gradually shifted from blue light (0.1582, 0.086) to near white light (0.2953, 0.2989). UV-excited single-phase white light-emitting phosphors for white LEDs were available.

关 键 词：无机固体化学 CaAl2Si2O8:Eu^2+ Mn^2+ 晶胞参数 光谱特性 能量传递 

分 类 号：O614.371[理学—无机化学] O614.338[理学—化学]