K_2MgSiO_4∶Eu~(3+),Tb~(3+)荧光粉的发光性质和能量传递
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摘要
采用高温固相法合成K_2MgSiO_4∶Eu~(3+),Tb~(3+)系列荧光材料.通过X射线衍射谱、光致发光谱以及荧光寿命对材料的物相结构和发光性质进行了表征和研究.结果表明:系列样品的X射线衍射图谱衍射峰与标准卡片吻合得很好,实验浓度范围内Eu~(3+)、Tb~(3+)单掺或共掺没有改变K_2MgSiO_4的晶体结构.由材料的光致发光谱可以看出:Eu~(3+)单掺K_2MgSiO_4样品在394nm(~(7 )F_0→~(5 )L_6)激发下,显示主峰为613nm(~(5 )D_0→~7F_2)处的红光发射;Tb~(3+)单掺K_2MgSiO_4样品在378nm(~(7 )F_6→~(5 )G_6)激发下,显示主峰为542nm(~(5 )D_4→~7F_5)处的绿光发射.当Eu~(3+)和Tb~(3+)共掺于K_2MgSiO_4基质中时,样品呈现出Eu~(3+)较强的特征发射,Tb~(3+)发射峰则较弱,并且随着掺入Tb~(3+)离子浓度的增加,Eu~(3+)的发射明显增强,Tb~(3+)的发射没有明显变化.另外,当固定Eu~(3+)浓度,逐渐增加Tb~(3+)离子掺杂浓度时,Eu~(3+)的荧光寿命逐渐增加;固定Tb~(3+)浓度,逐渐增加Eu~(3+)离子掺杂浓度时,Tb~(3+)的荧光寿命逐渐减小.这些现象确定了K_2MgSiO_4∶Eu~(3+),Tb~(3+)荧光材料中存在Tb~(3+)→Eu~(3+)的能量传递关系,使得K_2MgSiO_4基质中Eu~(3+)红光发射得到改善和提高.
A series of fluorescent materials K_2MgSiO_4∶Eu~(3+),Tb~(3+)were synthesized by the high temperature solid phase method.The phase structure and luminescent properties of the materials were characterized and studied by X-ray diffraction,photoluminescence and fluorescence lifetime.The results show that the X-ray diffraction pattern diffraction peaks of the series samples agree well with the standard card,Eu~(3+),Tb~(3+)single doping or co-doping could not change the crystal structure of K_2MgSiO_4in the experimental concentration range.It can be seen from the photoluminescence spectrum of the material that the photoluminescence spectrum of Eu~(3+)doped K_2MgSiO_4reveal a red light emission at 613nm(~(5 )D_0→~7F_2)with an excitation at 394nm(~7F_0→~(5 )L_6);With Tb~(3+)ion singly doped K_2MgSiO_4shows a green light emission at 542nm(~(5 )D_4→~7F_5)with an excitation at 378nm(~7F_6→~(5 )G_6).When Eu~(3+)and Tb~(3+)are co-doped in the K_2MgSiO_4,the sample exhibits a strong characteristic emission of Eu~(3+),the Tb~(3+)emission peak is weaker,and with the increase of the concentration of Tb~(3+)ions,the emission of Eu~(3+)is obviously enhanced,while there is no significant change in the emission of Tb~(3+).In addition,when the Eu~(3+)concentration is fixed and the Tb~(3+)ion doping concentration is gradually increased,the fluorescence lifetime of Eu~(3+)increased gradually;when the concentration of Tb~(3+)is fixed and the Eu~(3+)ion doping concentration is gradually increased,the fluorescence lifetime of Tb~(3+)decreased gradually.These phenomena determine the energy transfer relationship of Tb~(3+)→Eu~(3+)in K_2MgSiO_4∶Eu~(3+),Tb~(3+)fluorescent materials.This relationship improves and enhances Eu~(3+)red light emission in the K_2MgSiO_4matrix.
A series of fluorescent materials K_2MgSiO_4∶Eu~(3+),Tb~(3+)were synthesized by the high temperature solid phase method.The phase structure and luminescent properties of the materials were characterized and studied by X-ray diffraction,photoluminescence and fluorescence lifetime.The results show that the X-ray diffraction pattern diffraction peaks of the series samples agree well with the standard card,Eu~(3+),Tb~(3+)single doping or co-doping could not change the crystal structure of K_2MgSiO_4in the experimental concentration range.It can be seen from the photoluminescence spectrum of the material that the photoluminescence spectrum of Eu~(3+)doped K_2MgSiO_4reveal a red light emission at 613nm(~(5 )D_0→~7F_2)with an excitation at 394nm(~7F_0→~(5 )L_6);With Tb~(3+)ion singly doped K_2MgSiO_4shows a green light emission at 542nm(~(5 )D_4→~7F_5)with an excitation at 378nm(~7F_6→~(5 )G_6).When Eu~(3+)and Tb~(3+)are co-doped in the K_2MgSiO_4,the sample exhibits a strong characteristic emission of Eu~(3+),the Tb~(3+)emission peak is weaker,and with the increase of the concentration of Tb~(3+)ions,the emission of Eu~(3+)is obviously enhanced,while there is no significant change in the emission of Tb~(3+).In addition,when the Eu~(3+)concentration is fixed and the Tb~(3+)ion doping concentration is gradually increased,the fluorescence lifetime of Eu~(3+)increased gradually;when the concentration of Tb~(3+)is fixed and the Eu~(3+)ion doping concentration is gradually increased,the fluorescence lifetime of Tb~(3+)decreased gradually.These phenomena determine the energy transfer relationship of Tb~(3+)→Eu~(3+)in K_2MgSiO_4∶Eu~(3+),Tb~(3+)fluorescent materials.This relationship improves and enhances Eu~(3+)red light emission in the K_2MgSiO_4matrix.
引文
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[2]XIA Yu-fei,CHEN Jian,LIU Yan-gai,et al.Luminescence properties and energy transfer in K2MgSiO4∶Ce3+,Tb3+as a green phosphor[J].Materials Express,2016,6(1):37-44.
[3]YANG Rong,TANG Hui-dong.Synthesis and luminescence properties of red-emitting K2MgSiO4∶Eu3+phosphors[J].International Journal of Modern Physics B,2017,31(4):1744058.
[4]ZHANG Zhi-jun,CHEN Hao-hong,YANG Xin-xin,et al.Preparation and luminescent properties of Eu3+,and Tb3+,ions in the host of CaMoO4[J].Materials Science&Engineering B,2007,145(1):34-40.
[5]NARESH V,BUDDHUDU S.Energy transfer based enhanced red emission intensity from(Eu3+,Tb3+):LFBCd optical glasses[J].Journal of Luminescence,2013,137(9):15-21.
[6]ZHANG Xin-guo,ZHOU Li-ya,PANG Qi,et al.Tunable Luminescence and Ce3+→Tb3+→Eu3+Energy Transfer of Broadband-Excited and Narrow Line Red Emitting Y2SiO5∶Ce3+,Tb3+,Eu3+Phosphor[J].Journal of Physical Chemistry C,2014,118(14):7591-7598.
[7]YUAN Shuang-long,WANG Lu-ting,YANG Yun-xia,et al.Novel color-tunable Gd2O2CN2∶Tb3+,Eu3+,phosphors:Characterization and photoluminescence properties[J].Ceramics International,2016,42(10):12508-12511.
[8]张思远.稀土离子的光谱学[M].北京:科学出版社,2008.
[9]QIU Gui-ming,XU Cheng-ke,HUANG Chong.Preparation and luminescent properties of a green Ca2SnO4∶Tb3+phosphor[J].Spectroscopy&Spectral Analysis,2011,31(11):2906-2909.邱桂明,许成科,黄翀.Ca2SnO4∶Tb3+绿色荧光粉的制备及光致发光研究[J].光谱学与光谱分析,2011,31(11):2906-2909.
[10]WANG Jian,NING Gui-ling,GONG Wei-tao,et al.Synthesis and luminescence properties of a novel Eu3+,Tb3+,codoped Al18B4O33,whiskers by agel nano-coating method[J].Journal of Materials Science,2011,46(5):1259-1263.
[11]YANG Jun,ZHANG Cui-miao,LI Chun-xia,et al.Energy transfer and tunable luminescence properties of Eu3+in TbBO3 microspheres via a facile hydrothermal process[J].Inorganic Chemistry,2008,47(16):7262-7270.
[12]WAN Ying,HE Jiu-yang,MA Yuan-yuan,et al.Synthesis and luminescence properties of a new type of green fluorescent powder BaAl2Si2O8∶Tb3+,Ce3+[J].Spectroscopy&Spectral Analysis,2017,37(5):1595-1600.
[13]LIANG Zhi-juan,MO Fu-wang,ZHANG Xing-guo,et al.Optical properties and energy transfer of NaCaPO4∶Tb3+,Eu3+phosphors[J].Ceramics International,2014,40(5):7501-7506.
[14]TANG Hui-dong,YANG Rong,HUANG Yan-lin.A novel red-emitting Eu3+-doped Na2 MgSiO4 phosphor with high intensity of 5 D0-7F4transition[J].Journal of Alloys and Compounds,2017,714(8):263-269.
[15]SU Xiao-na,WAN Ying,ZHOU Zhi-xuan,et al.Luminescence properties and energy transfer of Na2CaSiO4∶Sm3+,Eu3+phosphor[J].Acta Physica Sinica,2017,66(23):91-97.苏小娜,万英,周芷萱,等.Na2CaSiO4∶Sm3+,Eu3+荧光粉的发光特性和能量传递[J].物理学报,2017,66(23):91-97.
[16]GUO Hai,ZHANG Hao,LI Jing-jing,et al.Blue-white-green tunable luminescence from Ba2Gd2Si4O13∶Ce3+,Tb3+phosphors excited by ultraviolet light[J].Optics Express,2010,18(26):27257.