Ba~(2+)共掺杂YPO_4∶Tb~(3+)荧光材料的水热合成与荧光性能
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摘要
采用水热法合成Ba~(2+)共掺杂YPO4∶Tb~(3+)荧光材料,并通过X射线衍射(XRD)、扫描电子显微镜(SEM)和荧光分光光度计等研究了合成样品的物相组成和荧光性能,并分析了Ba~(2+)掺杂量和反应体系pH值等对合成样品的物相结构及荧光性能的影响。结果表明,反应体系pH值和Ba~(2+)掺杂量直接影响所制备样品的结构与性能。少量Ba~(2+)(≤10%,原子分数,下同)共掺杂YPO4∶1%Tb~(3+)样品均为纯相四方晶系磷钇矿结构晶体,过量Ba~(2+)掺杂导致Ba_3(PO_4)_2杂质相的出现;pH值为6的水热环境下可获得高结晶度的单一相Ba~(2+)、Tb~(3+)共掺杂YPO4样品。激发和发射光谱测试结果表明,所制备的YPO4∶1%Tb~(3+),x%Ba~(2+)样品可被225nm的紫外光有效地激发而发射出强烈的Tb~(3+)特征的黄绿色光。一定量的Ba~(2+)共掺杂可以有效地提高YPO4∶1%Tb~(3+)样品的荧光性能,但过量(高于10%)的Ba~(2+)掺杂又会导致Tb~(3+)的荧光猝灭现象出现,最佳的Ba~(2+)共掺杂量为10%。所制备的YPO4∶1%Tb~(3+),10%Ba~(2+)样品在225nm紫外光激发下位于545nm处的发射带强度是YPO4∶1%Tb~(3+)样品的1.8倍。
Ba~(2+) co-doped YPO4∶Tb~(3+) phosphors were successfully synthesized by hydrothermal method.The crystal structure and optical properties of the as-synthesized samples were investigated by X-ray diffraction(XRD),scanning electron microscopy(SEM),photoluminescence(PL).The influences of Ba~(2+) co-doping concentration and precursor solution pH on the phase structure and luminescence properties of the as-products were investigated.The results show that the pH and Ba~(2+) co-doping concentration play the key role in the structure and luminescence properties of the as-synthesized samples.A small amount of Ba~(2+)(no more than10 at%)co-doped YPO4∶1 at%Tb~(3+)samples are single-phase crystals with tetragonal xenotime structure,and Ba_3(PO_4)_2 impurity phase can be observed in the sample co-doped with a large amount of Ba~(2+).The pure and high crystallinity Ba~(2+),Tb~(3+)co-doped YPO4 samples can be obtained at pH 6 condition.The results of excitation and emission spectra show that the YPO4∶1 at%Tb~(3+),xat% Ba~(2+) samples can be excited by 225 nm UV light and emit the characteristic yellow-green light of Tb~(3+).An appropriate amount of Ba~(2+)co-doped YPO4∶1 at% Tb~(3+)samples display enhanced luminescence,and a large amount of Ba~(2+)(more than 10 at%)co-doping in the YPO4∶1 at%Tb~(3+)samples can quench the Tb~(3+)emission.The optimized doping content of Ba~(2+)is 10 at%.The intensity of emission peak located at 545 nm of YPO4∶1 at%Tb~(3+),10 at% Ba~(2+)sample are 1.8 times as many of the YPO4∶1 at%Tb~(3+)sample.
Ba~(2+) co-doped YPO4∶Tb~(3+) phosphors were successfully synthesized by hydrothermal method.The crystal structure and optical properties of the as-synthesized samples were investigated by X-ray diffraction(XRD),scanning electron microscopy(SEM),photoluminescence(PL).The influences of Ba~(2+) co-doping concentration and precursor solution pH on the phase structure and luminescence properties of the as-products were investigated.The results show that the pH and Ba~(2+) co-doping concentration play the key role in the structure and luminescence properties of the as-synthesized samples.A small amount of Ba~(2+)(no more than10 at%)co-doped YPO4∶1 at%Tb~(3+)samples are single-phase crystals with tetragonal xenotime structure,and Ba_3(PO_4)_2 impurity phase can be observed in the sample co-doped with a large amount of Ba~(2+).The pure and high crystallinity Ba~(2+),Tb~(3+)co-doped YPO4 samples can be obtained at pH 6 condition.The results of excitation and emission spectra show that the YPO4∶1 at%Tb~(3+),xat% Ba~(2+) samples can be excited by 225 nm UV light and emit the characteristic yellow-green light of Tb~(3+).An appropriate amount of Ba~(2+)co-doped YPO4∶1 at% Tb~(3+)samples display enhanced luminescence,and a large amount of Ba~(2+)(more than 10 at%)co-doping in the YPO4∶1 at%Tb~(3+)samples can quench the Tb~(3+)emission.The optimized doping content of Ba~(2+)is 10 at%.The intensity of emission peak located at 545 nm of YPO4∶1 at%Tb~(3+),10 at% Ba~(2+)sample are 1.8 times as many of the YPO4∶1 at%Tb~(3+)sample.
引文
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23 Liu C,Hou D,Yan J,et al.Energy transfer and tunable luminescence of NaLa(PO3)4∶Tb3+/Eu3+under VUV and low-voltage electron beam excitation[J].J Phys Chem C,2014,118(6):3220.
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2 Gao Y Y,Zhan S P,Zhong H.Tuning of Ce3+doping on emissions of YPO4∶Tb3+,Ce3+microspheres and energy transfer between Ce3+and Tb3+[J].Chin J Nonferrous Metals,2012,22(12):3562(in Chinese).高永毅,占世平,钟慧.Ce3+对YPO4∶Tb3+,Ce3+微米球的发光调制及Tb3+与Ce3+间的能量传递[J].中国有色金属学报,2012,22(12):3562.
3 He Y,Zhao M,Song Y,et al.Effect of Bi 3+on fluorescence properties of YPO4∶Dy3+phosphors synthesized by a modified chemical co-precipitation method[J].J Lumin,2011,131(6):1144.
4 Yang J,Luo L,Chen Z,et al.Tb-doped YPO4phosphors:Polyacrylamide gel synthesis and optical properties[J].J Alloys Compd,2016,689:837.
5 Zhang L,Jiu H,Fu Y,et al.Preparation and photoluminescence enhancement of Li+and Eu3+co-doped YPO4hollow microspheres[J].J Rare Earths,2013,31(5):449.
6 Angiuli F,Cavalli E,Belletti A,et al.Synthesis and spectroscopic characterization of YPO4activated with Tb3+and effect of Bi 3+codoping on the luminescence properties[J].J Solid State Chem,2012,192:289.
7 Yang Y,Ding M,Song G,et al.Improved luminescence of YPO4∶Eu3+phosphors by codoping Ca2+[J].Chem Phys Lett,2015,639:67.
8 Zeng Xiaodao,Jia Xiaohui,Zhu Liping.Hydrothermal synthesis and luminescent properties of Co2+doped YPO4∶Eu3+phosphors[J].Rare Metals Cemented Carbides,2016(1):50(in Chinese).曾晓岛,贾晓卉,朱莉萍.Co2+掺杂YPO4∶Eu3+荧光材料的水热合成及其发光性能[J].稀有金属与硬质合金,2016(1):50.
9 Zhan Y,Du G,Chen N,et al.Photoluminescence properties of YVO4∶Eu3+,Ba2+nanoparticles prepared by an ion exchange method[J].Mater Sci Semicond Processing,2016,41:233.
10 Wang G,Qin W,Zhang D,et al.Enhanced photoluminescence of water soluble YVO4∶Ln3+(Ln=Eu,Dy,Sm,and Ce)nanocrystals by Ba2+doping[J].J Phys Chem C,2008,112(44):17042.
11 Li Keyan.Electronegativity scales in crystals and their applications[D].Dalian:Dalian University of Technology,2008(in Chinese).李克艳.晶体中的电负性标度及其应用[D].大连:大连理工大学,2008.
12 Zhang Feng.Preparation and photoluminescent properties of Eu3+,Tb3+activated oxysalt-based luminescence materials[D].Lanzhou:Lanzhou University,2012(in Chinese).张凤.Eu3+、Tb3+激活的几种含氧酸盐基发光材料的制备及其发光特性研究[D].兰州:兰州大学,2012.
13 Zhang Qi,Ma Yong,Deng Quan.Structural and optical properties of Sb-doped ZnO powders synthesized by hydrothermal method[J].J Chongqing University of Technology:Nat Sci,2012,26(8):61(in Chinese).张起,马勇,邓泉.水热法制备ZnO∶Sb粉体结构及光学性质[J].重庆理工大学学报:自然科学版,2012,26(8):61.
14 Fan Wenbo,Jiang Yuanru,Xu Ting.Synthesis,crystal structure and luminescent properties of Y,Pr and Tb-schiff base complexes[J].Mater Rev:Res,2015,29(6):15(in Chinese).范文博,江元汝,徐婷.稀土(Y、Pr、Tb)希夫碱配合物的合成、结构及荧光性质[J].材料导报:研究篇,2015,29(6):15.
15 Li X,Wang H,Guan L,et al.Influence of pH value on properties of YPO4∶Tb3+phosphor by co-precipitation method[J].J Rare Earths,2015,33(4):346.
16 Yan Yinglin,Wang Juan,Wang Liangliang.Influence of pH and CTAB on luminescent property of hydrothermally synthesized GdVO4∶Eu3+phosphors[J].Chin J Mater Res,2015(4):307(in Chinese).燕映霖,王娟,王亮亮.CTAB浓度和反应液的pH值对水热合成GdVO4∶Eu3+荧光粉性能的影响[J].材料研究学报,2015(4):307.
17 Li G,Liu S,Chu Z,et al.Synthesis and photoluminescence of coreshell structured spherical SiO2@YPO4∶Tb3+phosphors via sol-gel process[J].J Lumin,2012,132(11):2961.
18 Gu J,Zhong J,Liang H,et al.Competitive absorption of Eu3+and Tb3+codoped in NaGd(PO3)4 phosphors[J].Chem Phys Lett,2014,592:261.
19 Yang Liusai,Xie Aili,Yang Qintao.Influenced of hydrothermal and high temperature treatment on luminescence properties of BiPO4∶Tb3+nanocrystals[J].Chin J Mater Res,2016(2):156(in Chinese).杨流赛,谢爱理,杨勤桃.水热和高温烧结对BiPO4∶Tb3+纳米晶发光性能的影响[J].材料研究学报,2016(2):156.
20 Dou X,Zhao W,Song E,et al.Photoluminescence characterization and energy transfer of NaBa1-x-yPO4∶xCe3+,yTb3+phosphors[J].J Rare Earths,2012,30(8):739.
21 Su Ping,Li Bangxing.Theoretical analysis of spectra for Nd3+ions in CsCdBr3crystals[J].J Chongqing University of Technology:Nat Sci,2015(3):2(in Chinese).苏萍,李邦兴.掺杂Nd3+离子CsCdBr3晶体光谱的理论分析[J].重庆理工大学学报:自然科学版,2015(3):21.
22 Liu Xueying,Yang Jinyu,He Hanwei.Synthesis and optical properties of Tb3+doped Gd2Sn2O7nanophosphors[J].Mater Sci Eng Powder Metall,2014,19(6):978(in Chinese).刘雪颖,杨锦瑜,何捍卫.Tb3+掺杂Gd2Sn2O7纳米荧光材料的制备与光学性能[J].粉末冶金材料科学与工程,2014,19(6):978.
23 Liu C,Hou D,Yan J,et al.Energy transfer and tunable luminescence of NaLa(PO3)4∶Tb3+/Eu3+under VUV and low-voltage electron beam excitation[J].J Phys Chem C,2014,118(6):3220.
24 Yuan C,Xie H,Cai H,et al.Synthesis and luminescent properties of a novel green-emitting Tb(Ⅲ)complex and the excellent thermal stability for application[J].Opt Mater,2016,54:170.
25 Li Kaiyu,Wang Ruzhi,Qu Minghao.Downconversion materials preparation and the research of conversion efficiency in Pr3+,Yb3+co-doped YPO4[J].Chin J Lumin,2012,33(5):486(in Chinese).李开宇,王如志,曲铭浩.Pr3+,Yb3+共掺YPO4下转换材料的制备及其转光效率[J].发光学报,2012,33(5):486.