YPO_4:Ln~(3+)(Ln=Eu,Tb)球形荧光粉的合成及其发光性能优化
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摘要
采用水热法结合高温退火处理制备了YPO_4:Ln~(3+)(Ln=Eu,Tb)荧光粉。通过X射线粉末衍射(XRD)、扫描电镜(SEM)和荧光光谱(PL)对样品的结构、形貌和发光性能进行表征。结果表明:在水热条件下合成了含结晶水六角相结构的YPO_4·0.8H_2O:Eu~(3+)和YPO_4·0.8H2O:Tb~(3+)前躯体;经过800℃高温烧结2h后,前躯体失去结晶水后得到球形、尺寸均一、表面光滑、四方锆石结构的YPO_4:Eu~(3+)和YPO_4:Tb~(3+)荧光粉,颗粒平均粒径约为200nm。在396nm波长激发下,YPO_4:Eu~(3+)荧光粉可以获得Eu~(3+)离子的跃迁能级5D0→7FJ(J=1-4)特征发射,以磁偶极跃迁5D0→7F1(596nm)的发光强度最强,观.察到橙红色发射,且Eu~(3+)的最佳掺杂摩尔分数为11%。同时,YPO_4:Tb~(3+)荧光粉在372nm的光激发下,在548nm处的5D4→7F5跃迁具有最高的荧光强度,观察到绿光发射,且Tb~(3+)最佳掺杂摩尔分数为7%。
This study prepares YPO_4:Ln~(3+)(Ln=Eu,Tb)phosphors by hydrothermal method combined with high temperature sintering.The crystal structure,morphology and luminescent properties of the powders were characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and photoluminescence spectroscopy(PL),respectively.The results show that hexagonal structure YPO_4·0.8 H_2O:Eu~(3+)and YPO_4·0.8 H_2O:Tb~(3+)precursors with lattice water could be formed under hydrothermal condition.After sintering at 800 ℃ for 2 h,the tetragonal zircon structure YPO_4:Eu~(3+)and YPO_4:Tb~(3+)phosphors were obtained as the lattice water was released from hexagonal precursors,which are uniformly distributed spherical structure with about 200 nm in diameter.The emission spectrum of YPO_4:Eu~(3+)exhibits several sharp peaks corresponding to the transitions 5 D0→7 FJ(J=1-4)of Eu~(3+)under 396 nm excitation,among which the most intense luminescence intensity is at 596 nm,corresponding to 5 D0→7 F1 transition of Eu~(3+).The optimum doping mole concentration of Eu~(3+)is 11%.Furthermore,under excitation wavelength of 372 nm,YPO_4:Tb~(3+)spherical phosphors could generate a strong green emission at 548 nm of 5 D4→7 F5 transition,showing the optimum Tb~(3+)doping mole concentration of 7%.
This study prepares YPO_4:Ln~(3+)(Ln=Eu,Tb)phosphors by hydrothermal method combined with high temperature sintering.The crystal structure,morphology and luminescent properties of the powders were characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and photoluminescence spectroscopy(PL),respectively.The results show that hexagonal structure YPO_4·0.8 H_2O:Eu~(3+)and YPO_4·0.8 H_2O:Tb~(3+)precursors with lattice water could be formed under hydrothermal condition.After sintering at 800 ℃ for 2 h,the tetragonal zircon structure YPO_4:Eu~(3+)and YPO_4:Tb~(3+)phosphors were obtained as the lattice water was released from hexagonal precursors,which are uniformly distributed spherical structure with about 200 nm in diameter.The emission spectrum of YPO_4:Eu~(3+)exhibits several sharp peaks corresponding to the transitions 5 D0→7 FJ(J=1-4)of Eu~(3+)under 396 nm excitation,among which the most intense luminescence intensity is at 596 nm,corresponding to 5 D0→7 F1 transition of Eu~(3+).The optimum doping mole concentration of Eu~(3+)is 11%.Furthermore,under excitation wavelength of 372 nm,YPO_4:Tb~(3+)spherical phosphors could generate a strong green emission at 548 nm of 5 D4→7 F5 transition,showing the optimum Tb~(3+)doping mole concentration of 7%.
引文
[1] Yahiaoui Z,Hassairi M A,Dammak M.Synthesis and optical spectroscopy of YPO4:Eu3+orange-red phosphors[J].Journal of Electronic Materials,2017,46(8):4765-4773.
[2] Yahiaoui Z,Hassairi M A,Dammak M,et al.Tunable luminescence and energy transfer properties in YPO4:Tb3+,Eu3+/Tb3+phosphors[J].Journal of Luminescence,2018,194:96-101.
[3] FU Bing,OU Ya,LIU Huan,et al.Ba2+co-doped YPO4:Tb3+phosphors:hydrothermal synthesis and photoluminescence properties[J].Materials Review,2017,31(18):16-20.付兵,欧娅,刘欢,等.Ba2+共掺杂YPO4:Tb3+荧光材料的水热合成与荧光性能[J].材料导报,2017,31(18):16-20.
[4] HUO Qong-qian,YU Ben-wu,CHEN Xiao-li,et al.Hydrothermal preparation and white-light emission of YPO4:Dy3+,Eu3+phosphors[J].Journal of Optoelectronics·Laser,2015,26(11):2141-2147.霍涌前,于本武,陈小利,等.YPO4:Dy3+,Eu3+荧光粉的水热合成及白光发射[J].光电子·激光,2015,26(11):2141-2147.
[5] JIANG Chun-dong,ZHANG Ping,WU Jiang.The synthesis and light emitting research of YPO4:Gd,Eu phosphor[J].Science Technology and Engineering,2014,14(16):1-5.蒋春东,张萍,吴疆.YPO4:Gd,Eu荧光粉的制备和发光性能研究[J].科学技术与工程,2014,14(16):1-5.
[6] ZHANG Xiao-rong,REN Jiang-xue,OU Yang-yan,et al.Synthesis and fluorescence of YPO4·2H2O:Eu3+microflower structure[J].New Chemical Material,2016,44(5):67-69.张晓蓉,任建学,欧阳艳,等.YPO4·2H2O:Eu3+花状微米结构的合成及荧光性能研究[J].化工新型材料,2016,44(05):67-69.
[7] YANG Jin-yu,ZENG Xiao-dao,ZHU Li-ping,et al.Citric acid-assisted sol-gel synthesis and fluorescence research of Eu3+-doped YPO4 phosphors[J].Rare Metal and Cemented Carbides,2014,42(4):41-45.杨锦瑜,曾晓岛,朱莉萍,等.Eu3+掺杂YPO4荧光材料的柠檬酸辅助溶胶-凝胶法合成及其荧光性能研究[J].稀有金属与硬质合金,2014,42(4):41-45.
[8] ZHAO Ming-lei,LI Li-ping,LI Guang-she.Advances of solution chemistry in stabilizing different crystal phases of inorganic nano-compounds[J].CrystEngComm,2016,18(48):9209-9222.
[9] XIE Ji-xing,GENG Xiu-juan,GAO Rong-hua,et al.The preparation and luminescent properties of white phosphor Gd2(MoO4):Dy3+,Tm3+[J].Journal of Optoelectronics·Laser,2018,29(4):377-382.解吉星,耿秀娟,高荣华,等.白色荧光粉Gd2(MoO4):Dy3+,Tm3+的制备及发光性能[J].光电子·激光,2018,29(4):377-382.
[10]Gavrilovic T,Perisa J,Papan J,et al.Particle size effects on the structure and emission of Eu3+:LaPO4and EuPO4phosphors[J].Journal of Luminescence,2018,195:420-429.
[11]LI Zhao,XU Ke,JIANG Yuan-ru.Synthesis and luminescence properties of spherical NaY(MoO4)2:Sm3+phosphor[J].Journal of Synthetic Crystals,2016,45(2):525-528.李兆,徐克,江元汝.球形NaY(MoO4)2:Sm3+荧光粉的合成及荧光性能研究[J].人工晶体学报,2016,45(2):525-528.
[12]LI Zhao,ZHAO Xi-cheng,JIANG Yuan-ru.Preparation and photoluminescent property of sphere Y2.96Al5O12:0.04Ce3+phosphors for white light-emitting diodes[J].Spectroscopy and Spectral Analysis,2014,34(11):2918-2922.李兆,赵西成,江元汝.白光LED用球形Y2.96Al5O12:0.04Ce3+荧光粉的制备及光致发光[J].光谱学与光谱分析,2014,34(11):2918-2922.
[13]LI Xu,WANG Hao-yan,GUAN Li,et al.Influence of pH value on properties of YPO4:Tb3+phosphor by co-precipitation method[J].Journal of Rare Earths,2015,33(4):346-349.
[14]LI Guang-zhi,LIU Song-yan,CHU Zhen-sheng,et al.Synthesis and photoluminescence of core-shell structured spherical SiO2@YPO4:Tb3+phosphors via sol-gel process[J].Journal of Luminescence,2012,132(11):2961-2967.
[15]LIU Xu-yan,DING Nan,QU Chong-nian,et al.Controlled synthesis and luminescence properties of rare-earth doped YPO4 phosphor[J].Chinese Journal of Luminescence,2017,38(5):588-594.刘旭焱,丁楠,屈重年,等.稀土掺杂磷酸钇荧光粉的控制合成和发光性能[J].发光学报,2017,38(5):588-594.
[16]LI Xu-bo,DING Jian-hong,HUANG Qi-shu,et al.Luminescence of YPO4doped with Ce3+under UV excitation[J].Material Research and Application,2014,8(1):42-45.李许波,丁建红,黄奇书,等.紫外光激发(Y,Ce)PO4荧光粉的发光特性[J].材料研究与应用,2014,8(1):42-45.
[17]ZHANG Zhong-ju,SHI Jing,WANG Xiao-yan,et al.Vibrational and luminescent properties of LaPO4:Eu3+with different preparation conditions[J].Journal of Rare Earths,2016,34(11):1103-1110.
[18]ZHANG Yong-ming,SONG Guo-yi,CAO Qi-hua,et al.Preparation and luminescent properties of Eu3+doped GdPO4glass ceramic[J].Journal of Optoelectronics·Laser,2014,25(6):1124-1128.张永明,宋国轶,曹启华,等.Eu3+掺杂GdPO4微晶玻璃的制备及其发光特性的研究[J].光电子·激光,2014,25(6):1124-1128.
[19]WANG Fei,CHEN Hui-hui,TIAN Yi-guang,et al.Preparation and luminescent properties of red phosphor BaAl2Si2O8:Eu3+,Li+[J].Chinese Rare Earths,2017,38(2):80-86.王飞,陈慧慧,田一光,等.红色荧光粉BaAl2Si2O8:Eu3+,Li+的制备和发光性能研究[J].稀土,2017,38(2):80-86.
[20]LIU Cheng-lu,JIA Pei-yun,WANG Fang,et al.Synthesis and luminescence properties of YPO4:Eu nanrod-clusters[J].Chinese Journal of Synthetic Chemistry,2011,19(4):516-519.刘成露,贾佩云,王芳,等.纳米棒束YPO4:Eu的合成及其发光性能[J].合成化学,2011,19(4):516-519.
[21]YANG Liu-sai,PENG Si-yan,YU Le-shu,et al.Phase evolution and luminescence properties of CaHPO4:Tb3+nanocrystals[J].Journal of Optoelectronics·Laser,2015,26(12):2346-2350.杨流赛,彭思艳,余乐书,等.CaHPO4:Tb3+纳米晶的相演变与发光性能研究[J].光电子·激光,2015,26(12):2346-2350.
[22]YANG Liu-sai,PENG Si-yan,YU Le-shu,et al.Preparation and luminescence properties of monoclinic phase BiPO4:Tb3+nanocrystals[J].Journal of Materials Science&Engineering,2016,34(4):560-563.杨流赛,彭思艳,余乐书,等.低温单斜相BiPO4:Tb3+纳米晶的合成及其发光性能[J].材料科学与工程学报,2016,34(4):560-563.
[2] Yahiaoui Z,Hassairi M A,Dammak M,et al.Tunable luminescence and energy transfer properties in YPO4:Tb3+,Eu3+/Tb3+phosphors[J].Journal of Luminescence,2018,194:96-101.
[3] FU Bing,OU Ya,LIU Huan,et al.Ba2+co-doped YPO4:Tb3+phosphors:hydrothermal synthesis and photoluminescence properties[J].Materials Review,2017,31(18):16-20.付兵,欧娅,刘欢,等.Ba2+共掺杂YPO4:Tb3+荧光材料的水热合成与荧光性能[J].材料导报,2017,31(18):16-20.
[4] HUO Qong-qian,YU Ben-wu,CHEN Xiao-li,et al.Hydrothermal preparation and white-light emission of YPO4:Dy3+,Eu3+phosphors[J].Journal of Optoelectronics·Laser,2015,26(11):2141-2147.霍涌前,于本武,陈小利,等.YPO4:Dy3+,Eu3+荧光粉的水热合成及白光发射[J].光电子·激光,2015,26(11):2141-2147.
[5] JIANG Chun-dong,ZHANG Ping,WU Jiang.The synthesis and light emitting research of YPO4:Gd,Eu phosphor[J].Science Technology and Engineering,2014,14(16):1-5.蒋春东,张萍,吴疆.YPO4:Gd,Eu荧光粉的制备和发光性能研究[J].科学技术与工程,2014,14(16):1-5.
[6] ZHANG Xiao-rong,REN Jiang-xue,OU Yang-yan,et al.Synthesis and fluorescence of YPO4·2H2O:Eu3+microflower structure[J].New Chemical Material,2016,44(5):67-69.张晓蓉,任建学,欧阳艳,等.YPO4·2H2O:Eu3+花状微米结构的合成及荧光性能研究[J].化工新型材料,2016,44(05):67-69.
[7] YANG Jin-yu,ZENG Xiao-dao,ZHU Li-ping,et al.Citric acid-assisted sol-gel synthesis and fluorescence research of Eu3+-doped YPO4 phosphors[J].Rare Metal and Cemented Carbides,2014,42(4):41-45.杨锦瑜,曾晓岛,朱莉萍,等.Eu3+掺杂YPO4荧光材料的柠檬酸辅助溶胶-凝胶法合成及其荧光性能研究[J].稀有金属与硬质合金,2014,42(4):41-45.
[8] ZHAO Ming-lei,LI Li-ping,LI Guang-she.Advances of solution chemistry in stabilizing different crystal phases of inorganic nano-compounds[J].CrystEngComm,2016,18(48):9209-9222.
[9] XIE Ji-xing,GENG Xiu-juan,GAO Rong-hua,et al.The preparation and luminescent properties of white phosphor Gd2(MoO4):Dy3+,Tm3+[J].Journal of Optoelectronics·Laser,2018,29(4):377-382.解吉星,耿秀娟,高荣华,等.白色荧光粉Gd2(MoO4):Dy3+,Tm3+的制备及发光性能[J].光电子·激光,2018,29(4):377-382.
[10]Gavrilovic T,Perisa J,Papan J,et al.Particle size effects on the structure and emission of Eu3+:LaPO4and EuPO4phosphors[J].Journal of Luminescence,2018,195:420-429.
[11]LI Zhao,XU Ke,JIANG Yuan-ru.Synthesis and luminescence properties of spherical NaY(MoO4)2:Sm3+phosphor[J].Journal of Synthetic Crystals,2016,45(2):525-528.李兆,徐克,江元汝.球形NaY(MoO4)2:Sm3+荧光粉的合成及荧光性能研究[J].人工晶体学报,2016,45(2):525-528.
[12]LI Zhao,ZHAO Xi-cheng,JIANG Yuan-ru.Preparation and photoluminescent property of sphere Y2.96Al5O12:0.04Ce3+phosphors for white light-emitting diodes[J].Spectroscopy and Spectral Analysis,2014,34(11):2918-2922.李兆,赵西成,江元汝.白光LED用球形Y2.96Al5O12:0.04Ce3+荧光粉的制备及光致发光[J].光谱学与光谱分析,2014,34(11):2918-2922.
[13]LI Xu,WANG Hao-yan,GUAN Li,et al.Influence of pH value on properties of YPO4:Tb3+phosphor by co-precipitation method[J].Journal of Rare Earths,2015,33(4):346-349.
[14]LI Guang-zhi,LIU Song-yan,CHU Zhen-sheng,et al.Synthesis and photoluminescence of core-shell structured spherical SiO2@YPO4:Tb3+phosphors via sol-gel process[J].Journal of Luminescence,2012,132(11):2961-2967.
[15]LIU Xu-yan,DING Nan,QU Chong-nian,et al.Controlled synthesis and luminescence properties of rare-earth doped YPO4 phosphor[J].Chinese Journal of Luminescence,2017,38(5):588-594.刘旭焱,丁楠,屈重年,等.稀土掺杂磷酸钇荧光粉的控制合成和发光性能[J].发光学报,2017,38(5):588-594.
[16]LI Xu-bo,DING Jian-hong,HUANG Qi-shu,et al.Luminescence of YPO4doped with Ce3+under UV excitation[J].Material Research and Application,2014,8(1):42-45.李许波,丁建红,黄奇书,等.紫外光激发(Y,Ce)PO4荧光粉的发光特性[J].材料研究与应用,2014,8(1):42-45.
[17]ZHANG Zhong-ju,SHI Jing,WANG Xiao-yan,et al.Vibrational and luminescent properties of LaPO4:Eu3+with different preparation conditions[J].Journal of Rare Earths,2016,34(11):1103-1110.
[18]ZHANG Yong-ming,SONG Guo-yi,CAO Qi-hua,et al.Preparation and luminescent properties of Eu3+doped GdPO4glass ceramic[J].Journal of Optoelectronics·Laser,2014,25(6):1124-1128.张永明,宋国轶,曹启华,等.Eu3+掺杂GdPO4微晶玻璃的制备及其发光特性的研究[J].光电子·激光,2014,25(6):1124-1128.
[19]WANG Fei,CHEN Hui-hui,TIAN Yi-guang,et al.Preparation and luminescent properties of red phosphor BaAl2Si2O8:Eu3+,Li+[J].Chinese Rare Earths,2017,38(2):80-86.王飞,陈慧慧,田一光,等.红色荧光粉BaAl2Si2O8:Eu3+,Li+的制备和发光性能研究[J].稀土,2017,38(2):80-86.
[20]LIU Cheng-lu,JIA Pei-yun,WANG Fang,et al.Synthesis and luminescence properties of YPO4:Eu nanrod-clusters[J].Chinese Journal of Synthetic Chemistry,2011,19(4):516-519.刘成露,贾佩云,王芳,等.纳米棒束YPO4:Eu的合成及其发光性能[J].合成化学,2011,19(4):516-519.
[21]YANG Liu-sai,PENG Si-yan,YU Le-shu,et al.Phase evolution and luminescence properties of CaHPO4:Tb3+nanocrystals[J].Journal of Optoelectronics·Laser,2015,26(12):2346-2350.杨流赛,彭思艳,余乐书,等.CaHPO4:Tb3+纳米晶的相演变与发光性能研究[J].光电子·激光,2015,26(12):2346-2350.
[22]YANG Liu-sai,PENG Si-yan,YU Le-shu,et al.Preparation and luminescence properties of monoclinic phase BiPO4:Tb3+nanocrystals[J].Journal of Materials Science&Engineering,2016,34(4):560-563.杨流赛,彭思艳,余乐书,等.低温单斜相BiPO4:Tb3+纳米晶的合成及其发光性能[J].材料科学与工程学报,2016,34(4):560-563.