磷酸盐稀土荧光材料的制备与性能分析
摘要
本文采用高温固相法合成了以磷酸盐为基质适合UVLED激发的荧光材料。对所合成材料进行了XRD物相分析,并对其发射光谱和激发光谱进行了分析,研究了合成的荧光材料的发光性质与原理。主要内容如下：
(1)合成了BaZnP2O7:Tb3+绿色荧光粉。激发主峰值位于387 nm,表明BaZnPO4:Tb3+是一种适用于UVLED管芯激发的绿色荧光材料。分析了共掺Ce3+作为敏化剂及Tb3+含量对样品发光性能的影响。
(2)合成了NaBaPO4:Eu2+蓝色荧光粉,其激发主峰值位于378 nm,与UVLED管芯(350-410 nm)匹配。Eu2+含量较大时,Eu2+-Eu2+间共振能量传递增强,发生浓度猝灭现象。
(3)合成了NaBaPO4:Eu3+橙红色荧光粉,从它的发光性质可以看出：该荧光粉可作为红色补光粉弥补现有白光LED缺少红光的不足,也可以作为紫外芯片激发的红粉。分析了碱土金属离子Li+、Cl-和K+作为电荷补偿剂对样品发光性能的影响。
(4)合成了KCaPO4:Eu2+蓝绿色荧光粉。对样品进行了X射线衍射分析和发光特性研究,确定了掺杂浓度对样品发光特性的影响情况。讨论了Eu2+在基质中占据两个不同的格位的情况。
In this paper. some kinds of phosphate phosphor used for UVLED were fabricated by traditional high temperate solid stated method. Compared with Joint Committee on Powder Diffraction Standards. the crystal structure of the phosphors were studied. The excitation and emission spectra of the phosphors were investigated. and the luminescent mechanism of the phosphors were also analysed. The chief contents are given a s follows:
(1) The BaZnP2O7:Tb3+ phosphor was prepared. The excitation spectrum contains a broad band extending from 350 to 400 nm. which is coupled well with the emission of UVLED. The effects of co-doped Ce3- concentration on the emission intensity are also investigated.
(2) A novel blue-emitting phosphor NaBaPO4:Eu2+ was prepared. The main excitation peak is located at 378 nm. which matches the emission of UVLED(350-410 nm). The effect of doped Eu2+ concentration on the emission intensity was also investigated.
(3) The NaBaPO4:Eu3+ phosphor was prepared. It could be seen from its luminescent properties that this phosphor could be excited effectively by blue chip and UV chip and emited pure red light. So it can be used for the red phosphor in the white LED that composed by UV chip and multi color phosphors and the compensating phosphor in "blue +yellow" model. The role of charge compensation of Li+. K+ and Cl- to the emission intensity was studied. It was found that Li+ gave the best improvement to enhance the intensity of the emissions.
(4) The KCaPO4:Eu2+ phosphor appeared one anisomerous peak under near-ultraviolet (UV) excitation and the Gaussian fit of the PL spectrum with two emission bands at 480 nm and 540 nm were observed. Eu2- ions doped in two different Ca2+ sites:Eu(Ⅰ) and Eu(Ⅱ) in the host lattice, respectively.
(1)合成了BaZnP2O7:Tb3+绿色荧光粉。激发主峰值位于387 nm,表明BaZnPO4:Tb3+是一种适用于UVLED管芯激发的绿色荧光材料。分析了共掺Ce3+作为敏化剂及Tb3+含量对样品发光性能的影响。
(2)合成了NaBaPO4:Eu2+蓝色荧光粉,其激发主峰值位于378 nm,与UVLED管芯(350-410 nm)匹配。Eu2+含量较大时,Eu2+-Eu2+间共振能量传递增强,发生浓度猝灭现象。
(3)合成了NaBaPO4:Eu3+橙红色荧光粉,从它的发光性质可以看出：该荧光粉可作为红色补光粉弥补现有白光LED缺少红光的不足,也可以作为紫外芯片激发的红粉。分析了碱土金属离子Li+、Cl-和K+作为电荷补偿剂对样品发光性能的影响。
(4)合成了KCaPO4:Eu2+蓝绿色荧光粉。对样品进行了X射线衍射分析和发光特性研究,确定了掺杂浓度对样品发光特性的影响情况。讨论了Eu2+在基质中占据两个不同的格位的情况。
In this paper. some kinds of phosphate phosphor used for UVLED were fabricated by traditional high temperate solid stated method. Compared with Joint Committee on Powder Diffraction Standards. the crystal structure of the phosphors were studied. The excitation and emission spectra of the phosphors were investigated. and the luminescent mechanism of the phosphors were also analysed. The chief contents are given a s follows:
(1) The BaZnP2O7:Tb3+ phosphor was prepared. The excitation spectrum contains a broad band extending from 350 to 400 nm. which is coupled well with the emission of UVLED. The effects of co-doped Ce3- concentration on the emission intensity are also investigated.
(2) A novel blue-emitting phosphor NaBaPO4:Eu2+ was prepared. The main excitation peak is located at 378 nm. which matches the emission of UVLED(350-410 nm). The effect of doped Eu2+ concentration on the emission intensity was also investigated.
(3) The NaBaPO4:Eu3+ phosphor was prepared. It could be seen from its luminescent properties that this phosphor could be excited effectively by blue chip and UV chip and emited pure red light. So it can be used for the red phosphor in the white LED that composed by UV chip and multi color phosphors and the compensating phosphor in "blue +yellow" model. The role of charge compensation of Li+. K+ and Cl- to the emission intensity was studied. It was found that Li+ gave the best improvement to enhance the intensity of the emissions.
(4) The KCaPO4:Eu2+ phosphor appeared one anisomerous peak under near-ultraviolet (UV) excitation and the Gaussian fit of the PL spectrum with two emission bands at 480 nm and 540 nm were observed. Eu2- ions doped in two different Ca2+ sites:Eu(Ⅰ) and Eu(Ⅱ) in the host lattice, respectively.
引文
[1]Matsuzawa T, Aoki Y, Takeuchi N, etal. A new long phosphorescent phosphor with high brightness.SrAl2O4:Eu2+.Dy3+[J]. J.Electrochem.Soc,1996,143:2670-2673.
[2]Qiu J,Miura K,Inouye H.etal.Femtosecond laser-induced three-dimensional bright and long-lasting phosphorescence inside calcium aluminosilicate glasses doped with rare earth ions [J].Appl.Phys.Lett, 1998,73:1763-1765.
[3]Su Qiang, Li Chengyu, Lu Yuhua. Preparation of the glasses and glass-ceramics with long-lasting phosphorescence and photo-stimulated long-lasting phosphorescence for optical memory[P]. CN Patent,02117958.1.
[4]Kowatari M, Koyama D, Satoh Y, etal. The temperature dependence of luminescence from a long lasting phosphors exposed to ionizing radiation[J].Nuclear Instruments and Methods in Physics Research A,2002,480:431-439.
[5]张俊英,张林,王天民等.长余辉发光玻璃的研究进展[J].材料导报.2003.17(4)：17-20.
[6]杨志平,刘冲,郭智等.CaTiO3:Pr3+长余辉玻璃的制备与发光性能[J].发光学报.2005,26(4)：493-496.
[7]Katsumata T, Sakai R, Komuro S, et al. Growth and characteristics of long duration phosphors crystals[J]. J. Crystal Growth,1999.198/199:869-871.
[8]Kodama N, Takahashi T, Yamaga M, et al. Long-lasting phosphorescence in Ce3+-doped Ca2Al2SiO7 and CaYAl3O7 crystals[J]. Appl. Phys. Lett.1999,75:1715-1717.
[9]Jia W, Yuan H, Lu L. et al. Phosphorescent dynamics in SrAl2O4:Eu2+.Dy3+ single crystal fibers[J]. J. Lumin.,1998,76-77:424-428.
[10]Kato K, Tsutai I, Kamimura T, et al. Thermoluminescence properties of SrAl2O4:Eu sputtered films with long phosphorescence[J]. J. Lumin,1999,82:213-220.
[11]王海波,朱宪忠,任巨光.荧光粉涂敷法制白光LED前景广阔.[J].中国照明电器,2004,5：1-4.
[12]刘坚斌,李培咸,郝跃.高亮度GaN基蓝光与白光LED的研究进展.[J].量子电子学报,2005,22(10)：673-679.
[13]武毅.绿色光源—LED. [J]灯与照明.2005.30(2)：47-50.
[14]王进.光转换自光LED研究.[D].中国海洋大学2005：1-3.
[15]杨笑卫(译).高亮度、全光色LED.[J].中国照明电器,2001,4：23-25.
[16]Werner K. Higher. visibility for LEDs.[J]. IEEE Spectrum,1994,31(7):30-34.
[17]Sugawara H,Itaya K,Nozaki H. High brightness InGaAP freen light emitting diodes.[J]. Applied Physics Letters,1992,61 (15):1775-1777.
[18]蒋大鹏,赵成久,侯凤勤,刘学彦,范翊.张立功,褚明辉,申德振,范希武.白光发光二极管的制备技术及主要特性.发光学报,2003,24(4)：385-389.
[19]YAO Guang-qing, DUAN Jie-fei, REN Min, YU Hai-dong, LIN Jian-hua, Preparation and Luminescence of Blue Light Conversion Material YAG:Ce, [J].Chinese Journal of luminescence. 2001.10.Vol.22.Supp.21-23.
[20]孟继武.王燕辛.王晶.郑荣儿.光转换白光LED s的研究,光电子·激光,2003,14(6)：566-569.
[21]尹长安,赵成久,刘学彦,侯凤勤,郑岩,卢景贵.蒋大鹏.申德振,白光L E D的最新进展.发光学报,2000,21(4)：380-382.
[22]杨笑卫(译).高亮度、全光色L E D,中国照明电器,2001.4：23-25.
[23]刘行仁,薛胜薜,黄德森,林秀华.白光LED的现状和问题,光源与照明,2003,3：4-8.
[24]Yuexiao Pan, Mingmei Wu, Qiang Su. Comparative investigation on synthesis and photoluminescence of YAG:Ce phosphor. [J]. Materials Science and Engineering B,2004,106:251-256.
[25]Yuexiao Pan, Mingmei Wu, Qiang Su.Tailored photoluminescence of YAG:Ce phosphor. through various methods.[J]. Journal of Physics and Chemistry of Solids,2004.65:845-850.
[26]Qiang Li, Lian Gao, Dongsheng Yan. The crystal structure and spectra of nano-scale YAG:Ce3+[J]. Materials Chemistry and Physics,2000,64:41-44.
[27]Jun-Ho Yum, Seok-Soon Kim, Yung-Eun Sung. Y3Al5O12:Ce0.05 phosphor coatings on a flexible substrate for use in white light-emitting diodes. [J]. Colloids and Surfaces A:physicochem. Eng. Aspects,2004,251:203-207.
[28]Schlotter P, Schmidt R, Schneider J. Luminescence conversion of blue light emitting diodes. [J]. Applied Physics A 1997,64:417-418.
[29]Li Yongxiu. Li Yinyi, Min Yulin, Wu Yanli, Cheng Changming, Zhou Xuezhen, Gu Ziying. Synthesis of YAG:Ce3+ Phosphor by Polyacrylamide Gel Method and Promoting Action of αAl2O3 Seed Crystal on Phase Formation. [J]. Journal of rare earths,2005.23(5):517-520.
[30]徐叙瑢,苏勉曾.[M].发光学与发光材料.北京：化学工业出版社,2004,第1版：53-55.
[31]D. T. Palumbo, J. J. Brown,Jr. Electronic states of Mn2+-activated phosphors.[J]. Journal of the Electrochemical Society,1970,117:1184-1188.
[32]孙家跃等.固体发光材料.[M].北京：化学工业出版社,2003：7.
[33]杨志平,郭智,王文杰,朱胜超.Pr3+摩尔浓度对CaTiO3:Pr3-红色长余辉材料的影响.[J].功能材料与器件学报,2003,9(4)：473-476.
[34]M. Veith, S. Mthur, A. Kareiva, M. Jilavi, M. Zimmer, V. Huch. [J]. Mater. Chem.,1999,(9): 3069-3072.
[35]R. Manalert,M. N. Rahaman.[J].Mater.Sci..1996.(31):3453-3457.
[36]Yu Yaqin, Li Mei, Liu Shuzhen. Synthesis and properties of lanthanide element orthophosphate [J]. Chin. J. Silicate,1989,17(6):485-489(in Chinese).
[37]牛淑云,闵庆旺,付晓燕,张洪武纳米Mg3(PO4)2:Bi3+、Eu3-的发光性能与能量传递 辽宁师范大学学报 28(4)：433-435.
[38]石士考Ce3+与Tb3+共激活的BaMgF4体系的发光性质与能量传递河北大学学报(自然科学版),20(1)：22-24.
[39]吴根华,陈荣,张启运KAlF4:Ce,Tb磷光体的发光特性及Ce3+对Tb3+的敏化作用光谱学与光谱分析17(3)：6-9.
[40]Xingren Liu, Xiaojun Wang, Zhongkia Wang. Selectivelyeccited emission and energy transfer in yttrium aluminum garnet[J]. The American Physical Society.1989,39(15): 10633-10639.
[41]Yu Yaqin, Li Mei, Liu Shuzhen. Synthesis and properties of lanthanide element orthophosphate [J].Chin. J. Sili2 cate,1989,17(6):4852489 (in Chinese).
[42]毛向辉,吴振国,廉世勋.Eu离子在在光转换材料中作用的研究.[J].湖南师范大学自然科学学报,1994,6,17,2：56-58.
[43]谢平波,段昌奎,张慰萍等.纳米晶Y2SiO5:Eu的浓度猝灭研究.[J].发光学报,1998,19.1：19～23
[44]S.Daniel, B.Jerome, C.Dave. Selected Topics in Quantum Electronics[J]. IEEE 2002,82:310-320.
[45]S.Nakamura and G. Fasol[M].The Blue Laser Diode:GaN Based Light Emitters and Lasers Springer. Berlin,1996.
[46]D. Eisert. U. Strauss. S. Bader. H. J. Lugauer. M. Fehrer. B. Hahn. J. Baur. U. Zehnder. N. Stath. V. Harle, Inst. Pure. Appl. Phys. Conf. Ser.2000,1:841.
[47]毛向辉,吴振国,廉世勋。Eu离子在光转换材料中作用的研究[J].湖南师范大学学报(自然科学版),1994,17(2)：56-58.
[48]于广聪.新型稀土磷酸盐体系绿色荧光粉的研究[J].稀有金属材料与工程,1996,26(1)：44-47.
[49]牛春晖,曹望和,臧春雨.掺Er磷酸盐玻璃中红外发光特性研究[J].发光学报,2001,22(4)：357-360.
[50]Woanjen Yang,Tengming Chen, White-light generation and energy transfer in SrZn2(PO4)2:Eu, Mn phosphor for ultraviolet light-emitting diodes[J]. Applied Physics Letters,2006,88:101903.
[51]Kottaisamy M, Jagannathan R, The Journal of The Electrochemical Society.1995.142(9):3205.
[52]Yang Z P, Guo Z, Zhu S C et al Spectrosc. Spec. Anal.2004,24(12):1506.
[53]L.G. Van Uitert. J. Lumin.1984,29(1)1.
[54]许武亮,刘行仁.中国稀土学报.1993,11(2)116.
[55]李宗和,李奇,王艳结构化学.北京：北京师范大学出版社,1987：299.
[2]Qiu J,Miura K,Inouye H.etal.Femtosecond laser-induced three-dimensional bright and long-lasting phosphorescence inside calcium aluminosilicate glasses doped with rare earth ions [J].Appl.Phys.Lett, 1998,73:1763-1765.
[3]Su Qiang, Li Chengyu, Lu Yuhua. Preparation of the glasses and glass-ceramics with long-lasting phosphorescence and photo-stimulated long-lasting phosphorescence for optical memory[P]. CN Patent,02117958.1.
[4]Kowatari M, Koyama D, Satoh Y, etal. The temperature dependence of luminescence from a long lasting phosphors exposed to ionizing radiation[J].Nuclear Instruments and Methods in Physics Research A,2002,480:431-439.
[5]张俊英,张林,王天民等.长余辉发光玻璃的研究进展[J].材料导报.2003.17(4)：17-20.
[6]杨志平,刘冲,郭智等.CaTiO3:Pr3+长余辉玻璃的制备与发光性能[J].发光学报.2005,26(4)：493-496.
[7]Katsumata T, Sakai R, Komuro S, et al. Growth and characteristics of long duration phosphors crystals[J]. J. Crystal Growth,1999.198/199:869-871.
[8]Kodama N, Takahashi T, Yamaga M, et al. Long-lasting phosphorescence in Ce3+-doped Ca2Al2SiO7 and CaYAl3O7 crystals[J]. Appl. Phys. Lett.1999,75:1715-1717.
[9]Jia W, Yuan H, Lu L. et al. Phosphorescent dynamics in SrAl2O4:Eu2+.Dy3+ single crystal fibers[J]. J. Lumin.,1998,76-77:424-428.
[10]Kato K, Tsutai I, Kamimura T, et al. Thermoluminescence properties of SrAl2O4:Eu sputtered films with long phosphorescence[J]. J. Lumin,1999,82:213-220.
[11]王海波,朱宪忠,任巨光.荧光粉涂敷法制白光LED前景广阔.[J].中国照明电器,2004,5：1-4.
[12]刘坚斌,李培咸,郝跃.高亮度GaN基蓝光与白光LED的研究进展.[J].量子电子学报,2005,22(10)：673-679.
[13]武毅.绿色光源—LED. [J]灯与照明.2005.30(2)：47-50.
[14]王进.光转换自光LED研究.[D].中国海洋大学2005：1-3.
[15]杨笑卫(译).高亮度、全光色LED.[J].中国照明电器,2001,4：23-25.
[16]Werner K. Higher. visibility for LEDs.[J]. IEEE Spectrum,1994,31(7):30-34.
[17]Sugawara H,Itaya K,Nozaki H. High brightness InGaAP freen light emitting diodes.[J]. Applied Physics Letters,1992,61 (15):1775-1777.
[18]蒋大鹏,赵成久,侯凤勤,刘学彦,范翊.张立功,褚明辉,申德振,范希武.白光发光二极管的制备技术及主要特性.发光学报,2003,24(4)：385-389.
[19]YAO Guang-qing, DUAN Jie-fei, REN Min, YU Hai-dong, LIN Jian-hua, Preparation and Luminescence of Blue Light Conversion Material YAG:Ce, [J].Chinese Journal of luminescence. 2001.10.Vol.22.Supp.21-23.
[20]孟继武.王燕辛.王晶.郑荣儿.光转换白光LED s的研究,光电子·激光,2003,14(6)：566-569.
[21]尹长安,赵成久,刘学彦,侯凤勤,郑岩,卢景贵.蒋大鹏.申德振,白光L E D的最新进展.发光学报,2000,21(4)：380-382.
[22]杨笑卫(译).高亮度、全光色L E D,中国照明电器,2001.4：23-25.
[23]刘行仁,薛胜薜,黄德森,林秀华.白光LED的现状和问题,光源与照明,2003,3：4-8.
[24]Yuexiao Pan, Mingmei Wu, Qiang Su. Comparative investigation on synthesis and photoluminescence of YAG:Ce phosphor. [J]. Materials Science and Engineering B,2004,106:251-256.
[25]Yuexiao Pan, Mingmei Wu, Qiang Su.Tailored photoluminescence of YAG:Ce phosphor. through various methods.[J]. Journal of Physics and Chemistry of Solids,2004.65:845-850.
[26]Qiang Li, Lian Gao, Dongsheng Yan. The crystal structure and spectra of nano-scale YAG:Ce3+[J]. Materials Chemistry and Physics,2000,64:41-44.
[27]Jun-Ho Yum, Seok-Soon Kim, Yung-Eun Sung. Y3Al5O12:Ce0.05 phosphor coatings on a flexible substrate for use in white light-emitting diodes. [J]. Colloids and Surfaces A:physicochem. Eng. Aspects,2004,251:203-207.
[28]Schlotter P, Schmidt R, Schneider J. Luminescence conversion of blue light emitting diodes. [J]. Applied Physics A 1997,64:417-418.
[29]Li Yongxiu. Li Yinyi, Min Yulin, Wu Yanli, Cheng Changming, Zhou Xuezhen, Gu Ziying. Synthesis of YAG:Ce3+ Phosphor by Polyacrylamide Gel Method and Promoting Action of αAl2O3 Seed Crystal on Phase Formation. [J]. Journal of rare earths,2005.23(5):517-520.
[30]徐叙瑢,苏勉曾.[M].发光学与发光材料.北京：化学工业出版社,2004,第1版：53-55.
[31]D. T. Palumbo, J. J. Brown,Jr. Electronic states of Mn2+-activated phosphors.[J]. Journal of the Electrochemical Society,1970,117:1184-1188.
[32]孙家跃等.固体发光材料.[M].北京：化学工业出版社,2003：7.
[33]杨志平,郭智,王文杰,朱胜超.Pr3+摩尔浓度对CaTiO3:Pr3-红色长余辉材料的影响.[J].功能材料与器件学报,2003,9(4)：473-476.
[34]M. Veith, S. Mthur, A. Kareiva, M. Jilavi, M. Zimmer, V. Huch. [J]. Mater. Chem.,1999,(9): 3069-3072.
[35]R. Manalert,M. N. Rahaman.[J].Mater.Sci..1996.(31):3453-3457.
[36]Yu Yaqin, Li Mei, Liu Shuzhen. Synthesis and properties of lanthanide element orthophosphate [J]. Chin. J. Silicate,1989,17(6):485-489(in Chinese).
[37]牛淑云,闵庆旺,付晓燕,张洪武纳米Mg3(PO4)2:Bi3+、Eu3-的发光性能与能量传递 辽宁师范大学学报 28(4)：433-435.
[38]石士考Ce3+与Tb3+共激活的BaMgF4体系的发光性质与能量传递河北大学学报(自然科学版),20(1)：22-24.
[39]吴根华,陈荣,张启运KAlF4:Ce,Tb磷光体的发光特性及Ce3+对Tb3+的敏化作用光谱学与光谱分析17(3)：6-9.
[40]Xingren Liu, Xiaojun Wang, Zhongkia Wang. Selectivelyeccited emission and energy transfer in yttrium aluminum garnet[J]. The American Physical Society.1989,39(15): 10633-10639.
[41]Yu Yaqin, Li Mei, Liu Shuzhen. Synthesis and properties of lanthanide element orthophosphate [J].Chin. J. Sili2 cate,1989,17(6):4852489 (in Chinese).
[42]毛向辉,吴振国,廉世勋.Eu离子在在光转换材料中作用的研究.[J].湖南师范大学自然科学学报,1994,6,17,2：56-58.
[43]谢平波,段昌奎,张慰萍等.纳米晶Y2SiO5:Eu的浓度猝灭研究.[J].发光学报,1998,19.1：19～23
[44]S.Daniel, B.Jerome, C.Dave. Selected Topics in Quantum Electronics[J]. IEEE 2002,82:310-320.
[45]S.Nakamura and G. Fasol[M].The Blue Laser Diode:GaN Based Light Emitters and Lasers Springer. Berlin,1996.
[46]D. Eisert. U. Strauss. S. Bader. H. J. Lugauer. M. Fehrer. B. Hahn. J. Baur. U. Zehnder. N. Stath. V. Harle, Inst. Pure. Appl. Phys. Conf. Ser.2000,1:841.
[47]毛向辉,吴振国,廉世勋。Eu离子在光转换材料中作用的研究[J].湖南师范大学学报(自然科学版),1994,17(2)：56-58.
[48]于广聪.新型稀土磷酸盐体系绿色荧光粉的研究[J].稀有金属材料与工程,1996,26(1)：44-47.
[49]牛春晖,曹望和,臧春雨.掺Er磷酸盐玻璃中红外发光特性研究[J].发光学报,2001,22(4)：357-360.
[50]Woanjen Yang,Tengming Chen, White-light generation and energy transfer in SrZn2(PO4)2:Eu, Mn phosphor for ultraviolet light-emitting diodes[J]. Applied Physics Letters,2006,88:101903.
[51]Kottaisamy M, Jagannathan R, The Journal of The Electrochemical Society.1995.142(9):3205.
[52]Yang Z P, Guo Z, Zhu S C et al Spectrosc. Spec. Anal.2004,24(12):1506.
[53]L.G. Van Uitert. J. Lumin.1984,29(1)1.
[54]许武亮,刘行仁.中国稀土学报.1993,11(2)116.
[55]李宗和,李奇,王艳结构化学.北京：北京师范大学出版社,1987：299.