白光LED用硼酸盐荧光材料的合成及性能研究
摘要
首次利用高温固相法制备了黄色荧光粉Ca2BO3Cl：Eu2+,并研究了该荧光粉的发光特性以及制备过程中各种条件对荧光粉发光性质的影响。当原料于900℃下烧结2.5h,Eu2+浓度为1.5%时,可以得到性能优良的荧光粉。从样品的激发光谱和发射光谱可以看出：Ca2BO3Cl：Eu2+的激发峰位于413nm和475nm,与蓝光和紫外LED芯片匹配；发射谱为峰值位于573nm处的宽带谱,它既可与芯片发出的蓝光组合成白光,还可以作为紫外芯片激发的黄色荧光粉,与其它颜色荧光粉混合得到白光发射。制备了红色荧光粉CaAl2B2O7：Eu3+,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。利用固相法制备了Eu2+激活的Ba282P2O10绿色和Ca2B5O9Cl蓝色荧光粉,对样品进行了X射线衍射分析和发光特性研究,确定了掺杂浓度以及各组分含量对样品发光特性的影响情况。
The yellow phosphor Ca2BO3Cl:Eu2+ was prepared by high temperate solid stated method and the influence of different procedure conditions on its luminescent properties was studied. When initiative temperature was 900℃for 2.5 h and the concentration of Eu2+ was 1.5%, the high performance phosphor could be formed. It could be seen from excitation and emission spectra that the excitation peaks were at 413nm,475nm and the emission peak was at 573nm. This phosphor is very suitable for a color converter of white LED that uses blue LED as the primary light source. Also it can be used as a yellow phosphor excited by UV LED or mix with other color phosphors to product white light. The red phosphor CaAl2B2O7:Eu3+ was formed for the first time in this paper. 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 compensating phosphor in "blue +yellow" model and the red phosphor in the white LED that composed by UV chip and multi color phosphors.The Ba2B2P2O10:Eu2+ and Ca2B5O9Cl:Eu2+ were fabricated by solid stated method. The x-ray diffraction patterns and the luminescent properties were studied. And the effects of the concertration of Eu2+ and the ratio of elements on the luminescent properties were investigated.
The yellow phosphor Ca2BO3Cl:Eu2+ was prepared by high temperate solid stated method and the influence of different procedure conditions on its luminescent properties was studied. When initiative temperature was 900℃for 2.5 h and the concentration of Eu2+ was 1.5%, the high performance phosphor could be formed. It could be seen from excitation and emission spectra that the excitation peaks were at 413nm,475nm and the emission peak was at 573nm. This phosphor is very suitable for a color converter of white LED that uses blue LED as the primary light source. Also it can be used as a yellow phosphor excited by UV LED or mix with other color phosphors to product white light. The red phosphor CaAl2B2O7:Eu3+ was formed for the first time in this paper. 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 compensating phosphor in "blue +yellow" model and the red phosphor in the white LED that composed by UV chip and multi color phosphors.The Ba2B2P2O10:Eu2+ and Ca2B5O9Cl:Eu2+ were fabricated by solid stated method. The x-ray diffraction patterns and the luminescent properties were studied. And the effects of the concertration of Eu2+ and the ratio of elements on the luminescent properties were investigated.
引文
[1]陈大华.电光源在新世纪中的曙光。[J].中国照明电器,2001,11：5-12
[2]郝海涛.白光LED用荧光材料的制备及性能研究.2006,太原理工大学硕士论文,3-5.
[3]Maruska H.P., Tietjen.J.J. The preparation and properties of vapor-desited single-crystal-line GaN. Applied Physics Letter,1969(15):327
[4]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.
[5]武毅.绿色光源—LED.[J].灯与照明,2005,30(2)：47-50.
[6]Werner K. Higher. visibility for LEDs.[J].IEEE Spectrum,1994,31(7):30-34.
[7]Sugawara H, Itaya K, Nozaki H. High brightness InGaAP freen light emitting diodes. [J].Applied Physics Letter,1992,61 (15):1775-1777.
[8]王进.光转换白光LED研究.[D].中国海洋大学2005年1-3.
[9]杨笑卫(译).高亮度、全光色LED.[J].中国照明电器,2001,4：23-25.
[10]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.[J].发光学报,2003,24(4)：385-389.
[11]Yuji Uchida, Tatsumi Setomotoa, Tsunemasa Taguchia, Yoshinori Nakagawa,Kazuto Miyazakib. Characteristics of high-efficient InGaN-based white LED lighting. [J].Pro.SPIE.,2000,4079:120-126.
[12]孟继武,王燕辛,王晶,郑荣儿.光转换白光LEDs的研究.[J].光电子·激光,2003,14(6)：566-569.
[13]刘洁,孙家跃,石春山.与LED匹配的白光发射荧光体的研究进展.[J].化学通报,2005,6：417-424.
[14]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,[J].发光学报.2003.24(4)：385-389.
[15]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., 2001,22(10):(Supp)21-23.
[16]孟继武,王燕辛,王晶,郑荣儿.光转换白光LEDs的研究.[J].光电子光激光,2003,14(6)：566-569.
[17]尹长安,赵成久,刘学彦,侯凤勤,郑岩,卢景贵,蒋大鹏,中德振.白光LED的最新进展.[J].发光学报,
2000,21(4)：380-382.
[18]杨笑卫(译).高亮度、全光色L E D.[J].中国照明电器,2001,4：23-25.
[19]刘行仁,薛胜薜,黄德森,林秀华.白光LED的现状和问题.[J].光源与照明,2003,3：4-8.
[20]李旭.白光LED用荧光粉的性能和制备.2006,河北大学硕士论文,2-3.
[21]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.
[22]刘如熹,石景仁.白光发光二极管用钇铝石榴石萤光粉配方与机制研究.[J].发光学报,2002,20(6)：405-501.
[23]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.
[24]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.
[25]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.
[26]Jun-Ho Yum, Seok-Soon Kim, Yung-Eun Sung. Y3Al5O12:Ceo.o5 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.
[27]Schlotter P, Schmidt R, Schneider J. Luminescence conversion of blue light emitting diodes.[J].Applied Physics A 1997,64:417-418.
[28]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.
[29]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.
[30]M. Veith, S. Mthur, A. Kareiva, M. Jilavi, M. Zimmer, V. Huch. [J]. Mater. Chem.,1999, (9): 3069-3072.
[31]R. Manalert,M. N. Rahaman.[J].Mater.Sci.,1996,(31):3453-3457.
[32]田华.《基质组成对铝酸锶发光体的性能影响》.天津大学硕士学位论文,2003,17-19.
[33]徐叙瑢,《发光学与发光材料》.北京：化学工业出版社,2004,第1版：53-55.
[34]Jie Liu, Hongzhou Lian, Jiayue Sun, Shi Chunshan. Characterization and properties of green emitting Ca3SiO4Cl2:Eu2+ powder phosphor for white light-emitting diodes[J] Chemistry Letters. 2005,34:10-12.
[35]Z.C. Wu, J.X. Shi, J. Wang, H. Wu, Q. Su, M.L. Gong. Synthesis and luminescent properties of SrAl2O4:Eu2+ green-emitting phosphor for white LEDs.[J]. Materials Letters 2006,60 (29-30): 3499-3501.
[36]Zhiping Yang, Xu Li, Yong Yang, Xingmin Li. The influence of different conditions on the luminescent properties of YAG:Ce phosphor formed by combustion. [J]. Journal of Luminescence, 2007,122-123:707-709.
[37]Guodong Xia, Shengming Zhou, Junji Zhang, Jun Xu. Sructural and optical properties of Y3Al5O12:Ce3+ phosphors by sol-gel combustion method.[J]. Journal of Crystal Growth, 2005,279:357-362.
[38]Yuexiao Pan, MingmeiWu, Qiang Su. Comparative investigation on synthesis and photoluminescence of YAG:Ce phosphor [J]. Materials Science and Engineering,2004, B 106:251-256
[39]Yuexiao Pan, MingmeiWu, Qiang Su, Tailored photoluminescence of YAG:Ce phosphor through various methods, [J]. Journal of Physics and Chemistry of Solids,2004,65:845-850.
[40]中国科学院吉林物理所等.[M].固体发光,中国科技大学出版社,1976,4
[41]S Daniel, B Jerome, C Dave. Selected Topics in Quantum Electronics[J].IEEE 2002,82:310-320
[42]S. Nakamura and G. Fasol. [M].The Blue Laser Diode:GaN Based Light Emitters and Lasers Springer, Berlin,1996.
[43]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.
[44]Lingli Wang, Yuhua Wang, Hui Gao. The Role of Gd3+ in the Luminescence of Several Eu3+ Activated Borate Phosphors under VUV Excitation. [J] Journal of The Electrochemical Society.2006,153(11): 943-947.
[45]Rao R P. Tb3+ Activated Green Phosphors for Plasma Display Panel Applications. [J]. Journal of The Electrochemical Society.2003,150(8):165-171.
[46]Lianhua Tian, Byung-Yong Yu, Chong-Hong Pyun, New red phosphors BaZr(BO3)2 and SrAl2B2O7 doped with Eu3+ for PDP applications. [J]. Solid State Communications.2004,129(1):43-46.
[47]王健,瞿存德,高正中.稀土硼酸盐黄色荧光粉的合成.[J].北京化工大学学报.1998,25(4)：81-84.
[48]D.S. Thakare, S.K. Omanwar, S.V. Moharil, S.M. Dhopte, P.L. Muthal, V.K. Kondawar. Combustion synthesis of borate phosphors. [J]. Optical Materials,2007,29(12):1731-1735.
[49]Fang Ying, Zhuang Weidong, Sun Yimin, Teng Xiaoming, He Huaqiang, Huang Xiaowei. Luminescence Properties of Eu2+ and Mn2+ Co-Doped CagMg(SiO4)4Cl2.[J]. Journal of Rare Earths, 2004,22(1):122-125.
[50]董岩,蒋建清,肖睿,刘刚,陈会东,于金.(Y,Gd)BO3：Eu3+荧光粉的合成及粒度控制.[J].中国稀土学报,2004,2(2)：201-205.
[2]郝海涛.白光LED用荧光材料的制备及性能研究.2006,太原理工大学硕士论文,3-5.
[3]Maruska H.P., Tietjen.J.J. The preparation and properties of vapor-desited single-crystal-line GaN. Applied Physics Letter,1969(15):327
[4]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.
[5]武毅.绿色光源—LED.[J].灯与照明,2005,30(2)：47-50.
[6]Werner K. Higher. visibility for LEDs.[J].IEEE Spectrum,1994,31(7):30-34.
[7]Sugawara H, Itaya K, Nozaki H. High brightness InGaAP freen light emitting diodes. [J].Applied Physics Letter,1992,61 (15):1775-1777.
[8]王进.光转换白光LED研究.[D].中国海洋大学2005年1-3.
[9]杨笑卫(译).高亮度、全光色LED.[J].中国照明电器,2001,4：23-25.
[10]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.[J].发光学报,2003,24(4)：385-389.
[11]Yuji Uchida, Tatsumi Setomotoa, Tsunemasa Taguchia, Yoshinori Nakagawa,Kazuto Miyazakib. Characteristics of high-efficient InGaN-based white LED lighting. [J].Pro.SPIE.,2000,4079:120-126.
[12]孟继武,王燕辛,王晶,郑荣儿.光转换白光LEDs的研究.[J].光电子·激光,2003,14(6)：566-569.
[13]刘洁,孙家跃,石春山.与LED匹配的白光发射荧光体的研究进展.[J].化学通报,2005,6：417-424.
[14]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,[J].发光学报.2003.24(4)：385-389.
[15]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., 2001,22(10):(Supp)21-23.
[16]孟继武,王燕辛,王晶,郑荣儿.光转换白光LEDs的研究.[J].光电子光激光,2003,14(6)：566-569.
[17]尹长安,赵成久,刘学彦,侯凤勤,郑岩,卢景贵,蒋大鹏,中德振.白光LED的最新进展.[J].发光学报,
2000,21(4)：380-382.
[18]杨笑卫(译).高亮度、全光色L E D.[J].中国照明电器,2001,4：23-25.
[19]刘行仁,薛胜薜,黄德森,林秀华.白光LED的现状和问题.[J].光源与照明,2003,3：4-8.
[20]李旭.白光LED用荧光粉的性能和制备.2006,河北大学硕士论文,2-3.
[21]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.
[22]刘如熹,石景仁.白光发光二极管用钇铝石榴石萤光粉配方与机制研究.[J].发光学报,2002,20(6)：405-501.
[23]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.
[24]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.
[25]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.
[26]Jun-Ho Yum, Seok-Soon Kim, Yung-Eun Sung. Y3Al5O12:Ceo.o5 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.
[27]Schlotter P, Schmidt R, Schneider J. Luminescence conversion of blue light emitting diodes.[J].Applied Physics A 1997,64:417-418.
[28]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.
[29]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.
[30]M. Veith, S. Mthur, A. Kareiva, M. Jilavi, M. Zimmer, V. Huch. [J]. Mater. Chem.,1999, (9): 3069-3072.
[31]R. Manalert,M. N. Rahaman.[J].Mater.Sci.,1996,(31):3453-3457.
[32]田华.《基质组成对铝酸锶发光体的性能影响》.天津大学硕士学位论文,2003,17-19.
[33]徐叙瑢,《发光学与发光材料》.北京：化学工业出版社,2004,第1版：53-55.
[34]Jie Liu, Hongzhou Lian, Jiayue Sun, Shi Chunshan. Characterization and properties of green emitting Ca3SiO4Cl2:Eu2+ powder phosphor for white light-emitting diodes[J] Chemistry Letters. 2005,34:10-12.
[35]Z.C. Wu, J.X. Shi, J. Wang, H. Wu, Q. Su, M.L. Gong. Synthesis and luminescent properties of SrAl2O4:Eu2+ green-emitting phosphor for white LEDs.[J]. Materials Letters 2006,60 (29-30): 3499-3501.
[36]Zhiping Yang, Xu Li, Yong Yang, Xingmin Li. The influence of different conditions on the luminescent properties of YAG:Ce phosphor formed by combustion. [J]. Journal of Luminescence, 2007,122-123:707-709.
[37]Guodong Xia, Shengming Zhou, Junji Zhang, Jun Xu. Sructural and optical properties of Y3Al5O12:Ce3+ phosphors by sol-gel combustion method.[J]. Journal of Crystal Growth, 2005,279:357-362.
[38]Yuexiao Pan, MingmeiWu, Qiang Su. Comparative investigation on synthesis and photoluminescence of YAG:Ce phosphor [J]. Materials Science and Engineering,2004, B 106:251-256
[39]Yuexiao Pan, MingmeiWu, Qiang Su, Tailored photoluminescence of YAG:Ce phosphor through various methods, [J]. Journal of Physics and Chemistry of Solids,2004,65:845-850.
[40]中国科学院吉林物理所等.[M].固体发光,中国科技大学出版社,1976,4
[41]S Daniel, B Jerome, C Dave. Selected Topics in Quantum Electronics[J].IEEE 2002,82:310-320
[42]S. Nakamura and G. Fasol. [M].The Blue Laser Diode:GaN Based Light Emitters and Lasers Springer, Berlin,1996.
[43]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.
[44]Lingli Wang, Yuhua Wang, Hui Gao. The Role of Gd3+ in the Luminescence of Several Eu3+ Activated Borate Phosphors under VUV Excitation. [J] Journal of The Electrochemical Society.2006,153(11): 943-947.
[45]Rao R P. Tb3+ Activated Green Phosphors for Plasma Display Panel Applications. [J]. Journal of The Electrochemical Society.2003,150(8):165-171.
[46]Lianhua Tian, Byung-Yong Yu, Chong-Hong Pyun, New red phosphors BaZr(BO3)2 and SrAl2B2O7 doped with Eu3+ for PDP applications. [J]. Solid State Communications.2004,129(1):43-46.
[47]王健,瞿存德,高正中.稀土硼酸盐黄色荧光粉的合成.[J].北京化工大学学报.1998,25(4)：81-84.
[48]D.S. Thakare, S.K. Omanwar, S.V. Moharil, S.M. Dhopte, P.L. Muthal, V.K. Kondawar. Combustion synthesis of borate phosphors. [J]. Optical Materials,2007,29(12):1731-1735.
[49]Fang Ying, Zhuang Weidong, Sun Yimin, Teng Xiaoming, He Huaqiang, Huang Xiaowei. Luminescence Properties of Eu2+ and Mn2+ Co-Doped CagMg(SiO4)4Cl2.[J]. Journal of Rare Earths, 2004,22(1):122-125.
[50]董岩,蒋建清,肖睿,刘刚,陈会东,于金.(Y,Gd)BO3：Eu3+荧光粉的合成及粒度控制.[J].中国稀土学报,2004,2(2)：201-205.