Eu~（2+）掺杂碱土金属卤磷酸盐蓝色荧光粉的制备与性质研究
摘要
白光LED具有低工作电压、低功耗、高流明效率和长寿命等一系列优点,是一种环保和节能的新型照明光源。因此白光LED及相关发光材料成为现在研究的热点。本文针对白光LED用长波紫光和紫外光激发的蓝色荧光材料进行研究。
本文首先对白光LED用蓝色荧光粉的研究现状、发展趋势以及各种制备方法进行了详细的综述。从高显色性白光LED需求的角度选择(SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+)蓝色荧光粉为研究对象。采用高温固相法在弱还原气氛中成功制备(SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+)蓝色荧光粉。详细研究了反应原料、烧结温度、Eu~(2+)激活剂浓度对荧光粉发光性质的影响。研究表明温度在1200℃,Eu~(2+)掺杂比为0.15时(SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+)蓝色荧光粉的发光峰在450nm并且可被200nm- 440nm波段有效激发。
进一步基于Eu~(2+)与Tb~(3+)之间的能量传递设计制备(SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(3+),Tb~(3+)荧光粉。样品在长波紫光和紫外光激发下呈蓝光与绿光的混合发光,发光颜色随Tb3+掺杂浓度可从蓝色调节为蓝绿色,从而可进一步提高白光LED的显色性。
本文对高显色性白光LED用发光材料的研制有重要意义。
White light-emitting diode (W-LED), as a novel kind of‘green lighting’, has many advantages over incadescent and fluorescent lamps, such as low working voltage, low power consumption, high luminous efficiency and long life. Therefore, W-LED and related phosphors have attracted worldwide attention. In this Master Thesis, we focus our research on blue-emitting phosphors that can be excited by long-wave ultraviolet or violet LED chips and will have practical applications in W-LED.
We review in the first part of thesis the present situation and future trends of W-LED and blue-emitting phosphors, with emphasis placed on the mechanism of W-LED, various kinds of phosphors and various preparation methods. For the demand of high color rendering W-LED, we chose (SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+) blue-emitting phosphor powder as the object of our study, and use high-temperature solid-state reaction method to prepare the phosphor powders in a weak reducing atmosphere. A detailed investigation on the reaction parameters, including kinds and relative ratio of raw materials, sintering temperature and Eu~(2+) activator concentration was conducted in terms of luminescent properties of phosphors powder. Our study show that optimal reaction parameters are: sintering temperature is 1200℃, Eu~(2+) doping level is 0.15. By these parameters, the (SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+) phosphor powder show bright blue emission around 450nm and can be efficiently excited by violet and ultraviolet light (200nm- 440nm).
Further we employed the energy transfer between Tb~(3+) and Eu~(2+) and prepared a novel series of phosphors using (SrCaBa)_3(PO_4)_2·SrCl_2 as host material. Our study show that emission color can be adjusted from blue to blue green by the ratio of Tb~(3+) to Eu~(2+), with line-like Tb~(3+) green emission overlapped on band-like Eu~(2+) blue emission. This novel series of phosphors may have promising applications in high-color-rendering W-LED.
本文首先对白光LED用蓝色荧光粉的研究现状、发展趋势以及各种制备方法进行了详细的综述。从高显色性白光LED需求的角度选择(SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+)蓝色荧光粉为研究对象。采用高温固相法在弱还原气氛中成功制备(SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+)蓝色荧光粉。详细研究了反应原料、烧结温度、Eu~(2+)激活剂浓度对荧光粉发光性质的影响。研究表明温度在1200℃,Eu~(2+)掺杂比为0.15时(SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+)蓝色荧光粉的发光峰在450nm并且可被200nm- 440nm波段有效激发。
进一步基于Eu~(2+)与Tb~(3+)之间的能量传递设计制备(SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(3+),Tb~(3+)荧光粉。样品在长波紫光和紫外光激发下呈蓝光与绿光的混合发光,发光颜色随Tb3+掺杂浓度可从蓝色调节为蓝绿色,从而可进一步提高白光LED的显色性。
本文对高显色性白光LED用发光材料的研制有重要意义。
White light-emitting diode (W-LED), as a novel kind of‘green lighting’, has many advantages over incadescent and fluorescent lamps, such as low working voltage, low power consumption, high luminous efficiency and long life. Therefore, W-LED and related phosphors have attracted worldwide attention. In this Master Thesis, we focus our research on blue-emitting phosphors that can be excited by long-wave ultraviolet or violet LED chips and will have practical applications in W-LED.
We review in the first part of thesis the present situation and future trends of W-LED and blue-emitting phosphors, with emphasis placed on the mechanism of W-LED, various kinds of phosphors and various preparation methods. For the demand of high color rendering W-LED, we chose (SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+) blue-emitting phosphor powder as the object of our study, and use high-temperature solid-state reaction method to prepare the phosphor powders in a weak reducing atmosphere. A detailed investigation on the reaction parameters, including kinds and relative ratio of raw materials, sintering temperature and Eu~(2+) activator concentration was conducted in terms of luminescent properties of phosphors powder. Our study show that optimal reaction parameters are: sintering temperature is 1200℃, Eu~(2+) doping level is 0.15. By these parameters, the (SrCaBa)_3(PO_4)_2·SrCl_2:Eu~(2+) phosphor powder show bright blue emission around 450nm and can be efficiently excited by violet and ultraviolet light (200nm- 440nm).
Further we employed the energy transfer between Tb~(3+) and Eu~(2+) and prepared a novel series of phosphors using (SrCaBa)_3(PO_4)_2·SrCl_2 as host material. Our study show that emission color can be adjusted from blue to blue green by the ratio of Tb~(3+) to Eu~(2+), with line-like Tb~(3+) green emission overlapped on band-like Eu~(2+) blue emission. This novel series of phosphors may have promising applications in high-color-rendering W-LED.
引文
[1]吴占超.磷、铝酸盐荧光粉的制备[D];[博士学位论文].广州:中山大学物理学院,2007
[2]刘行仁,白光LED的现状和问题[C]照明科技论坛论文集;上海;2002
[3]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.321.
[4]王晓明,郭伟玲,高国等,LED.新一代照明光源.现代显示,2005,53:15.19.
[5]刘行仁,薛胜薜,黄德森,林秀华,白光LED现状和问题.光源与照明,2003.3:4.8.
[6]刘行仁,发光学报[J],1996,17(supp):88
[7]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.323.
[8] S.Shionoya,W.M.Yen,Phosphor Handbook,CRC Press,1999
[9]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.201.
[10] Nakamura,S.;Fasol, The Blue Laser Diode[J].Springer.Berlin.1997
[11]尹长安,赵成久,刘学彦,侯风勤,郑岩,卢景贵,蒋大鹏,申德振,白光LED的最新进展.发光学报,2000,21:380.382.
[12]彭万华,我国超高亮度及白光LED产业的现状与发展.激光与红外,2005,35:223-227
[13]刘其鹏.白光LED荧光粉的研制与光谱特性研究[D];[硕士学位论文].长春:长春理工大学,2008
[14] M.Inokuti and F.Hirayama,Influence of energhy transfer by the exchange mechanism on donor Luminescence[J],J.Chem.Phys.1965,43(6),1978-1989.
[15] T.Forster,10th spiers memoriallecture transfer mechanisms of electronic excitation[J],Dicuss Faraday Soc,1959,27,7-17
[16] N.Nakamura,L.deng,Proc.SPLE-Int[J].Soc.Opt.Eng.2001,W4445,137-147
[17] K.Bando,lnGaN/YAG white LED for mobile devices and general illuminations,S1D Conference Record of the International Display Research Conference.2001,545-548.
[18] W.Jennifer,D.Earl,Optimization of cerium doped gamets uing combinatorial chemistry for application asluminescent phosphors in white LEDs,Mater.Res Soc.Symp.Proc.1999, 560,65-70
[19] S.Zhang.W.Zhuang,C.Zhao,Y.Hu,H.He,and X.Huang,study on(Y,Gd)3(AI,Ga)5O12:Ce3+ phosphor,J. Rare Earths.2004,22(I),118-121
[20] R.J.Xie, H.Naoto, K. Sakuma Y. Yamoto and M. Mitomo,Appl.Phys.Lett 2004, 84, 5404-5406
[21] R.J. Xie, N.Hirosaki, M.Mitomo, K.Sakuma, N. Kimura, Appl. Phys.Lett.2006,89,241103
[22] L.Y.Qun,J.E.J.vansteen,etal,Luminesence properties of red-emission M2Si5Ng:Eu2+(M=Ca,Sr,Ba)LED convertsion phosphors.J.A11oy Compound,2005,90,04
[23] J.K.Park,K.J.Choi,J.H.Yeon,S.J.Lee,etal.Appl.Phys.Lett 2006,88,04351
[24] J.S.Yoo,S.H.Kim,W.T.Yoo,G.Y.Hong,K.P.Kim,J.Rowland,and P.H.Holloway. J.Electrochem Soc., 2005, 152, G382-G385
[25] H.S.Jang and D.Y.Jeon,Appl.Phys Lett.90,041906(2007)
[26] J. Liu, J. Sun and C. Shi Mater. Lett. 2006, 60, 2830-2833
[27] M.P. Saradhi, U.V.Varadaraju.Chem.Mater.2006,18, 5267-5272.
[28]徐剑,张新民,张剑辉.郭象峰,苏锵中山大学学报(自然科学版).2004年03期.
[29] C. Xu, L. Ma, L. Can, Z. Xu,Z. Lou, X. Liu, X. Xu,Thin Solid Films.1997, 306, 160-162
[30]张英兰,赵绪义,吉林大学自然科学报,1997,(4):52-54
[31] L.D,Huh, J.H. Shim, Y.H. Kim, Y. R. Do, J.Electrochem.Soc.2003,150,H57-H60
[32] P.Yang, J. Lin, G. Yao.稀土学报(英文版).2005年05期
[33]孙家跃,夏志国,杜海燕.光谱学与光谱分析.2005年11期
[34] W. M.Yen, H. Yanmamoto.Phosphor Handbook.1051页
[35] J. Liu, H.Z. Lian, C.S. Shi, J.V.Sun. J.Electrochem.Soc.152(11),G880-G884
[36] J. Liu, C. Shi,Opt. Mater. 2007,29, 1591-1594
[37]李长学等,发光学报[J] 1988,2,25
[38] Y Narukawa,K lzuno Appl.[J]Phys,Lett,2002.L371-L373
[39] A.Setlur,W. J.Heward, G. Yan, A. M.Srivastava, R.G. Chandran,M. V.Shankar Chem.Mater. 2006,18,3314-3322,
[40]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.293.
[41]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.294.
[42]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.295.
[43]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.296.
[44] N. Hirosaki,R. Xie,K. Kironto,T. Sekiguchi,Y. Yamamoto,T. Suehiro, M. Mitomo,Appl.Phys.Lett.86,211905(2005)
[45]刘行仁,王晓军,金伟华,中国粉体技术[J],2001,7,
[46]赵春雷,黄小卫,张书生,庄卫东,何华强.中国稀土学报2002年06期
[47]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.599-603.
[48]陈哲.Eu2+荧光粉的制备[D];[博士学位论文].上海:华中科技大学,2006
[49] I W Lenggoro, B Xia, H Mizashima, et al. Synthesis of LaPO4: Ce,Tb phosphor particles by spray pyrolysis. Mater. Lett., 2001,50(2-3): 92-96
[50] B S Jeon, G Y Hong, Y K I Yoo, et al. Spherical BaMgAl10O17:Eu2+phosphor prepared by aerosolpyrolysis technique for PDP applications [J]. J. Electrochem. Soc., 2001, 148(9): H128-131
[51] E. J Kim, Y C Kang, H D Park, et al. UV and VUV characteristics of (Y,Gd)2O3: Eu phosphor particles prepared by spray pyrolysis from polymeric precursors. Mater. Res. Bull., 2003, 38(3): 515-524
[52] K Y Jung, Y C Kang. Preparation of BaMgAl10O17: Eu blue phosphor by flame-assisted spray pyrolysis: photoluminescence properties of powder and film under VUV excitation [J]. Mater. Lett., 2004,58(16): 2161-2165
[53] Y C Kang, S B Park, et al. Preparation of nonaggregated Y2O3: Eu phosphor particles by spray pyrolysis method [J].Mater. Res. Bull., 1999, 14(6):2611-2614
[54]闵庆旺.纳米稀土磷酸盐发光材料的制备[D];[硕士学位论文].沈阳:辽宁师范大学,2003
[55]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.285.
[2]刘行仁,白光LED的现状和问题[C]照明科技论坛论文集;上海;2002
[3]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.321.
[4]王晓明,郭伟玲,高国等,LED.新一代照明光源.现代显示,2005,53:15.19.
[5]刘行仁,薛胜薜,黄德森,林秀华,白光LED现状和问题.光源与照明,2003.3:4.8.
[6]刘行仁,发光学报[J],1996,17(supp):88
[7]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.323.
[8] S.Shionoya,W.M.Yen,Phosphor Handbook,CRC Press,1999
[9]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.201.
[10] Nakamura,S.;Fasol, The Blue Laser Diode[J].Springer.Berlin.1997
[11]尹长安,赵成久,刘学彦,侯风勤,郑岩,卢景贵,蒋大鹏,申德振,白光LED的最新进展.发光学报,2000,21:380.382.
[12]彭万华,我国超高亮度及白光LED产业的现状与发展.激光与红外,2005,35:223-227
[13]刘其鹏.白光LED荧光粉的研制与光谱特性研究[D];[硕士学位论文].长春:长春理工大学,2008
[14] M.Inokuti and F.Hirayama,Influence of energhy transfer by the exchange mechanism on donor Luminescence[J],J.Chem.Phys.1965,43(6),1978-1989.
[15] T.Forster,10th spiers memoriallecture transfer mechanisms of electronic excitation[J],Dicuss Faraday Soc,1959,27,7-17
[16] N.Nakamura,L.deng,Proc.SPLE-Int[J].Soc.Opt.Eng.2001,W4445,137-147
[17] K.Bando,lnGaN/YAG white LED for mobile devices and general illuminations,S1D Conference Record of the International Display Research Conference.2001,545-548.
[18] W.Jennifer,D.Earl,Optimization of cerium doped gamets uing combinatorial chemistry for application asluminescent phosphors in white LEDs,Mater.Res Soc.Symp.Proc.1999, 560,65-70
[19] S.Zhang.W.Zhuang,C.Zhao,Y.Hu,H.He,and X.Huang,study on(Y,Gd)3(AI,Ga)5O12:Ce3+ phosphor,J. Rare Earths.2004,22(I),118-121
[20] R.J.Xie, H.Naoto, K. Sakuma Y. Yamoto and M. Mitomo,Appl.Phys.Lett 2004, 84, 5404-5406
[21] R.J. Xie, N.Hirosaki, M.Mitomo, K.Sakuma, N. Kimura, Appl. Phys.Lett.2006,89,241103
[22] L.Y.Qun,J.E.J.vansteen,etal,Luminesence properties of red-emission M2Si5Ng:Eu2+(M=Ca,Sr,Ba)LED convertsion phosphors.J.A11oy Compound,2005,90,04
[23] J.K.Park,K.J.Choi,J.H.Yeon,S.J.Lee,etal.Appl.Phys.Lett 2006,88,04351
[24] J.S.Yoo,S.H.Kim,W.T.Yoo,G.Y.Hong,K.P.Kim,J.Rowland,and P.H.Holloway. J.Electrochem Soc., 2005, 152, G382-G385
[25] H.S.Jang and D.Y.Jeon,Appl.Phys Lett.90,041906(2007)
[26] J. Liu, J. Sun and C. Shi Mater. Lett. 2006, 60, 2830-2833
[27] M.P. Saradhi, U.V.Varadaraju.Chem.Mater.2006,18, 5267-5272.
[28]徐剑,张新民,张剑辉.郭象峰,苏锵中山大学学报(自然科学版).2004年03期.
[29] C. Xu, L. Ma, L. Can, Z. Xu,Z. Lou, X. Liu, X. Xu,Thin Solid Films.1997, 306, 160-162
[30]张英兰,赵绪义,吉林大学自然科学报,1997,(4):52-54
[31] L.D,Huh, J.H. Shim, Y.H. Kim, Y. R. Do, J.Electrochem.Soc.2003,150,H57-H60
[32] P.Yang, J. Lin, G. Yao.稀土学报(英文版).2005年05期
[33]孙家跃,夏志国,杜海燕.光谱学与光谱分析.2005年11期
[34] W. M.Yen, H. Yanmamoto.Phosphor Handbook.1051页
[35] J. Liu, H.Z. Lian, C.S. Shi, J.V.Sun. J.Electrochem.Soc.152(11),G880-G884
[36] J. Liu, C. Shi,Opt. Mater. 2007,29, 1591-1594
[37]李长学等,发光学报[J] 1988,2,25
[38] Y Narukawa,K lzuno Appl.[J]Phys,Lett,2002.L371-L373
[39] A.Setlur,W. J.Heward, G. Yan, A. M.Srivastava, R.G. Chandran,M. V.Shankar Chem.Mater. 2006,18,3314-3322,
[40]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.293.
[41]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.294.
[42]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.295.
[43]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.296.
[44] N. Hirosaki,R. Xie,K. Kironto,T. Sekiguchi,Y. Yamamoto,T. Suehiro, M. Mitomo,Appl.Phys.Lett.86,211905(2005)
[45]刘行仁,王晓军,金伟华,中国粉体技术[J],2001,7,
[46]赵春雷,黄小卫,张书生,庄卫东,何华强.中国稀土学报2002年06期
[47]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.599-603.
[48]陈哲.Eu2+荧光粉的制备[D];[博士学位论文].上海:华中科技大学,2006
[49] I W Lenggoro, B Xia, H Mizashima, et al. Synthesis of LaPO4: Ce,Tb phosphor particles by spray pyrolysis. Mater. Lett., 2001,50(2-3): 92-96
[50] B S Jeon, G Y Hong, Y K I Yoo, et al. Spherical BaMgAl10O17:Eu2+phosphor prepared by aerosolpyrolysis technique for PDP applications [J]. J. Electrochem. Soc., 2001, 148(9): H128-131
[51] E. J Kim, Y C Kang, H D Park, et al. UV and VUV characteristics of (Y,Gd)2O3: Eu phosphor particles prepared by spray pyrolysis from polymeric precursors. Mater. Res. Bull., 2003, 38(3): 515-524
[52] K Y Jung, Y C Kang. Preparation of BaMgAl10O17: Eu blue phosphor by flame-assisted spray pyrolysis: photoluminescence properties of powder and film under VUV excitation [J]. Mater. Lett., 2004,58(16): 2161-2165
[53] Y C Kang, S B Park, et al. Preparation of nonaggregated Y2O3: Eu phosphor particles by spray pyrolysis method [J].Mater. Res. Bull., 1999, 14(6):2611-2614
[54]闵庆旺.纳米稀土磷酸盐发光材料的制备[D];[硕士学位论文].沈阳:辽宁师范大学,2003
[55]徐叙瑢,苏勉曾.发光学与发光材料[M].北京:化学工业出版社和材料科学与工程出版中心,2004.285.