稀土硅酸盐荧光粉制备及其性能的研究
摘要
硅酸盐基质具有良好的化学稳定性和热稳定性,长期以来人们都重视对硅酸盐基质荧光粉的研究和开发。单一基质白光荧光粉因具有流明效率高、色彩还原性好等特点,所以对其研究的意义重大。
本文主要采用高温固相法,合成了M2SiO4:Dy3+,Eu3+(M=Mg, Ca)系列LED用荧光粉,并对样品相应结构特性和近紫外光激发下的发光特性进行了研究。
系列样品M2SiO4:Dy3+,Eu3+(M=Mg, Ca)的X射线粉末衍射数据与JCPDS标准卡片符合得很好,这表明我们合成的材料是碱土金属硅酸盐,属于正硅酸盐体系。
在对掺Dy3+荧光粉的光谱分析可知,样品的吸收峰位于325nm、350nm、365nm和386nm附近,分别对应Dy3+离子6H15/2→6P3/2,6H15/2→6P7/2,6H15/2→6P5/2,6H15／2→4M21/2的跃迁。其用386nm紫外光激发,在位于480nm、492nm、575nm附近出现发射峰,分别对应于Dy3+离子4F9／2→6H15／2的跃迁,579nm对应于Dy3+离子4F9／2→6H13／2的发射跃迁。
制备了Dy3+,Eu3+共掺杂样品,对其的光谱分析表明,明显增加了红光区发射此外还有橙色光590nm、红色光616nm、653nm、704nm处的发射,以上均为Eu3+的5D0→7FJ(J=1,2,3,4)能级的跃迁发射。稀土Eu3+离子的加入对样品发光所对应色坐标及色温影响较大。
合成并分析了二元系碱土金属阳离子样品(MgxCa1-x) 2SiO4:Dy3+,Eu3+的紫外光谱特性,研究了碱土离子比例不同对光谱及色坐标的影响。
本论文中图23幅,表8个,参考文献45篇。
Silicate matrix has good chemical stability and thermal stability. People have focused a lot of attention on the research and development of silicate phosphor matrix for a long time. Due to the high lumens efficiency, good color reproduction characteristics of single matrix white phosphor, the research on it has great significance.
In this paper, series samples of white LED phosphor M2SiO4:Dy3+, Eu3+(M= Mg, Ca) have been synthesized by high temperature solid state, and the corresponding structure characteristics and near-UV excited luminescent properties of the samples were studied.
The X-ray powder diffraction data of series samples M2SiO4: Dy3+,Eu3+(M= Mg, Ca) have good agreement with JCPDS standard card, which shows that the synthetic material is alkaline earth metal silicate, belonged to silicate system.
The excitation spectra of Ca2SiO4:Dy3+ show strong absorption near 325nm,350nm, 365nm and 386nm due to H15/2→6P3/2,6H15/2→6P7/2,6H15/2→6P5/2,6H15/2→4M21/2 transition of Dy3+. The emission light is at about 480nm、492nm、575nm under 386nm UV excitation. The emission at 482nm and 492nm (Blue) attribute to the 4F9/2→6H15/2 transition and 579nm (Yellow) attributes to the 4F9/2→6H13/2 transition.
Series samples of co-doped Dy3+, Eu3+ M2SiO4 (M=Mg, Ca) have been synthesized. The spectra show that in addition to Dy3+ emission bands in blue and yellow of the characteristic peak, there are four other peaks at orange area 590nm, red area 616nm,653nm,704nm due to the Eu3+ in the 5D0→7FJ(J=1,2,3,4). Red light district of emission has been enhanced. The doped rare earth ions Eu3+ luminescence of samples has great impact in color coordinates (CIE) and color temperature.
Still we prepared (MgxCa1-x)2SiO4: Dy3+,Eu3+ phosphors and analyzed under UV excitation. Different ratios of alkaline earth ions in the sample affect the spectrum and the color coordinates (CIE).
There are 23 figures,8 tables and 45 references in this paper.
本文主要采用高温固相法,合成了M2SiO4:Dy3+,Eu3+(M=Mg, Ca)系列LED用荧光粉,并对样品相应结构特性和近紫外光激发下的发光特性进行了研究。
系列样品M2SiO4:Dy3+,Eu3+(M=Mg, Ca)的X射线粉末衍射数据与JCPDS标准卡片符合得很好,这表明我们合成的材料是碱土金属硅酸盐,属于正硅酸盐体系。
在对掺Dy3+荧光粉的光谱分析可知,样品的吸收峰位于325nm、350nm、365nm和386nm附近,分别对应Dy3+离子6H15/2→6P3/2,6H15/2→6P7/2,6H15/2→6P5/2,6H15／2→4M21/2的跃迁。其用386nm紫外光激发,在位于480nm、492nm、575nm附近出现发射峰,分别对应于Dy3+离子4F9／2→6H15／2的跃迁,579nm对应于Dy3+离子4F9／2→6H13／2的发射跃迁。
制备了Dy3+,Eu3+共掺杂样品,对其的光谱分析表明,明显增加了红光区发射此外还有橙色光590nm、红色光616nm、653nm、704nm处的发射,以上均为Eu3+的5D0→7FJ(J=1,2,3,4)能级的跃迁发射。稀土Eu3+离子的加入对样品发光所对应色坐标及色温影响较大。
合成并分析了二元系碱土金属阳离子样品(MgxCa1-x) 2SiO4:Dy3+,Eu3+的紫外光谱特性,研究了碱土离子比例不同对光谱及色坐标的影响。
本论文中图23幅,表8个,参考文献45篇。
Silicate matrix has good chemical stability and thermal stability. People have focused a lot of attention on the research and development of silicate phosphor matrix for a long time. Due to the high lumens efficiency, good color reproduction characteristics of single matrix white phosphor, the research on it has great significance.
In this paper, series samples of white LED phosphor M2SiO4:Dy3+, Eu3+(M= Mg, Ca) have been synthesized by high temperature solid state, and the corresponding structure characteristics and near-UV excited luminescent properties of the samples were studied.
The X-ray powder diffraction data of series samples M2SiO4: Dy3+,Eu3+(M= Mg, Ca) have good agreement with JCPDS standard card, which shows that the synthetic material is alkaline earth metal silicate, belonged to silicate system.
The excitation spectra of Ca2SiO4:Dy3+ show strong absorption near 325nm,350nm, 365nm and 386nm due to H15/2→6P3/2,6H15/2→6P7/2,6H15/2→6P5/2,6H15/2→4M21/2 transition of Dy3+. The emission light is at about 480nm、492nm、575nm under 386nm UV excitation. The emission at 482nm and 492nm (Blue) attribute to the 4F9/2→6H15/2 transition and 579nm (Yellow) attributes to the 4F9/2→6H13/2 transition.
Series samples of co-doped Dy3+, Eu3+ M2SiO4 (M=Mg, Ca) have been synthesized. The spectra show that in addition to Dy3+ emission bands in blue and yellow of the characteristic peak, there are four other peaks at orange area 590nm, red area 616nm,653nm,704nm due to the Eu3+ in the 5D0→7FJ(J=1,2,3,4). Red light district of emission has been enhanced. The doped rare earth ions Eu3+ luminescence of samples has great impact in color coordinates (CIE) and color temperature.
Still we prepared (MgxCa1-x)2SiO4: Dy3+,Eu3+ phosphors and analyzed under UV excitation. Different ratios of alkaline earth ions in the sample affect the spectrum and the color coordinates (CIE).
There are 23 figures,8 tables and 45 references in this paper.
引文
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[2]毛兴武,张艳雯,周建军,祝大卫编著。新一代绿色光源LED及其应用技术。北京：人民邮电出版社,2008,25-33。
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[14]杨志平, 刘玉峰,王利伟,等。用于白光LED的单一基质白光荧光粉Ca2SiO3Cl2: Eu2+,Mn2+的发光性质[J]。物理学报,2007,56(1)：546—-550。
[15]孙晓园,张家骅,张霞,等。新一代白光LED照明用一种适于近紫外光激发的单一白光荧光粉[J]。发光学报,2005,26(3)：404—-406。
[16]李建宇编著。稀土发光材料及其应用。北京：化学工业出版社,2003,11-14。
[17]Shibata N, et al. Phys Stat Sol (A),2003,200:58.
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[19]WU H, ZHANG X M, GUO C F, et al. Three-band white light from InGaN-based blue LED chip precoated with green/red phosphors [J]. IEEE Photonics Tech Lett,2005,17(6): 1160-1162.
[20]Su Qiang. J. Lumi,1983,28(1):11.
[21]彭子飞,余军保,罗彩芹,徐铸。燃烧法制备Zn2SiO4:Eu3+红色荧光粉及其发光性[J]。中国稀土学报。2008,26(2)：234-237
[22]杨志平,刘玉峰。Eu2+激活的Ca3SiO5绿色荧光粉的制备和发光特性研究[J].物理学报。2004.55(9)：4949-4950.
[23]尹长安,赵成久,刘学彦等。发光快报,2000,21(4)：380。
[24]徐晶,夏威,邓华,边福强,肖志国。高性能Sr2 一 Bax SiO4:Eu+荧光材料的合成及发光[J]。发光学报,2009,30(5)：617-622
[25]S. Murakami, Y. Anzai, H. Itoh, Mitsubishi Denki Giho,1978,52:701.
[26]NARUKAWA Y, NILI I, IZUND K, et al. Phosphor-conversion white light emitting diode using InGaN near-ultraviolet chip [J]. Jpn J Appl Phys,2002,41:L371-L373.
[27]SHEU J K, CHANG S J, KUO C H, et al. IEEE Photonics Tech Lett,15(1):18-20.
[28]Phosphor Handbook,1999, P415.
[29]孙晓园,张家骅,张霞等。新一代白光LED照明用一种适于近紫外光激发的单一白
光荧光粉[J]。发光学报,2005,26(3)：404。
[30]Su Qiang, Pei Zhiwu, Chi Lisheng, et al. The yellow-to-blue intensity ratio (Y/B) of Dy3+ emission [J]. Journal of Alloys and Compounds,1993,192:25-27.
[31]Su Qiang, Pei Zhiwu, Lin Jun, et al. Luminescence of Dy3+ enhanced by sensitization [J]. Journal of Alloys and Compounds,1995,225:103-106.
[32]徐叙瑢,苏勉曾主编。发光学与发光材料。北京：化学工业出版社,2004,592。
[33]Xiaoming Liu, Cuikun Lin, and Jun Lin. White light Emission from Eu3+ in CaIn2O4 host lattices [J]. APPLIED PHYSICS LETTERS,2007,90,081904
[34]Jun L, Dirk U S, KB M M.. Thin Solid Flims,2000,360:39.
[35]陈仲林等。中国照明电器,1999,6：5。
[36]臧李纳等。稀有金属,2000,24(6)：410。
[37]张迈生等。发光学报,1999,20(3)：258。
[38]张迈生等。材料导报,2001,15(2)：70。
[39]林元华,张中太,张枫等。材料导报,2000,14(1)：35。
[40]T. R. N. Kutty, R. Jannathan. Mater Res. Bull.,1990,25:1355.
[41]Kim J S, Jeon P E, Choi J C, et al. Warm-white-light emitting diode utilizing a single-phase full-color Ba3MgSi2O8:Eu2+, Mn2+ phosphor [J]. Appl. Phys. Lett.,2004, 84(15):2931-2933.
[42]Kim J S, Jeon P E, Park Y H, et al. White-light generation through ultraviolet-emitting diode and white-emitting phosphor [J]. Appl. Phys. Lett.,2004,85(17):3696-3698.
[43]Yang P, Yao G, Lin J. Opt Mater,2004,26:327.
[44]孙家跃,杜海燕,胡文祥编著。固体发光材料。北京：化学工业出版社,2003,88-92。
[45]Yonghu Chen,Xuerui Cheng, Miao Liu,Zeming Qi, Chaoshu Shi. Comparison study of the luminescent properties of the white-light long afterglow phosphors:Ca_xMgSi_2O_(5+x): Dy3+(x=1,2,3)[J].Journal of Luminescence.2009,129,531-535.
[2]毛兴武,张艳雯,周建军,祝大卫编著。新一代绿色光源LED及其应用技术。北京：人民邮电出版社,2008,25-33。
[3]雷玉堂,黎慧。光学与光电技术,2003,12：33。
[4]方志烈编著。半导体照明技术。北京：电子工业出版社,2009,37。
[5]张中太,张俊英编著。无机光致发光材料及应用。北京：化学工业出版社,2005,188。
[6]Junji Kido, Masato Kimura, Katsutoshi Nagai. Science,1995,267:1332.
[7]Xie Zhi-yuan, Li Yan-qin, Huang Jing-song, et al. Synthetic Metals,1999,106:71.
[8]Z Y Xie, Feng, J S Huang, et al. Synthetic Metals,2000,108:81.
[9]Zhang Bu-xin, Zhu Wen-qing, Jiang Xue-yin, et al. J. of Optoelectronics Laser,2001,12(2): 112.
[10]M Mazzeo, J Thompson, R I R Blyth, et al. Physica E,2002,13:1243.
[11]崔元日。浅谈城市照明与节约能源。照明视界,2007(4)：1。
[12]只友一行,城市隆秀等。三菱电线工业时报,2002,第99号(7月)：35。
[13]Kim J S,Lim K T,Jeong Y S, et al. Full-color Ba3MgSi2O8:Eu2+,Mn2+ phosphors for white-light-emitting diodes[J]. Sol. Stat. Comm,2005, (135):21-24。
[14]杨志平, 刘玉峰,王利伟,等。用于白光LED的单一基质白光荧光粉Ca2SiO3Cl2: Eu2+,Mn2+的发光性质[J]。物理学报,2007,56(1)：546—-550。
[15]孙晓园,张家骅,张霞,等。新一代白光LED照明用一种适于近紫外光激发的单一白光荧光粉[J]。发光学报,2005,26(3)：404—-406。
[16]李建宇编著。稀土发光材料及其应用。北京：化学工业出版社,2003,11-14。
[17]Shibata N, et al. Phys Stat Sol (A),2003,200:58.
[18]余宪恩编著。实用发光材料与光致发光机理。北京：中国轻工业出版社,1997,44。
[19]WU H, ZHANG X M, GUO C F, et al. Three-band white light from InGaN-based blue LED chip precoated with green/red phosphors [J]. IEEE Photonics Tech Lett,2005,17(6): 1160-1162.
[20]Su Qiang. J. Lumi,1983,28(1):11.
[21]彭子飞,余军保,罗彩芹,徐铸。燃烧法制备Zn2SiO4:Eu3+红色荧光粉及其发光性[J]。中国稀土学报。2008,26(2)：234-237
[22]杨志平,刘玉峰。Eu2+激活的Ca3SiO5绿色荧光粉的制备和发光特性研究[J].物理学报。2004.55(9)：4949-4950.
[23]尹长安,赵成久,刘学彦等。发光快报,2000,21(4)：380。
[24]徐晶,夏威,邓华,边福强,肖志国。高性能Sr2 一 Bax SiO4:Eu+荧光材料的合成及发光[J]。发光学报,2009,30(5)：617-622
[25]S. Murakami, Y. Anzai, H. Itoh, Mitsubishi Denki Giho,1978,52:701.
[26]NARUKAWA Y, NILI I, IZUND K, et al. Phosphor-conversion white light emitting diode using InGaN near-ultraviolet chip [J]. Jpn J Appl Phys,2002,41:L371-L373.
[27]SHEU J K, CHANG S J, KUO C H, et al. IEEE Photonics Tech Lett,15(1):18-20.
[28]Phosphor Handbook,1999, P415.
[29]孙晓园,张家骅,张霞等。新一代白光LED照明用一种适于近紫外光激发的单一白
光荧光粉[J]。发光学报,2005,26(3)：404。
[30]Su Qiang, Pei Zhiwu, Chi Lisheng, et al. The yellow-to-blue intensity ratio (Y/B) of Dy3+ emission [J]. Journal of Alloys and Compounds,1993,192:25-27.
[31]Su Qiang, Pei Zhiwu, Lin Jun, et al. Luminescence of Dy3+ enhanced by sensitization [J]. Journal of Alloys and Compounds,1995,225:103-106.
[32]徐叙瑢,苏勉曾主编。发光学与发光材料。北京：化学工业出版社,2004,592。
[33]Xiaoming Liu, Cuikun Lin, and Jun Lin. White light Emission from Eu3+ in CaIn2O4 host lattices [J]. APPLIED PHYSICS LETTERS,2007,90,081904
[34]Jun L, Dirk U S, KB M M.. Thin Solid Flims,2000,360:39.
[35]陈仲林等。中国照明电器,1999,6：5。
[36]臧李纳等。稀有金属,2000,24(6)：410。
[37]张迈生等。发光学报,1999,20(3)：258。
[38]张迈生等。材料导报,2001,15(2)：70。
[39]林元华,张中太,张枫等。材料导报,2000,14(1)：35。
[40]T. R. N. Kutty, R. Jannathan. Mater Res. Bull.,1990,25:1355.
[41]Kim J S, Jeon P E, Choi J C, et al. Warm-white-light emitting diode utilizing a single-phase full-color Ba3MgSi2O8:Eu2+, Mn2+ phosphor [J]. Appl. Phys. Lett.,2004, 84(15):2931-2933.
[42]Kim J S, Jeon P E, Park Y H, et al. White-light generation through ultraviolet-emitting diode and white-emitting phosphor [J]. Appl. Phys. Lett.,2004,85(17):3696-3698.
[43]Yang P, Yao G, Lin J. Opt Mater,2004,26:327.
[44]孙家跃,杜海燕,胡文祥编著。固体发光材料。北京：化学工业出版社,2003,88-92。
[45]Yonghu Chen,Xuerui Cheng, Miao Liu,Zeming Qi, Chaoshu Shi. Comparison study of the luminescent properties of the white-light long afterglow phosphors:Ca_xMgSi_2O_(5+x): Dy3+(x=1,2,3)[J].Journal of Luminescence.2009,129,531-535.