磷酸盐稀土荧光材料的制备及性能研究
摘要
本文采用高温固相法合成了几种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,并对其激发光谱和发射光谱进行了研究,解释了所合成荧光材料的发光性质与原理。主要内容如下：
(1)合成了BaZnP2O7:Eu3+橙红色荧光粉,分析了碱土金属离子Li+、Na+和Cl-作为电荷补偿剂及Eu3+含量对样品发光性能的影响。
(2)合成了NaCaPO4:Eu2+绿色荧光粉,其激发主峰值位于400nm,与UVLED管芯(350-410nm)匹配。考察了Eu2+含量对样品发光性能的影响。
(3)合成了NaCaPO4:Tb3+绿色荧光粉,其激发主峰值与UVLED管芯匹配。分析了碱土金属离子Li+、Na+和K+作为电荷补偿剂及Tb3+含量对样品发光性能的影响。
(4)研究了Eu2+和Mn2+共掺杂的BaZnP2O7的光谱特性,随Mn2+浓度的增加,Eu2+的发射峰强度减小而Mn2+的发射峰强度增强,表明在BaZnP2O7:Eu2+,Mn2+中Eu2+对Mn2+的发光有明显的敏化作用。根据Dexter电多极相互作用的能量传递几率公式判断出Eu2+对Mn2+的能量传递属于电偶极-电四极相互作用引起的共振能量传递。
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 emission and excitation spectra of the phosphor were investigated, and the luminescent mechanism of the phosphors were analysed. The chief contents are given as follows:
(1) The BaZnP2O7:Eu3+phosphor was prepared. The role of charge compensation of Li+, Na+ and Cl- and doped-Eu3+ concentration to the emission intensity was studied.
(2) A novel green-emitting phosphor NaCaPO4:Eu2+ was prepared. The excitation spectrum is a broad band extending from 250 to 450 rm, which matches the emission of UVLED(350-410 nm). The effect of doped Eu2+ concentration on the emission intensity was also investigated.
(3) The NaCaPO4: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 doped-Tb3+ concentration and charge compensations of Li+, Na+ and K+ on the emission intensity are also investigated.
(4)The spectra characteristic of BaZnP2O7:Eu2+, Mn2+ was studied. With the increasing Mn2+ dopant content, the intensity of Eu2+ was observed to decrease, but the intensity of Mn2+ was simultaneously found to increase. It is suggested that Mn2+ ion is sensitized by Eu2+ ion. According to the Dexter's energy transfer formula of multipolar interaction, we have demonstrated that the energy transfer between Eu2+ and Mn2+ is due to the electric dipole-quadripole interaction of the resonance transfer.
(1)合成了BaZnP2O7:Eu3+橙红色荧光粉,分析了碱土金属离子Li+、Na+和Cl-作为电荷补偿剂及Eu3+含量对样品发光性能的影响。
(2)合成了NaCaPO4:Eu2+绿色荧光粉,其激发主峰值位于400nm,与UVLED管芯(350-410nm)匹配。考察了Eu2+含量对样品发光性能的影响。
(3)合成了NaCaPO4:Tb3+绿色荧光粉,其激发主峰值与UVLED管芯匹配。分析了碱土金属离子Li+、Na+和K+作为电荷补偿剂及Tb3+含量对样品发光性能的影响。
(4)研究了Eu2+和Mn2+共掺杂的BaZnP2O7的光谱特性,随Mn2+浓度的增加,Eu2+的发射峰强度减小而Mn2+的发射峰强度增强,表明在BaZnP2O7:Eu2+,Mn2+中Eu2+对Mn2+的发光有明显的敏化作用。根据Dexter电多极相互作用的能量传递几率公式判断出Eu2+对Mn2+的能量传递属于电偶极-电四极相互作用引起的共振能量传递。
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 emission and excitation spectra of the phosphor were investigated, and the luminescent mechanism of the phosphors were analysed. The chief contents are given as follows:
(1) The BaZnP2O7:Eu3+phosphor was prepared. The role of charge compensation of Li+, Na+ and Cl- and doped-Eu3+ concentration to the emission intensity was studied.
(2) A novel green-emitting phosphor NaCaPO4:Eu2+ was prepared. The excitation spectrum is a broad band extending from 250 to 450 rm, which matches the emission of UVLED(350-410 nm). The effect of doped Eu2+ concentration on the emission intensity was also investigated.
(3) The NaCaPO4: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 doped-Tb3+ concentration and charge compensations of Li+, Na+ and K+ on the emission intensity are also investigated.
(4)The spectra characteristic of BaZnP2O7:Eu2+, Mn2+ was studied. With the increasing Mn2+ dopant content, the intensity of Eu2+ was observed to decrease, but the intensity of Mn2+ was simultaneously found to increase. It is suggested that Mn2+ ion is sensitized by Eu2+ ion. According to the Dexter's energy transfer formula of multipolar interaction, we have demonstrated that the energy transfer between Eu2+ and Mn2+ is due to the electric dipole-quadripole interaction of the resonance transfer.
引文
[1]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.
[2]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.
[3]武毅.绿色光源-LED.[J].灯与照明,2005,30(2)：47-50.
[4]王进.光转换白光LED研究.[D].中国海洋大学2005年,1-3.
[5]杨笑卫(译).高亮度、全光色LED.[J].中国照明电器,2001,4：23-25.
[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 Letters,1992,61(15):1775-1777.
[8]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.
[9]张书生,庄卫东,赵春雷。助熔剂对Y3Al5O12：Ce荧光粉性能的影响.[J].中国稀土学报,2002,6：605-607.
[10]刘如熹,石景仁。白光发光二极管用钇铝石榴石荧光粉的配方与机制研究.[J].中国稀土学报,2002.6：495-501.
[11]Jacobs R R, Krupke W F, Weber M. Measurement of excited-state-absorption loss for Ce3+ in Y3Al5O12 and implications for tunable 5d→4f rare earth laser. [J]. Applied Physics Letters,1978,33:410-412.
[12]Blasse G, Bril A. A new phosphor for flying-spot cathode-ray tubes for color television: yellow-emitting Y3Al5O12. [J]. Applied Physics Letters.1967,11:53-55.
[13]张若桦,申泮文.稀土元素化学.[M].天津：科技出版社,1987.
[14]《固体发光》编写组.固体发光.[M].安徽：中国科技大学出版社,1976.
[15]D. T. Palumbo, J. J. Brown, Jr. Electronic states of Mn2+-activated phosphors. [J]. Journal of the Electrochemical Society,1970,117:1184-1188.
[16]孙家跃等.固体发光材料.[M].北京：化学工业出版社,2003：7.
[17]Shuji Nakamura, Gerhard Fasol, The Blue Laser Diode [M]. GaN Based Light Emitters and Lasers Springer, Berlin,1996.
[18]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
[19]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.
[20]Woan-Jen Yang, Teng-Ming 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
[21]毛向辉,吴振国,廉世勋,Eu2+离子在光转换材料中作用的研究.[J].湖南师范大学学报,1994,17(2)：56-58.
[22]Lingdong Sun, Cheng Qian, Chunsheng Liao. Luminescent properties of Li doped nanosized Y2O3:Eu.[J]. Solid State Communications,2001,119(6):393-396.
[23]余锡宾,杨良准,杨仕平,周春蕾,许晓琳,唐锦锋,彭秀东.SrZnO2:Eu3+,Li+长波紫外激发红光荧光体的合成及发光性能研究[J].中国稀土学报,2005,23(5)：533-536
[24]Kenichi YAMADA, Masato OHTA, Tsunemasa TAGUCHI, J. Light&Vis. Env[J],2004,28(2):73-80
[25]Joung Kyu Park, Kyoung Jae Choi, Jeong Ho Yeon, Seung Jae Lee, Chang Hae Kim. Embodiment of the warm white-light-emitting diodes by using a Ba2+ codoped Sr3SiO5:Eu2+ phosphor. [J]. Applied Physics Letters,2006,88:043511.
[26]Xiaoming Liu, Cuikun Lin, and Jun Lin. White light emission from Eu3+ in CaIn2O4 host lattices[J]. Applied Physics Letters,2007,90:081904
[27]J. S. Kim, P. E. Jeon, J. C. Choi, et al. Emission color variation of M2SiO4:Eu2+ (M=Ba, Sr, Ca) phosphors for light-emitting diode. [J]. Solid State Communications, 2005,133:187-190.
[28]. Jong Su Kim, Yun Hyung park, Sun Myung Kim, et al. Temperature-dependent emission spectra of M2SiO4:Eu2+ (M=Ba, Sr, Ca) phosphors for green and greenish white LEDs[J]. Solid State Communications,2005,133:445-448.
[29]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.
[30]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,2006,55(9)：4946-4950.
[31]Z. C. Wu, J. X. Shi, J. Wang, M. L. Gong, and Q. Su. A novel blue-emitting phosphor LiSrPO4:Eu2+ for white LEDs. [J]. Journal of Solid State Chemistry 2006; 179(8): 2356-2360.
[32]M. S. Waite. Luminescence of Alkali-Alkaline Earth-Phosphates Activated with Eu2+.[J]. Journal of the Electrochemical Society.1974; 121(8):1122-1123
[33]Fang Ying, Zhuang Weidong, Sun Yimin, Teng Xiaoming, He Huaqiang, Huang Xiaowei. Luminescence Properties of Eu2+ and Mn2+ Co-Doped Ca8Mg(SiO4)4Cl2. [J]. Journal of Rare Eerths,2004; 22:(1):122-125
[34]G. Blasse. Philips Res[M]. Rep.1969; 24:131-136.
[35]J. Qiu, K. Miura, N. Sugimoto, K. Hirao. Preparation and fluorescence properties of fluoroaluminate glasses containing Eu2+ ions. [J]. Journal of Non-Crystalltine Solids, 1997,213/214:266-270.
[36]D. L. Dexter. A Theory of Sensitized Luminescence in Solids. [J]. Journal of Chemical Physics 1953,21(5):836-850.
[37]Yu-Sheng Tang and Shu-Fen Hu. Thermally stable luminescence of KSrP04:Eu2+ phosphor for white light UV light-emitting diodes[J]. Applied Physics Letters,2007,90:151108
[38]胡建国,万国江,胡学芳,马林,闫世润,王惠琴,徐燕.磷酸钡钙：铈、锰红色荧光粉的研制.[J].中国稀土学报,2005,5：537-540.
[39]Woan-Jen Yang, Teng-Ming Chen. White-light generation and energy transfer in SrZn2(P04)2:Eu, Mn phosphor for ultraviolet light-emitting diodes. [J]. Applied Physics Letters.2006,88(10):101903.
[40]Yonghu Chen, Chaoshu Shi, Wuzhao Yan, Zeming Qi, Yibing Fu. Energy transfer between Pr3+ and Mn2+ in SrB4O7:Pr, Mn. [J] Applied Physics Letters.2006,88(6):061906.
[41]乔彬,张中太,唐子龙,张俊英,王晓欣.Eu2+,Mn2+共激活碱土镁硅酸盐基红色荧光粉的发光性能.[J].中国稀土学报,2003,21(2)：192-195.
[42]庞彦龙.BaMgAl10O17:Eu2+,Mn2+中Eu2+→Mn2+的能量传递.[J].光谱实验室,2006,23(5)：918-920.
[43]Caldino U. G, Munoz A. F, Rubio J.0. J. Phys. Condens. Matter,1993 5 195
[44]D. Curie,刘洪楷.群论在发光光谱学中的应用.[J].物理学进展.1985,5(2)：206.
[45]L. G. Van Uitert. An empirical relation fitting the position in energy of the lower d-band edge for Eu2+ or Ce3+ in various compounds.[J]. Journal of Luminescence. 1984,29(1):1-9.
[46]Curie D. Luminescence in Crystals. [M]. England London, Methuen 1963.
[2]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.
[3]武毅.绿色光源-LED.[J].灯与照明,2005,30(2)：47-50.
[4]王进.光转换白光LED研究.[D].中国海洋大学2005年,1-3.
[5]杨笑卫(译).高亮度、全光色LED.[J].中国照明电器,2001,4：23-25.
[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 Letters,1992,61(15):1775-1777.
[8]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.
[9]张书生,庄卫东,赵春雷。助熔剂对Y3Al5O12：Ce荧光粉性能的影响.[J].中国稀土学报,2002,6：605-607.
[10]刘如熹,石景仁。白光发光二极管用钇铝石榴石荧光粉的配方与机制研究.[J].中国稀土学报,2002.6：495-501.
[11]Jacobs R R, Krupke W F, Weber M. Measurement of excited-state-absorption loss for Ce3+ in Y3Al5O12 and implications for tunable 5d→4f rare earth laser. [J]. Applied Physics Letters,1978,33:410-412.
[12]Blasse G, Bril A. A new phosphor for flying-spot cathode-ray tubes for color television: yellow-emitting Y3Al5O12. [J]. Applied Physics Letters.1967,11:53-55.
[13]张若桦,申泮文.稀土元素化学.[M].天津：科技出版社,1987.
[14]《固体发光》编写组.固体发光.[M].安徽：中国科技大学出版社,1976.
[15]D. T. Palumbo, J. J. Brown, Jr. Electronic states of Mn2+-activated phosphors. [J]. Journal of the Electrochemical Society,1970,117:1184-1188.
[16]孙家跃等.固体发光材料.[M].北京：化学工业出版社,2003：7.
[17]Shuji Nakamura, Gerhard Fasol, The Blue Laser Diode [M]. GaN Based Light Emitters and Lasers Springer, Berlin,1996.
[18]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
[19]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.
[20]Woan-Jen Yang, Teng-Ming 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
[21]毛向辉,吴振国,廉世勋,Eu2+离子在光转换材料中作用的研究.[J].湖南师范大学学报,1994,17(2)：56-58.
[22]Lingdong Sun, Cheng Qian, Chunsheng Liao. Luminescent properties of Li doped nanosized Y2O3:Eu.[J]. Solid State Communications,2001,119(6):393-396.
[23]余锡宾,杨良准,杨仕平,周春蕾,许晓琳,唐锦锋,彭秀东.SrZnO2:Eu3+,Li+长波紫外激发红光荧光体的合成及发光性能研究[J].中国稀土学报,2005,23(5)：533-536
[24]Kenichi YAMADA, Masato OHTA, Tsunemasa TAGUCHI, J. Light&Vis. Env[J],2004,28(2):73-80
[25]Joung Kyu Park, Kyoung Jae Choi, Jeong Ho Yeon, Seung Jae Lee, Chang Hae Kim. Embodiment of the warm white-light-emitting diodes by using a Ba2+ codoped Sr3SiO5:Eu2+ phosphor. [J]. Applied Physics Letters,2006,88:043511.
[26]Xiaoming Liu, Cuikun Lin, and Jun Lin. White light emission from Eu3+ in CaIn2O4 host lattices[J]. Applied Physics Letters,2007,90:081904
[27]J. S. Kim, P. E. Jeon, J. C. Choi, et al. Emission color variation of M2SiO4:Eu2+ (M=Ba, Sr, Ca) phosphors for light-emitting diode. [J]. Solid State Communications, 2005,133:187-190.
[28]. Jong Su Kim, Yun Hyung park, Sun Myung Kim, et al. Temperature-dependent emission spectra of M2SiO4:Eu2+ (M=Ba, Sr, Ca) phosphors for green and greenish white LEDs[J]. Solid State Communications,2005,133:445-448.
[29]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.
[30]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,2006,55(9)：4946-4950.
[31]Z. C. Wu, J. X. Shi, J. Wang, M. L. Gong, and Q. Su. A novel blue-emitting phosphor LiSrPO4:Eu2+ for white LEDs. [J]. Journal of Solid State Chemistry 2006; 179(8): 2356-2360.
[32]M. S. Waite. Luminescence of Alkali-Alkaline Earth-Phosphates Activated with Eu2+.[J]. Journal of the Electrochemical Society.1974; 121(8):1122-1123
[33]Fang Ying, Zhuang Weidong, Sun Yimin, Teng Xiaoming, He Huaqiang, Huang Xiaowei. Luminescence Properties of Eu2+ and Mn2+ Co-Doped Ca8Mg(SiO4)4Cl2. [J]. Journal of Rare Eerths,2004; 22:(1):122-125
[34]G. Blasse. Philips Res[M]. Rep.1969; 24:131-136.
[35]J. Qiu, K. Miura, N. Sugimoto, K. Hirao. Preparation and fluorescence properties of fluoroaluminate glasses containing Eu2+ ions. [J]. Journal of Non-Crystalltine Solids, 1997,213/214:266-270.
[36]D. L. Dexter. A Theory of Sensitized Luminescence in Solids. [J]. Journal of Chemical Physics 1953,21(5):836-850.
[37]Yu-Sheng Tang and Shu-Fen Hu. Thermally stable luminescence of KSrP04:Eu2+ phosphor for white light UV light-emitting diodes[J]. Applied Physics Letters,2007,90:151108
[38]胡建国,万国江,胡学芳,马林,闫世润,王惠琴,徐燕.磷酸钡钙：铈、锰红色荧光粉的研制.[J].中国稀土学报,2005,5：537-540.
[39]Woan-Jen Yang, Teng-Ming Chen. White-light generation and energy transfer in SrZn2(P04)2:Eu, Mn phosphor for ultraviolet light-emitting diodes. [J]. Applied Physics Letters.2006,88(10):101903.
[40]Yonghu Chen, Chaoshu Shi, Wuzhao Yan, Zeming Qi, Yibing Fu. Energy transfer between Pr3+ and Mn2+ in SrB4O7:Pr, Mn. [J] Applied Physics Letters.2006,88(6):061906.
[41]乔彬,张中太,唐子龙,张俊英,王晓欣.Eu2+,Mn2+共激活碱土镁硅酸盐基红色荧光粉的发光性能.[J].中国稀土学报,2003,21(2)：192-195.
[42]庞彦龙.BaMgAl10O17:Eu2+,Mn2+中Eu2+→Mn2+的能量传递.[J].光谱实验室,2006,23(5)：918-920.
[43]Caldino U. G, Munoz A. F, Rubio J.0. J. Phys. Condens. Matter,1993 5 195
[44]D. Curie,刘洪楷.群论在发光光谱学中的应用.[J].物理学进展.1985,5(2)：206.
[45]L. G. Van Uitert. An empirical relation fitting the position in energy of the lower d-band edge for Eu2+ or Ce3+ in various compounds.[J]. Journal of Luminescence. 1984,29(1):1-9.
[46]Curie D. Luminescence in Crystals. [M]. England London, Methuen 1963.