镓酸盐发光材料的制备及发光性能的研究
摘要
随着平板显示器如场发射显示器和真空荧光显示器的发展，阴极发光材料的要求也越来越高。为了得到高亮度，高效率的荧光粉，基质材料的选择是比较重要的一个环节。氧化物荧光粉就因为其良好的热稳定性广泛受到关注。而镓酸盐由于具有更好的化学稳定性，较窄的禁带宽度，更适合用来作为荧光粉材料。本文通过溶胶—凝胶法和固相法分别合成了ZnGa_2O_4和SrGa_2O_4荧光粉。讨论了不同类型的激活剂(Eu，V，Mo，In，Y，Al)，敏化剂，煅烧温度，保温时间和激活剂浓度对荧光粉发光性能的影响。利用X射线衍射(XRD)分析相结构和组成，荧光分光荧光计(PL)检测发光性能，TG-DTA分析反应过程，SEM观察了发光粉的形貌，实验结果表明：
(1)通过柠檬酸溶胶-凝胶法可合成出ZnGa_2O_4∶Eu荧光体，当Zn∶Ga为1∶4时，所得成品的最强发射峰位于613nm处，说明Eu~(3+)离子占据了非反演对称中心的位置，属于Eu~(3+)特征~5D_0→~7F_2跃迁，其对应于红色光谱。而通过添加不同的敏化剂，在ZnGa_2O_4∶R∶Eu(R∶Ba，Sr，In，Mo，V)中，能有效提高发光强度。
(2)采用固相法合成SrGa_2O_4荧光粉，XRD结果表明：SrGa_2O_4属单斜晶系，晶胞参数a=9.43(?)，b=9.00(?)，c=8.39(?)，β=89.06°，属P2_1／n(No．14)空间群。光谱数据表明：SrGa_2O_4∶Eu~(3+)荧光粉的发射主峰在610nm，Eu~(3+)离子占据了非反演对称中心的位置。当Eu~(3+)离子浓度大于1mol％时，位于590，610nm附近的2个发射峰均出现劈裂现象，即有2个~5D_0→~7F_1(586，597nm)、2个~5D_0→~7F_2(609，615nm)发射峰，~7F_2劈裂出两个分支的强度比例随Eu~(3+)浓度的变化而变化。
(3)采用固相反应法合成了SrGa_2O_4∶Eu∶Gd，Gd作为Eu的敏化剂与Eu之间存在能量迁移，其最强发射峰位于613nm，属于Eu~(3+)离子的~5D_0→~7F_2跃迁，发光强度得到增强。
(4)固相法合成Zn_(0.5)Sr_(0.5)Ga_2O_4∶Eu荧光粉。Zn_(0.5)Sr_(0.5)Ga_2O_4∶0.02Eu的发光强度最佳。
The development of flat panel display devices such as field emission displays (FEDs) and vacuum fluorescent displays (VFDs) requires highly efficient cathodoluminescent materials. It is important for the bright and efficient phosphor to choose the group material. Oxide phosphor is noticed because of the excellent heat stability. Gallate have high chemical stability and narrow band-gap, so it fit to be used as phosphor. This paper reported the synthesis of phosphor ZnGa_2O_4 and ZnGa_2O_4 and discussed the influences of activator, sensitizer, calcined temperatures, duration, and concentrations of activator on luminescent properties. Phase compositions and luminescent properties of the phosphors were investigated and detected by using XRD and phosphor luminometer (PL). The reaction process is analyzed by the TG-DTA and the appearance of the phosphor is observed by SEM.
(1) ZnGa_2O_4:Eu phosphor is synthesized by the sol-gel process , which is completely reacted with ratio of Zn : Ga=l : 4．The main peak at 610 nm can be ascribed to ~5D_0→F of Eu~(3+) , corresponding to red light. Eu~(3+) ion occupies a site with lacking inversion symmetry in ZnGaO host lattice. It could be change the luminescent intensity by
(2) The Eu~(3+) doped SrGa_2O_4 phosphor was prepared with the conventional solid state reaction method. The phase composition was characterized by powder X-ray diffractometry. The result shows that the producing powder belongs to monoclinic crystal system with its lattice constants: a=9．43(?), b=9．00(?), c=8．39(?),β=89．06°, and with space group P21/ n (No. 14) . The excitation and emission spectra were measured. The main peak at 610nm can be ascribed to the electric dipole transition ~5D_0→~7F_2, which indicates that Eu~(3+) occupies a site lacking inversion symmetry. The peaks at 590nm and 610nm transition emission split to two peaks respectively, ~5D_0→~7F_1, (586, 597nm) and ~5D_0→~7F_2 (609, 615nm) due to the crystal-field in the conditions of concentration of Eu with more than 1%. The strength ratio of two parts for the splitting peak ~7F_2can be changed according to the concentration of Eu.
(3) The phosphor of SrGa_2O_4: Eu : Gd was prepared with the conventional solid-state reaction method. Gd is sensitizer of Eu, there is energy transform between Gd and Eu. The main peak at 613 nm can be ascribed to ~5D_0→~7F_2 of Eu~(3+) . The luminescent intensity is improved.
(4) The Zn_(0．5) Sr_(0．5) Ga_2O_4 : Eu prepared by solid-state method. The results of the experiment show that the produced powder is the mixture of ZnGa_2O_4 and SrGa_2O_4．
(1)通过柠檬酸溶胶-凝胶法可合成出ZnGa_2O_4∶Eu荧光体，当Zn∶Ga为1∶4时，所得成品的最强发射峰位于613nm处，说明Eu~(3+)离子占据了非反演对称中心的位置，属于Eu~(3+)特征~5D_0→~7F_2跃迁，其对应于红色光谱。而通过添加不同的敏化剂，在ZnGa_2O_4∶R∶Eu(R∶Ba，Sr，In，Mo，V)中，能有效提高发光强度。
(2)采用固相法合成SrGa_2O_4荧光粉，XRD结果表明：SrGa_2O_4属单斜晶系，晶胞参数a=9.43(?)，b=9.00(?)，c=8.39(?)，β=89.06°，属P2_1／n(No．14)空间群。光谱数据表明：SrGa_2O_4∶Eu~(3+)荧光粉的发射主峰在610nm，Eu~(3+)离子占据了非反演对称中心的位置。当Eu~(3+)离子浓度大于1mol％时，位于590，610nm附近的2个发射峰均出现劈裂现象，即有2个~5D_0→~7F_1(586，597nm)、2个~5D_0→~7F_2(609，615nm)发射峰，~7F_2劈裂出两个分支的强度比例随Eu~(3+)浓度的变化而变化。
(3)采用固相反应法合成了SrGa_2O_4∶Eu∶Gd，Gd作为Eu的敏化剂与Eu之间存在能量迁移，其最强发射峰位于613nm，属于Eu~(3+)离子的~5D_0→~7F_2跃迁，发光强度得到增强。
(4)固相法合成Zn_(0.5)Sr_(0.5)Ga_2O_4∶Eu荧光粉。Zn_(0.5)Sr_(0.5)Ga_2O_4∶0.02Eu的发光强度最佳。
The development of flat panel display devices such as field emission displays (FEDs) and vacuum fluorescent displays (VFDs) requires highly efficient cathodoluminescent materials. It is important for the bright and efficient phosphor to choose the group material. Oxide phosphor is noticed because of the excellent heat stability. Gallate have high chemical stability and narrow band-gap, so it fit to be used as phosphor. This paper reported the synthesis of phosphor ZnGa_2O_4 and ZnGa_2O_4 and discussed the influences of activator, sensitizer, calcined temperatures, duration, and concentrations of activator on luminescent properties. Phase compositions and luminescent properties of the phosphors were investigated and detected by using XRD and phosphor luminometer (PL). The reaction process is analyzed by the TG-DTA and the appearance of the phosphor is observed by SEM.
(1) ZnGa_2O_4:Eu phosphor is synthesized by the sol-gel process , which is completely reacted with ratio of Zn : Ga=l : 4．The main peak at 610 nm can be ascribed to ~5D_0→F of Eu~(3+) , corresponding to red light. Eu~(3+) ion occupies a site with lacking inversion symmetry in ZnGaO host lattice. It could be change the luminescent intensity by
(2) The Eu~(3+) doped SrGa_2O_4 phosphor was prepared with the conventional solid state reaction method. The phase composition was characterized by powder X-ray diffractometry. The result shows that the producing powder belongs to monoclinic crystal system with its lattice constants: a=9．43(?), b=9．00(?), c=8．39(?),β=89．06°, and with space group P21/ n (No. 14) . The excitation and emission spectra were measured. The main peak at 610nm can be ascribed to the electric dipole transition ~5D_0→~7F_2, which indicates that Eu~(3+) occupies a site lacking inversion symmetry. The peaks at 590nm and 610nm transition emission split to two peaks respectively, ~5D_0→~7F_1, (586, 597nm) and ~5D_0→~7F_2 (609, 615nm) due to the crystal-field in the conditions of concentration of Eu with more than 1%. The strength ratio of two parts for the splitting peak ~7F_2can be changed according to the concentration of Eu.
(3) The phosphor of SrGa_2O_4: Eu : Gd was prepared with the conventional solid-state reaction method. Gd is sensitizer of Eu, there is energy transform between Gd and Eu. The main peak at 613 nm can be ascribed to ~5D_0→~7F_2 of Eu~(3+) . The luminescent intensity is improved.
(4) The Zn_(0．5) Sr_(0．5) Ga_2O_4 : Eu prepared by solid-state method. The results of the experiment show that the produced powder is the mixture of ZnGa_2O_4 and SrGa_2O_4．
引文
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[63] Kobzareva V P, Kovba L M and Lopato L M, Equilibrium diagram of theSrO-Ga_2O_3 system[J]. Russ. J. Inorg. Chem, 1976,21(6): 903-904.
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[65] Kahlenberg V, Fischer R X and Shaw C S J, Polymorphism of StrontiumMonogallate: The Framework Structures of SrGa_2O_4 and ABW Type SrGa2O4 [J].Journal of Solid State Chemistry, 2000,153(2): 294-300.magnetoplumbite compounds SrM_(12)O_(19)(M=Al, Fe, Ga). Journal of Solid StateChemistry, 1990, 87(1): 186-194.
[68] Kohlenberg V, Parise J B and Kristallogr Z, Sr_3Ga_4O_9 a strontium gallate with anew type of tetrahedral layer structure[J]. zeitschrift fur kristallographie, 2001, 216(4):210-214.
[69] Kahlenberg V, The Crystal Structures of the Strontium Gallates Sr_(10)Ga_6O_(19) andSr_3Ga_2O_6[J]. Journal of Solid State Chemistry, 2001,160(2): 421-429.
[70] Kitai A H , Xiao T and Liu G, Doped amorphous and crystalline gallium oxides,alkaline earth gallates and doped zinc germinate phosphors as electroluminescentmaterials[P]. Canada: WO 97/02721,23 January 1997.
[1] Kim J S, Park H L, Kim G C, Kim T W, Hwang Y H, Kim H K, Mho S I, Han S D, Luminescence enhancement of ZnGa_2CvMn~(2+) by Ge~(4+) and Li~+ doping[J]. Solid State Communications, 2003,126(9): 515-518.
[2] Hsu K H, Yang M R, Chen K S. A study of ZnGa_2O_4 phosphor prepared by the solid method [J]. Journal of Materials Science: Materials in Electronics, 1998,9: 283-288.
[3]刘素琴。李朝建，黄可龙，张学英，全玉．ZnGa204的制备及其光学性能【J】．应 用化学，2005，22(3)：0300-0303．
[4] Xu Z H , Li Y X, Liu Z F, Xiong Z, Low-temperature Synthesis of Nanocrystalline ZnGa_2O_4:Tb~(3+) Phosphors via Pechini Method[J]. Materials Science and Engineering, 2004, Bl 10(3): 302-306.
【5】于敏，林君，周永慧．柠檬酸．凝胶法合成ZnGa_2O_4：Mn~(2+)，Eu~(3+) 及其发光性能的 研究【J】．发光学报．2002，23(3)：0287-0290．
[6] Hirano M . Hydrothermal synthesis and characterization of ZnGa_2O_4 spinel fine particles[J]. Journal of Materials Chemistry, 2000,10:469-472.
[7] Jeong I K , Park H L, Mho S I. Two self-activated optical centers of blue emission in zinc gallate[J]. Solid State Communications, 1998,105(3): 179-183.
[8] Kim Jong Su , Kwon Ae Kyung, Kim Jin Su, Park Hong Lee, Kim Gwang Chul, Han Sang do. Optical and structural properties of ZnGa_2O_4: Eu~(3+) nanophosphor by hydrothermal method[J]. Journal of Luminescence, 2007,122-123:851-854.
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[3] 刘晃清，秦伟平和张继森，ZrO_2中Eu~(3+)的发光特性[J]．光谱学与光谱分析，2005，25(1)：19-22．
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[5] 陈永虎，刘波，施朝淑，Zimmerer G，GdPO_4∶Eu~(3+)和GdBO_3∶Eu~(3+)中”Gd-Eu”间的能量传递，中国稀土学报，2005，23(4)：429-433．
[2]徐叙珞，发光材料与显示技术【M】，3，北京：化学工业出版社，2003，3．10．
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【54】董国义，韦志仁，李志强，共激活剂Br~-，I~-对ZnS：Mn，Cu·X发光中心的影响[J]河北大学学报(自然科学版)，2001，21(1)：41-44．
[55】邓春林，邱克辉．Ce~(3+)和Tb~(3+)共激活的硫化物发光材料的合成及发光性质[J】．成都理工大学学报(自然科学版)，2003，30(4)：409-4 1 2．
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[61] Xu Z H , Li Y X, Liu Z F, Xiong Z, Low-temperature Synthesis of NanocrystallineZnGa_2O_4:Tb~(3+) Phosphors via Pechini Method[J]. Materials Science and Engineering,2004, Bl 10(3): 302-306.
[62] Glasser F P and Dent Glasser L S, Crystal chemistry of some AB_2O_4 compounds[J].J. Am. Ceram. Soc, 1963,46:377-380.
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[68] Kohlenberg V, Parise J B and Kristallogr Z, Sr_3Ga_4O_9 a strontium gallate with anew type of tetrahedral layer structure[J]. zeitschrift fur kristallographie, 2001, 216(4):210-214.
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[70] Kitai A H , Xiao T and Liu G, Doped amorphous and crystalline gallium oxides,alkaline earth gallates and doped zinc germinate phosphors as electroluminescentmaterials[P]. Canada: WO 97/02721,23 January 1997.
[1] Kim J S, Park H L, Kim G C, Kim T W, Hwang Y H, Kim H K, Mho S I, Han S D, Luminescence enhancement of ZnGa_2CvMn~(2+) by Ge~(4+) and Li~+ doping[J]. Solid State Communications, 2003,126(9): 515-518.
[2] Hsu K H, Yang M R, Chen K S. A study of ZnGa_2O_4 phosphor prepared by the solid method [J]. Journal of Materials Science: Materials in Electronics, 1998,9: 283-288.
[3]刘素琴。李朝建，黄可龙，张学英，全玉．ZnGa204的制备及其光学性能【J】．应 用化学，2005，22(3)：0300-0303．
[4] Xu Z H , Li Y X, Liu Z F, Xiong Z, Low-temperature Synthesis of Nanocrystalline ZnGa_2O_4:Tb~(3+) Phosphors via Pechini Method[J]. Materials Science and Engineering, 2004, Bl 10(3): 302-306.
【5】于敏，林君，周永慧．柠檬酸．凝胶法合成ZnGa_2O_4：Mn~(2+)，Eu~(3+) 及其发光性能的 研究【J】．发光学报．2002，23(3)：0287-0290．
[6] Hirano M . Hydrothermal synthesis and characterization of ZnGa_2O_4 spinel fine particles[J]. Journal of Materials Chemistry, 2000,10:469-472.
[7] Jeong I K , Park H L, Mho S I. Two self-activated optical centers of blue emission in zinc gallate[J]. Solid State Communications, 1998,105(3): 179-183.
[8] Kim Jong Su , Kwon Ae Kyung, Kim Jin Su, Park Hong Lee, Kim Gwang Chul, Han Sang do. Optical and structural properties of ZnGa_2O_4: Eu~(3+) nanophosphor by hydrothermal method[J]. Journal of Luminescence, 2007,122-123:851-854.
[1] Blasse G, Chemistry and physics of R-activated phosphors[J]. Handbook on the Physics and Chemistry of Rare Earths, 1979, 4: 237-274.
[2] 郭培民，北京大学博士后出站工作报告，北京，2003：104-105．
[3] 刘晃清，秦伟平和张继森，ZrO_2中Eu~(3+)的发光特性[J]．光谱学与光谱分析，2005，25(1)：19-22．
[4] 张思远，晶体中f6组态的荧光和点对称性[J]，发光与显示，1983，3：18-23．
[5] 陈永虎，刘波，施朝淑，Zimmerer G，GdPO_4∶Eu~(3+)和GdBO_3∶Eu~(3+)中”Gd-Eu”间的能量传递，中国稀土学报，2005，23(4)：429-433．