干燥方式对NaY(WO_4)_2:Dy~(3+),Eu~(3+)荧光粉粒度及上转换发光性能的影响
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摘要
采用水热法合成了Dy~(3+)和Eu~(3+)共掺杂的NaY(WO_4)_2上转换荧光粉,用XRD, SEM和荧光光谱(PL)等方法对不同干燥方式所得样品的晶体结构、微观形貌、晶粒尺寸及上转换发光性能进行了分析。结果表明,合成样品均为四方白钨矿结构的NaY(WO_4)_2,空间群为I41/a,掺入Dy~(3+)和Eu~(3+)未改变基质晶格;常规干燥、喷雾干燥、冷冻干燥及真空干燥后荧光粉的尺寸分别为817.91, 486.04,388.74和349.82nm,真空干燥的样品分散性最好。在793nm近红外光激发下,冷冻干燥样品的上转换发光性能最佳,与干燥过程中粉体团聚程度减弱及表面层缺陷减少有关。576 nm处的黄光发射峰来自Dy~(3+)的4F9/2→6H13/2跃迁,595 nm处的橙光、616和655 nm处的红光发射峰分别归属于Eu~(3+)的~5D_0→~7F_1, ~5D_0→~7F_2和~5D_0→~7F_3跃迁。荧光粉的CIE色坐标均位于红光区,表现出良好的红光发射特性,在发光二极管和彩色显示等光电领域具有潜在应用价值。
Trivalent Dy~(3+) and trivalent Eu~(3+) ions co-doped NaY(WO_4)_2 upconversion phosphors were synthesized via traditional hydrothermal process. The effects of drying routes on the crystal structure, morphology, particle size and upconversion luminescence properties were investigated, and characterized by XRD, SEM, and photoluminescence spectrum(PL). The results showed that all the synthesized samples had the tetragonal scheelite structure with the space group I41/a, and the doping Dy~(3+) and Eu~(3+) ions did not evoke the changes of the host lattice parameters. In addition, the shape and size of products could be changed simply and effectively by different drying methods. The particle sizes of the phosphorsdrying by normal, spray, freeze and vacuum methods were 817.91, 486.04, 388.74 and 349.82 nm, respectively. It should be noted that the excellent dispersion of the particles were obtained by vacuum drying method. Under near infrared light excitation at 793 nm, the sample obtained by freeze drying had the better upconversion luminescence property than samples synthesized by normal drying, spray drying and vacuum drying. The possible reason for the above phenomenon were spread uniform, reunite decrease and surface defect layer decrease of powder particles during the freeze drying process. The NaY(WO_4)_2:Dy~(3+), Eu~(3+) phosphors exhibited yellow emission band at 576 nm corresponding to the 4 F69/2→H13/2 transition of Dy~(3+) ions, orange emitting lights(595 nm) were from the transition of ~5D_0→~7F_1 of Eu~(3+) ions, and red emitting lights at 616 and 655 nm, which were assigned to the energy level transition of ~5D_0→~7F_2 and ~5D_0→~7 F_3 of Eu~(3+) ions, respectively. Moreover, the ideal red chromaticity was exhibited by the CIE color coordinates of NaY(WO3+4)2:Dy~(3+), Eu~(3+) phosphors. In view of this, the NaY(WO_4)_2:Dy, Eu~(3+) phosphors might have potential application in photoelectric device areas, such as light emitting diodes and color display systems.
Trivalent Dy~(3+) and trivalent Eu~(3+) ions co-doped NaY(WO_4)_2 upconversion phosphors were synthesized via traditional hydrothermal process. The effects of drying routes on the crystal structure, morphology, particle size and upconversion luminescence properties were investigated, and characterized by XRD, SEM, and photoluminescence spectrum(PL). The results showed that all the synthesized samples had the tetragonal scheelite structure with the space group I41/a, and the doping Dy~(3+) and Eu~(3+) ions did not evoke the changes of the host lattice parameters. In addition, the shape and size of products could be changed simply and effectively by different drying methods. The particle sizes of the phosphorsdrying by normal, spray, freeze and vacuum methods were 817.91, 486.04, 388.74 and 349.82 nm, respectively. It should be noted that the excellent dispersion of the particles were obtained by vacuum drying method. Under near infrared light excitation at 793 nm, the sample obtained by freeze drying had the better upconversion luminescence property than samples synthesized by normal drying, spray drying and vacuum drying. The possible reason for the above phenomenon were spread uniform, reunite decrease and surface defect layer decrease of powder particles during the freeze drying process. The NaY(WO_4)_2:Dy~(3+), Eu~(3+) phosphors exhibited yellow emission band at 576 nm corresponding to the 4 F69/2→H13/2 transition of Dy~(3+) ions, orange emitting lights(595 nm) were from the transition of ~5D_0→~7F_1 of Eu~(3+) ions, and red emitting lights at 616 and 655 nm, which were assigned to the energy level transition of ~5D_0→~7F_2 and ~5D_0→~7 F_3 of Eu~(3+) ions, respectively. Moreover, the ideal red chromaticity was exhibited by the CIE color coordinates of NaY(WO3+4)2:Dy~(3+), Eu~(3+) phosphors. In view of this, the NaY(WO_4)_2:Dy, Eu~(3+) phosphors might have potential application in photoelectric device areas, such as light emitting diodes and color display systems.
引文
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[15]张平,李玲霞,徐明霞.花状Sr3Al2O6:Eu2+晶体的干燥方式与发光性能[J].天津大学学报,2008,41(1):44-47.Zhang P,Li L X,Xu M X.Drying methods and characterization of Sr3Al2O6:Eu2+crystallite with flower-like morphology[J].Journal of Tianjin University,2008,41(1):44-47.
[16]Wu S H,Cheng H C.Preparation and characterization of nanosized ZnGa2O4 phosphors[J].Cheminform,2004,35(39):H159-H163.
[17]Liu X,Li L,Noh H,et al.Controllable synthesis of uniform CaMoO4:Eu3+,M+(M=Li,Na,K)microspheres and optimum luminescence properties[J].RSC Advances,2015,5(13):9441-9454.
[2]刘剑.粉体团聚的控制措施[J].粉末冶金工业,2015,25(4):54-57.Liu J.Introduction of control measures for powder aggregation[J].Powder Metallurgy Industry,2015,25(4):54-57.
[3]杨应国,胡小华,庞明.干燥技术在制备纳米粉体中的应用[J].安徽化工,2005,31(2):28-30.Yang Y G,Hu X H,Pang M.The application of drying techniques to prepara nanoscale powder[J].Anhui Chemical Industry,2005,31(2):28-30.
[4]郜盛夏,陈毅彬,曾人杰.无团聚YAG:Ce3+荧光粉的制备与表征[J].发光学报,2010,31(6):806-811.Gao S X,Chen Y B,Zeng R J.Preparation and characterization of agglomerate-free YAG:Ce3+phosphor by co-precipitating and spray drying[J].Chinese Journal of Luminescence,2010,31(6):806-811.
[5]周志鹏.Nd:YAG纳米粉体合成的初步研究[D].邯郸:中国舰船研究院,2012:23-42.Zhou Z P.Preliminary study on the synthesis of Nd doped yttrium aluminum garnet nanoparticles[D].Handan:China Ship Research and Development Academy,2012:23-42.
[6]孙言.化学共沉淀法合成钆镓铝石榴石闪烁材料及性能研究[D].宁波:宁波大学,2014:56-58.Sun Y.Preparation and characterization of gadolinium aluminum gallium garnet scintillator material via co-precipitation method[D].Ningbo:Ningbo University,2014:56-58.
[7]Wei X T,Zhao J B,Zhang W P,et al.Cooperative energy transfer in Eu3+,Yb3+codoped Y2O3 phosphor[J].Journal of Rare Earths,2010,28(2):166-170.
[8]Li C R,Li S F,Dong B,et al.Intense up-conversion emissions of Yb3+/Dy3+co-doped Al2O3 nanopowders pre-pared by non-aqueous sol gel method[J].Chinese Physics B,2012,21(9):1-4.
[9]王雅静,史忠祥,魏蕾,等.816 nm光激发下Sm3+掺杂NaY(WO4)2上转换发光性能的研究[J].化工新型材料,2016,44(3):155-157.Wang Y J,Shi Z X,Wei L,et al.Study on upconversion luminescence properties of NaY(WO4)2:Sm3+phosphors at 816 nm laser excitation[J].New Chemical Materials,2016,44(3):155-157.
[10]史忠祥,王晶,关昕.Nd3+/Yb3+/Tm3+共掺杂NaY(WO4)2纳米晶的制备及其上转换发光性能[J].硅酸盐学报,2018,46(1):136-141.Shi Z X,Wang J,Guan X.Preparation and upconversion luminescence properties of Nd3+/Yb3+/Tm3+co-doped NaY(WO4)2nanocrystals[J].Journal of the Chinese Ceramic Society,2018,46(1):136-141.
[11]陈小兵,余双平,邓淑华,等.纳米粉体干燥方法的研究进展[J].无机盐工业,2004,36(1):7-9.Chen X B,Yu S P,Deng S H,et al.Development of research on drying techniques of mmanometer powders[J].Inorganic Chemicals Industry,2004,36(1):7-9.
[12]王雅静,史忠祥,刘小川,等.NaY(WO4)2:Dy3+荧光粉的制备及其上转换发光性能[J].过程工程学报,2014,14(4):689-693.Wang Y J,Shi Z X,Liu X C,et al.Study on synthesis and upconversion luminescence properties of NaY(WO4)2:Dy3+phosphors[J].The Chinese Journal of Process Engineering,2014,14(4):689-693.
[13]王萍,杨定明,何晓林,等.蓝光激发的Na2ZnSiO4:Eu3+红色荧光粉的合成及发光特性[J].硅酸盐学报,2015,43(1):93-97.Wang P,Yang D M,He X L,et al.Synthesis and luminescence properties of red-emitting phosphor Na2ZnSiO4:Eu3+under blue light excitation[J].Journal of the Chinese Ceramic Society,2015,43(1):93-97.
[14]Hadi R,Hossein M,Seyed P S.Improvement of Eu3+emissions in oxyfluoride glass and nano glass-ceramic by electron beam irradiation[J].Journal of Luminescence,2017,187:535-539.
[15]张平,李玲霞,徐明霞.花状Sr3Al2O6:Eu2+晶体的干燥方式与发光性能[J].天津大学学报,2008,41(1):44-47.Zhang P,Li L X,Xu M X.Drying methods and characterization of Sr3Al2O6:Eu2+crystallite with flower-like morphology[J].Journal of Tianjin University,2008,41(1):44-47.
[16]Wu S H,Cheng H C.Preparation and characterization of nanosized ZnGa2O4 phosphors[J].Cheminform,2004,35(39):H159-H163.
[17]Liu X,Li L,Noh H,et al.Controllable synthesis of uniform CaMoO4:Eu3+,M+(M=Li,Na,K)microspheres and optimum luminescence properties[J].RSC Advances,2015,5(13):9441-9454.