YVO_4:Eu~(3+),Bi~(3+)红色荧光粉的水热合成及其荧光性能
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摘要
以Y_2O_3、Eu_2O_3、Bi(NO_3)_3·H_2O、浓HNO_3、偏钒酸铵、氨水、无水乙醇和一缩二乙二醇为原料,采用聚乙烯吡咯烷酮(PVP)辅助水热法合成YVO_4:Eu~(3+), Bi~(3+)纳米颗粒。使用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)和荧光光谱(FL)等手段对产品进行了表征和分析。结果表明:合成的样品为YVO_4:Eu~(3+), Bi~(3+)纳米颗粒,均具有四方晶相结构,其微结构随反应溶液的的pH值变化。YVO_4:Eu~(3+), Bi~(3+)纳米颗粒在619 nm处有较强的红光发射(电偶极跃迁~5D_0→~7F_2),在594 nm有较弱的橙光发射(磁偶极跃迁~5D_0→~7F_1)。随着Eu/Bi比值的增大材料的荧光先增强后减弱,在Eu/Bi比值为5时样品的红光发射最强。溶液的pH值影响YVO_4:Eu~(3+), Bi~(3+)纳米晶的发光强度,其中pH值为10时的样品其红光发射最强。并探讨了YVO_4:Eu~(3+), Bi~(3+)纳米晶的发光机理。
Red phosphor nanoparticles YVO_4:Eu~(3+),Bi~(3+) have been successfully prepared via a facile hydrothermal method with Y_2O_3, Eu_2O_3, HNO_3, Bi(NO_3)_3·H_2O, NH_4VO_3, NH_3·H_2O, HNO_3, EtOH and diethylene glycol(DEG) as raw materials and polyvinyl pyrrolidone(PVP) as accessory ingredient. The as-prepared products were characterized by XRD, SEM, IR and PL. The results show that, all the samples are well crystallized and assigned to be the tetragonal crystal structure as the YVO_4 phase. Their microstructure varied with the pH value of solutions. The YVO_4:Eu~(3+), Bi~(3+) nanoparticles exhibit simultaneously orange(at 594 nm)and red(at 619 nm) emissions. The broad orange-red emissions can be attributed to the ~5D_0→~7F_1 and ~5D_0→~7F_2 transition of Eu~(3+)ion in YVO_4 matrix. As the ratio of Eu~(3+)/Bi~(3+) increases, the fluorescence intensities increase first and then weaken, while reach the strongest red emission at n_(Eu)~(3+)/n_(Bi)~(3+) =5. Besides, the pH value presents influence on the intensities of the YVO_4:Eu~(3+), Bi~(3+) nanoparticles to some extent. The YVO_4:Eu~(3+),Bi~(3+) nanoparticles prepared in the solution with pH = 10 exhibits the strongest red emission. Finally, the mechanism related with the Bi~(3+) →Eu~(3+)energy transfer in YVO_4:Eu~(3+), Bi~(3+) nanoparticles was also discussed.
Red phosphor nanoparticles YVO_4:Eu~(3+),Bi~(3+) have been successfully prepared via a facile hydrothermal method with Y_2O_3, Eu_2O_3, HNO_3, Bi(NO_3)_3·H_2O, NH_4VO_3, NH_3·H_2O, HNO_3, EtOH and diethylene glycol(DEG) as raw materials and polyvinyl pyrrolidone(PVP) as accessory ingredient. The as-prepared products were characterized by XRD, SEM, IR and PL. The results show that, all the samples are well crystallized and assigned to be the tetragonal crystal structure as the YVO_4 phase. Their microstructure varied with the pH value of solutions. The YVO_4:Eu~(3+), Bi~(3+) nanoparticles exhibit simultaneously orange(at 594 nm)and red(at 619 nm) emissions. The broad orange-red emissions can be attributed to the ~5D_0→~7F_1 and ~5D_0→~7F_2 transition of Eu~(3+)ion in YVO_4 matrix. As the ratio of Eu~(3+)/Bi~(3+) increases, the fluorescence intensities increase first and then weaken, while reach the strongest red emission at n_(Eu)~(3+)/n_(Bi)~(3+) =5. Besides, the pH value presents influence on the intensities of the YVO_4:Eu~(3+), Bi~(3+) nanoparticles to some extent. The YVO_4:Eu~(3+),Bi~(3+) nanoparticles prepared in the solution with pH = 10 exhibits the strongest red emission. Finally, the mechanism related with the Bi~(3+) →Eu~(3+)energy transfer in YVO_4:Eu~(3+), Bi~(3+) nanoparticles was also discussed.
引文
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[2]Wang J,Xu Y H.Hojamberdiev M,et al.A facile route to synthesize luminescent YVO4:Eu3+porous nanoplates[J].J.Non-Cryst.Solids,2009,355:903
[3]Liu X L,Zhou F,Gu M,et al.Fabrication of highly a-axis-oriented Gd2O3:Eu3+thick film and its luminescence properties[J].Opt.Mater.,2008,31:126
[4]Hong B C,Kawano K.Syntheses of CaF2:Eu nanoparticles and the modified reducing TCRA treatment to divalent Eu ion[J].Opt.Mater.,2008,30:952
[5]Chi J Y,Chen J S,Liu C Y,et al.Phosphor converted LEDs with omnidirectional-reflector coating[J].Opt.Express,2009,17:23530
[6]Tanaka S,Fujihara S.Luminescent antireflective coatings with disordered surface nanostructures fabricated by liquid processes[J].Langmuir,2011,27:2929
[7]Levine A K,Palilla F C.A new,highly efficient red-emitting cathodoluminescent phosphor(YVO4:Eu)for color television[J].Appl.Phys.Lett.,1964,5:118
[8]Neeraj S,Kijima N,Cheetham A K.Novel red phosphors for solid state lighting;the system BixLn1-xVO4:Eu3+/Sm3+(Ln=Y,Gd)[J].Solid State Commun.,2004,131:65
[9]Takeshita S,Isobe T,Niikura S.Low-temperature wet chemical synthesis and photoluminescence properties of YVO4:Bi3+,Eu3+nano-phosphors[J].J.Luminescence,2008,128:1515
[10]Hu J Q,Bando Y,Golberg D.Self-catalyst growth and optical properties of novel SnO2fishbone-like nanoribbons[J].Chem.Phys.Lett.,2003,372:758
[11]Iso Y,Takeshita S,Isobe T.Effects of annealing on the photoluminescence properties of Citrate-Capped YVO4:Bi3+,Eu3+Nanophosphor[J].J.Phys.Chem.,2014,118C:11006
[12]Chen Y C,Wu Y C,Wang D Y,et al.Controlled synthesis and luminescent properties of monodispersed PEI-modified YVO4:Bi3+,Eu3+nanocrystals by a facile hydrothermal process[J].J.Mater.Chem.,2012,22:7961
[13]Chen L,Chen K J,Lin C C,et al.Combinatorial approach to the development of a single mass YVO4:Bi3+,Eu3+phosphor with red and green dual colors for high color rendering white light-emitting diodes[J].J.Comb.Chem.,2010,12:587
[14]Xu W,Song H W,Yan D T,et al.YVO4:Eu3+,Bi3+UV to visible conversion nano-films used for organic photovoltaic solar cells[J].J.Mater.Chem.,2011,21:12331
[15]Rambabu D P,Amalnerkar B,Buddhudu B B K S.Fluorescence spectra of Eu3+-doped LnVO4(Ln=La and Y)powder phosphors[J].Mater.Res.Bull.,2000,35:929
[16]Liu G C,Dong H,Wei Q M,et al.Preparation and luminescence of mesoporous LaVO4:Eu3+[J].Chinese Journal of Materials Research,2014,28(1):1(刘国聪,董辉,韦庆敏等.介孔LaVO4:Eu3+的制备和荧光性能[J].材料研究学报,2014,28:1)
[17]Jvu D B R.Optical Absorption intensities of rare-earth ions[J].Phys.Rev.,1962.127:750
[18]Panigrahi B S,Peter S,Viswanathan K S,et al.Fluorescence enhancement of Tb3+in Tb-aromatic acid complexes:correlation of synergistic enhancement with the structure of the ligand[J].Spectrochim.Acta,1995,51A:2289
[19]Nu?ez N,Sabek J,García-Sevillano J,et al.Solvent-controlled synthesis and luminescence properties of uniform Eu:YVO4Nanophosphors with different morphologies[J].Eur.J.Inorg.Chem.,2013,8:1301
[20]Huang C K,Chen Y C,Hung W B,et al.Enhanced light harvesting of Si solar cells via luminescent down-shifting using YVO4:Bi3+,Eu3+nanophosphors[J].Prog.Photovolt.,2013,21:1507
[21]Xu X R,Su M Z.Luminescence and Luminescence Materials[M].Chemical Industry Press,2004:178(徐叙2),苏勉曾.发光学与发光材料[M].化学工业出版社,2004:178)
[22]Datta R K.Bismuth in yttrium vanadate and yttrium europium vanadate phosphors[J].J.Electrochem.Soc.,1967,114:1057
[23]Liu G C,Duan X C,Li H B,et al.Novel polyhedron-like t-LaVO4:Dy3+nanocrystals:Hydrothermal synthesis and photoluminescence properties[J].J.Cryst.Growth,2008,310:4689