橙红色荧光粉NaBa_(1-x)PO_4:xEu~(3+)中Eu~(3+)的占位情况及光谱性质
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摘要
采用高温固相法合成了NaBa_(1-x)PO_4:xEu~(3+)系列橙红色荧光粉。用X射线衍射、扫描电子显微镜、荧光光谱以及色坐标等手段对荧光粉的晶体结构和发光性能进行表征;考察了Eu~(3+)的掺杂摩尔量对荧光粉的晶体结构和发光性能的影响。结果表明:Eu~(3+)的掺杂并没有改变荧光粉的晶体类型,但是导致了晶格收缩,其基质主相是六方晶系的NaBaPO_4。在393 nm近紫外光激发下,最强发射峰和次强发射峰分别位于红光616 nm和橙光591 nm附近,分别属于Eu~(3+)的~5D_0→~7F_2和~5D_0→~7F_1特征跃迁。Eu~(3+)的掺杂量为0.20 mol时荧光粉的发射峰强度最大。Eu~(3+)的光谱性质及其占据基质晶格中Ba(Ⅱ)和Ba(Ⅰ)位点的比例随Eu~(3+)掺杂量的变化而变化,改变Eu~(3+)的掺杂量可以有效调节荧光粉发射光谱中的红、橙光比例。其中荧光粉NaBa_(0.80)PO_4:0.20Eu~(3+)的性能优异,适合与近紫外LED芯片相匹配发光。
A series of orange-red light-emitting phosphors NaBa_(1-x)PO_4:xEu~(3+) were synthesized by a high-temperature solid-state method.The crystal structure and luminescence properties of phosphors were characterized by X-ray diffractometer, scanning electron microscope, fluorescence spectrophotometer and chromaticity coordinates.The effect of Eu~(3+) doping content on the crystal structure and luminescence properties of the phosphors was investigated.The results show that doped Eu~(3+) has liitle effect on the crystal form of phosphors, but leads to contraction of the lattice.The main phase is NaBaPO_4, and the crystal form belongs to a hexagonal crystal system.The maximum emission peak and the sub-maximal emission peak are located in red light at 616 nm and orange light at 591 nm under the excitation of near-ultraviolet light at 393 nm, belonging to ~5D_0→~7F_2 and ~5D_0→~7F_1 transition of Eu~(3+), respectively.The emission peak intensity of phosphors is most intense when the doping content of Eu~(3+) is 0.20 mol.The spectral properties and the ratio of Eu~(3+) occupying Ba(Ⅱ) and Ba(Ⅰ) sites of matrix crystal are affected by doped Eu~(3+) content.Changing the doping concentration of Eu~(3+) can effectively regulate the ratio of red and orange light in the emission spectrum of phosphors.The phosphor NaBa_(0.80)PO_4:0.20Eu~(3+) has the superior performance and is suitable for matching with the near ultraviolet(UV) LED chip.
A series of orange-red light-emitting phosphors NaBa_(1-x)PO_4:xEu~(3+) were synthesized by a high-temperature solid-state method.The crystal structure and luminescence properties of phosphors were characterized by X-ray diffractometer, scanning electron microscope, fluorescence spectrophotometer and chromaticity coordinates.The effect of Eu~(3+) doping content on the crystal structure and luminescence properties of the phosphors was investigated.The results show that doped Eu~(3+) has liitle effect on the crystal form of phosphors, but leads to contraction of the lattice.The main phase is NaBaPO_4, and the crystal form belongs to a hexagonal crystal system.The maximum emission peak and the sub-maximal emission peak are located in red light at 616 nm and orange light at 591 nm under the excitation of near-ultraviolet light at 393 nm, belonging to ~5D_0→~7F_2 and ~5D_0→~7F_1 transition of Eu~(3+), respectively.The emission peak intensity of phosphors is most intense when the doping content of Eu~(3+) is 0.20 mol.The spectral properties and the ratio of Eu~(3+) occupying Ba(Ⅱ) and Ba(Ⅰ) sites of matrix crystal are affected by doped Eu~(3+) content.Changing the doping concentration of Eu~(3+) can effectively regulate the ratio of red and orange light in the emission spectrum of phosphors.The phosphor NaBa_(0.80)PO_4:0.20Eu~(3+) has the superior performance and is suitable for matching with the near ultraviolet(UV) LED chip.
引文
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[2]WANG J J,JIA C X.Synthesis and luminescence of Y2O3:Eu3+nanoparticles by the coprecipitation[J].Ferroelectrics,2015,482(1):129-135.
[3]王磊,董杰,黄平,等.碱土金属离子对红色长余辉材料Y2O2S:Eu3+,M2+(M=Mg,Ca,Sr,Ba),Ti4+纳米阵列发光性能的影响[J].发光学报,2014,35(5):553-557.WANG Lei,DONG Jie,HUANG Ping,et al.Chin J Lumin(in Chinese),2014,35(5):553-557.
[4]吴疆,张萍,蒋春东,等.橙红色荧光粉Ca3Y2Si3O12:Sm3+的制备及发光特性[J].发光学报,2014,35(7):772-776.WU Jiang,ZHANG Ping,JIANG Chundong,et al.Chin J Lumin(in Chinese),2014,35(7):772-776.
[5]FENG G,JIANG W H,LIU J,et al.Luminescent properties of novel red-emitting M7Sn(PO4)6:Eu3+(M=Sr,Ba)for light-emitting diodes[J].Luminescence,2018,33(2):455-460.
[6]VERGEER P,VLUGT T J H,KOX M H F,et al.Quantum cutting by cooperative energy transfer in Ybx Y1-x PO4:Tb3+[J].Phys Rev B,2005,71(1):014119.
[7]ELMMARI L,EL KOUMIRI M,ZSCHOKKE-GR?NACHER I,et al.Elaboration and non linear properties of ortho-phosphate solid solutions AIBII1-xMIIxPO4(AI=monovalent cation,BII&MII=diwalent cation)[J].Ferroelectrics,1994,158(1):19-24.
[8]LIU J S,WU Z C,GONG M L,et al.Thermally stable luminescence of blue LiSrPO4:Eu2+phosphor for near-UV light-emitting diodes[J].Appl Phys B,2008,93(2):583-587.
[9]WANG Z L,LIANG H B,GONG M L,et al.Luminescence investigation of Eu3+activated double molybdates red phosphors with scheelite structure[J].J Alloy Compd,2007,432(1/2):308-312.
[10]杨志平,王凤和,郭颖楠,等.白光二极管用荧光粉Li Ba PO4:Tb3+的制备及发光性质[J].硅酸盐学报,2010,38(6):1107-1111.YANG Zhiping,WANG Fenghe,GUO Yingnan,et al.J Chin Ceram Soc,2010,38(6):1107-1111.
[11]张素银.Eu2+,3+掺杂ABPO4(A=Li,Na,K,B=Mg,Ca,Sr,Ba)的发光性能及结构研究[D].苏州:苏州大学,2012.ZHANG Suyin.Studies of luminescence characteristics and microstructure of Eu2+,3+-doped ABPO4(A=Li,Na,K,B=Ma,Ca,Sr,Ba)(in Chinese,dissertation).Suzhou:Soochow University,2012.
[12]谌基兴,林林,朱晓娟,等.NaBaPO4:Eu3+,Yb3+的近红外下转换机制[J].人工晶体学报,2014,43(12):3169-3174.CHEN Jixing,LIN Lin,ZHU Xiaojuan,et al.J Synth Cryst(in Chinese),2014,43(12):3169-3174.
[13]周立亚,王玮,张宁宁,等.NaCa1-x-yBay PO4:Eu3+红色荧光粉的合成及发光性质研究[J].化学通报,2011,74(4):346-350.ZHOU Liya,WANG Wei,ZHANG Ningning,et al.Chem Bull(in Chinese),2011,74(4):346-350.
[14]DOU X H,ZHAO W R,SONG E H,et al.Photoluminescence characterization of Ca10Na(PO4)7:Eu3+red-emitting phosphor[J].Spectrochim Acta A,2011,78(2):821-825.
[15]李盼来,王蕴珠,王志军,等.Li BaPO4:Eu3+材料的制备及发光特性[J].发光学报,2011,32(7):665-669.LI Panlai,WANG yunzhu,WANG Zhijun,et al.Chin J Lumin(in Chinese),2011,32(7):665-669.
[16]王志军,李盼来,杨志平,等.KBa PO4:Eu3+红色发光材料的光谱特性[J].光子学报,2011,40(3):336-339.WANG Zhijun,LI Panlai,YANG Zhiping,et al.Acta Photon Sin(in Chinese)2011,40(3):336-339.
[17]郑敏,陈一胜,张继忠,等.红色荧光粉Na BaPO4:Eu3+的制备及其性能研究[J].四川有色金属,2009(3):18-22.ZHENG Min,CHEN Yisheng,ZHANG Jizhong.et al.Sichuan Nonferrous Met(in Chinese),2009(3):18-22.
[18]PIRES A M,DAVOLOS M R.Luminescence of europium(Ⅲ)and manganese(Ⅱ)in barium and zinc orthosilicate[J].Chem Mater,2001,13(1):21-27.
[19]朱宪忠,储成林.阳离子取代对Lu3Ga5O12:Tb3+晶体结构与发光性能的影响[J].光学学报,2015,35(5):259-266.ZHU Xianzhong,CHU Chenglin.[J].Acta Opt Sin(in Chinese),2015,35(5):259-266.
[20]李登宇,王海波,朱月华,等.近紫外白光LED用KBa2(NbO3)5:Eu3+红色荧光粉的合成与发光性能[J].人工晶体学报,2015,44(7):1768-1772.LI Dengyu,WANG Haibo,ZHU Yuehua,et al.J Synth Cryst(in Chinese),2015,44(7):1768-1772.
[21]LI X,GUAN L,LI X N,et al.Luminescent properties of Na BaPO4:Eu3+red-emitting phosphor for white light-emittinng diodes[J].Powder Technol,2010,200(1/2):12-15.
[22]卓芳平,张伟,火军明,等.Na2CaSiO4:RE3+(RE=Ce3+,Tb3+,Eu3+)的制备及发光特性[J].发光学报,2012,33(3):238-242.ZHUO Fangping,ZHANG Wei,HUO Mingjun,et al.Chin J Lumin(in Chinese),2012,33(3):238-242.
[23]WANG R F,ZHOU L Y,WANG Y L.Luminescent properties of MMgP2O7:Eu3+(M=Ca,Sr,Ba)phosphor[J].J Rare Earth,2011,29(11):1045-1048.
[24]刘影,俞淳善,顾光瑞,等.共掺Mo6+离子的Ca4La NbW4O20:Eu3+荧光粉的发光特性[J].发光学报,2013,34(9):1113-1117.LIU Ying,YU Chunshan,GU Guangrui,et al.Chin J Lumin(in Chinese),2013,34(9):1113-1117.
[25]ZHANG S Y,WEI D L,ZHU R,et al.The luminescence and structural characterisitics of Eu3+-doped NaBaPO4 phosphor[J].Ceram Int,2011,37(8):3697-3702.
[26]余华,孙健,刘宝荣,等.Eu3+离子在微晶玻璃研究中的探针作用[J].物理学报,2006,55(11):6152-6156.YU Hua,SUN Jian,LIU Baorong,et al.Acta Phys Sin(in Chinese),2006,55(11):6152-6156.
[27]吴亚楠.白光LED用Ba3(PO4)2:Eu3+体系红色荧光粉的制备及其光学性能[D].秦皇岛:河北科技师范学院,2014.WU Yanan.Synthesis and optical properties of Ba3(P04)2;Eu3+red phosphorsor white LED(in Chinese,dissertation).Qinhuangdao:Hebei Normal University of Science&Technology,2014.
[28]YANG L Y,WANG J X,DONG X T,et al.Synthesis of Y2O2S:Eu3+luminescent nanobelts via electrospinning combined with sulfurization technique[J].J Mater Sci,2013,48(2):644-650.