发光增强的红色荧光粉Li_6Zr_2O_7:Eu~(3+)的微波固相合成
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摘要
以硝酸锆、硝酸锂、Eu(NO_3)_3·6H_2O为原料,采用微波固相烧结法合成了系列红色荧光粉Li_6Zr_2O_7:Eu~(3+)。利用XRD和荧光光度计对样品的组成和发光性能进行了表征。考察了烧结时间、烧结温度及Eu~(3+)的含量对荧光粉发光性能的影响。XRD分析结果表明,Li_6Zr_2O_7:Eu~(3+)荧光粉为纯相晶体结构。根据离子电负性标度可知,Eu~(3+)(1.433)会优先取代电负性相近Zr~(4+)的位置(1.610)。当微波烧结时间为10 min、烧结温度为500℃、Eu~(3+)在晶体中的含量为14%时(以Li_6Zr_2O_7的物质的量为基准,下同),在465 nm激发下,制备得到的Li_6Zr_2O_7:0.14Eu~(3+)荧光粉在615 nm处产生最强的红光发射,且发射光谱在615 nm的强度是激发光谱在465 nm强度的1.54倍。此时荧光粉色坐标为X=0.65,Y=0.35,具有很高的色纯度,与商用红色荧光粉(0.63,0.34)相比更接近国家标准(0.67,0.33)。
A series of red-emitting phosphors Li_6Zr_2O_7:Eu~(3+)were synthesized by microwave solid phase sintering using zirconium nitrate,lithium nitrate and Eu(NO_3)_3·6H_2O as raw materials.The composition and luminescence properties of the samples were characterized by XRD and fluorescence photometer.The effects of sintering time,sintering temperature and content of Eu~(3+)on the luminescence properties of the phosphors were investigated.The results showed that the samples had crystal phases of Li_6Zr_2O_7:Eu~(3+)According to ionic electronegativity scale,Eu~(3+)(1.433)ions gave priority to replacing the position of Zr~(4+)(1.610)ions,which had similar electronegativity.When the sintering time was 10 min,the sintering temperature was 500℃,the content of Eu~(3+)ions was 14%of molar amount of Li_6Zr_2O_7,under 465 nm excitation,the prepared phosphor Li_6Zr_2O_7:0.14Eu~(3+)generated the strongest red emission at 615 nm.Its emission spectrum at 615 nm was 1.54 times stronger than that of excitation spectrum at 465 nm.At this point,its fluorescence pink coordinate was X=0.65,Y=0.35.The phosphor Li_6Zr_2O_7:0.14Eu~(3+)had very high color purity,closer to the national standard(0.67,0.33)than the commercial red-emitting phosphor(0.63,0.34).
A series of red-emitting phosphors Li_6Zr_2O_7:Eu~(3+)were synthesized by microwave solid phase sintering using zirconium nitrate,lithium nitrate and Eu(NO_3)_3·6H_2O as raw materials.The composition and luminescence properties of the samples were characterized by XRD and fluorescence photometer.The effects of sintering time,sintering temperature and content of Eu~(3+)on the luminescence properties of the phosphors were investigated.The results showed that the samples had crystal phases of Li_6Zr_2O_7:Eu~(3+)According to ionic electronegativity scale,Eu~(3+)(1.433)ions gave priority to replacing the position of Zr~(4+)(1.610)ions,which had similar electronegativity.When the sintering time was 10 min,the sintering temperature was 500℃,the content of Eu~(3+)ions was 14%of molar amount of Li_6Zr_2O_7,under 465 nm excitation,the prepared phosphor Li_6Zr_2O_7:0.14Eu~(3+)generated the strongest red emission at 615 nm.Its emission spectrum at 615 nm was 1.54 times stronger than that of excitation spectrum at 465 nm.At this point,its fluorescence pink coordinate was X=0.65,Y=0.35.The phosphor Li_6Zr_2O_7:0.14Eu~(3+)had very high color purity,closer to the national standard(0.67,0.33)than the commercial red-emitting phosphor(0.63,0.34).
引文
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[2]Li Panlai(李盼来),Wang Zhendong(王振动),Luo Zhiyuan(罗志远),et al.Progress of phosphors for UV and near-UV based white LEDs[J].Jouranl of Synthetic Crystals(人工晶体学报),2015,44(11):2954-2963.
[3]Zhu Yuehua(朱月华),Wang Haibo(王海波),Jiang Qingsong(姜青松),et al.Status and development on the phosphors excited by ultraviolet LED[J].China Light&Lighting(中国照明电器),2014,(8):1-5.
[4]Zhang Gongguo(张功国),Zhang Chunxian(张春仙).Research progress on phosphors excited by near ultravioletfor white light emitting diodes[J].Journal of Jining University(济宁学院学报),2012,33(6):34-38.
[5]Shi Qiang(史强),Zhang Junying(张俊英),Zhang Bingyuan(张丙元),et al.Progress on single-host phophrs used for white LED[J].Material Review(材料导报),2011,25(11):53-57.
[6]Zhu G,Wang Y H,Ci Z P,et al.Ca5La5(SiO4)3(PO4)3O2:Ce3+,Mn2+:A color-tunable phosphor with efficient energy transfer for white-light-emitting diodes[J].Journal of the Electrochemical Society,2011,158:J236-J242.
[7]Huang C,Chen T.Novel yellow-emitting Sr8MgLn(PO4)7:Eu2+(Ln=Y,La)phosphors for application in white LEDs with excellent color rendering index[J].Inorg Chem,2011,50(12):5725-5730.
[8]Huang W,Yoshimura F,Ueda K,et al.Chemical pressure control for photoluminescence of MSi Al2O3N2:Ce3+/Eu2+(M=Sr,Ba)oxynitride phosphors[J].Chem Mater,2014,26(6):2075-2085.
[9]Long Q,Wang C,Ding J,et al.Synthesis and luminescence properties of a novel red-emitting LiSr4(BN2)3:Eu2+phosphor[J].Dalton Trans,2015,13(32):14507-14513.
[10]Jiang L H,Pang R,Li D,et al.Tri-chromatic white-light emission from a single-phase Ca9Sc(PO4)7:Eu2+,Tb3+,Mn2+phosphor for LEDapplications[J].Dalton Trans,2015,44(39):17241-17250.
[11]Liu Jie(刘杰),Jiang Man(江漫),Mei Yongmei(梅咏梅),et al.Single-phased white phosphor for white light emitting diodes[J].Progress in Chemistry(化学进展),2013,25(12):2016-2079.
[12]Li K Y,Xue D F.Estimation of electronegativity values of elements in different valence states[J].Journal of Physical Chemistry A,2006,110(39):11332-11337.
[13]Li K Y,Kang C Y,Xue D F.Effect of electrostatic and size on dopant occupancy in lithium niobate single crystal[J].Inorganic Chemistry,2013,52(17):10206-10210.
[14]Li Gong(李宫),Chen Kunfeng(陈昆峰),Jin Jingyi(金京一),et al.La3+-doped NiCo layered double hydroxide nanosheets and their supercapacitive performance[J].Chinese Journal of Applied Chemistry(应用化学),2017,34(1):71-75.
[15]Peter A J,Banu I B S.Enhanced photoluminescence of Li3Ba2Gd3(MoO4)8:Eu3+red phosphor synthesized by mechanochemically assisted direct solid state reaction method at room temperature[J].J Mater Sci Mater Electron,2015,26(4):2045-2052.
[16]Wu H M,Chen H,Liu Y F,et al.Highly uniform NaLa(MoO4)2:Eu3+microspheres:microwave-assisted hydrothermal synthesis,growthmechanism and enhanced luminescent properties[J].J Mater Sci Mater Electron,2014,25:3109-3115.
[17]Liao J H,Zhou D,Yang B,et al.Sol-gelpreparation and photoluminescence properties of CaLa2(MoO4)4:Eu3+phosphors[J].Journal of Luminescence,2013,134(1):533-538.
[18]Ghosh P,Mudring A V.Phase selective synthesis of quantum cutting nanophosphors and the observation of a spontaneous room temperature phase transition[J].Nanoscale,2016,8(15):8160-8169.
[19]You F T,Huang S H,Liu S M,et al.VUV excited luminescence of MGdF4:Eu3+(M=Na,K,NH4)[J].Journal of Luminescence,2004,110(3):95-99.
[20]Tian B N,Chen B J,Tian Y,et al.Visible quantum cutting in Ba Gd2ZnO5:Eu3+phosphor[J].Ceram Int,2004,38:3537-3540.
[21]Lai Zhenyu(赖振宇),Xu Guangliang(徐光亮),Liu Min(刘敏),et al.Effects of microwave heating on preparation of Mn-Zn ferrite nanoparticles[J].Inorganic Chemicals Industry(无机盐工业),2007,39(6):15-17.
[22]Li Guifang(李桂芳),Yang Qian(杨倩),Wei Yunge(卫云鸽).Synthesis and photoluminescence properties of double perovskite Na LaMgWO6:Eu3+red phosphors[J].Journal of Inorganic Materials(无机材料学报),2017,32(9):936-942.
[23]Huang S H,Lou L R.Concentration dependence of sensitizer fluorescence intensity in energy transfer[J].Chinese Journal of Luminescence,1990,11(1):1-7.
[24]Tian Y,Chen B J,Tian B N,et al.Concentration dependent luminescence and energy transfer of flower-like Y2(MoO4)3:Dy3+phosphors[J].J Alloys Compd,2011,509(20):6096-6101.