基质组成变化及电荷补偿对NaM_4(VO_4)_3∶Eu~(3+)(M=Mg,Ca)荧光性能的调控
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摘要
利用高温固相法制备NaMg_(4-x)Ca_x(VO_4)_3∶0.01Eu~(3+)(x=0～2)、NaMg_(2.1)Ca_(1.9-y)(VO_4)_3∶yEu~(3+)(y=0～0.19)、NaMg_(2.1)Ca_(1.9-y)(VO_4)_3∶yEu~(3+),yX~-(X=Cl,F)和NaMg_(2.1)Ca_(1.9-2y)(VO_4)_3∶yEu~(3+),yM~+(M=Li,Na,K)系列荧光粉,采用X射线粉末衍射仪、扫描电子显微镜和荧光分光光度计对样品进行了结构和性能表征。探讨基质结构变化和Li~+、Na~+、K~+、F~-、Cl~-等阴阳离子的电荷补偿作用对VO■和Eu~(3+)发光性能的影响以及能量传递机理。研究表明立方相NaMg_2Ca_2(VO_4)_3比四方相NaMg_4(VO_4)_3更能被紫外光有效激发,同时发射基质的蓝绿光和铕离子的红光,且VO■和Eu~(3+)之间的能量传递效率达到42.21%。电荷补偿剂能显著提高Eu~(3+)的发射强度,同时基质发光强度减弱表明电荷补偿剂增强了基质与激活剂离子间的能量传递。通过控制合成条件可以得到单一基质白光发射荧光粉。
NaMg_(4-x)Ca_x(VO_4)_3∶0.01 Eu~(3+)(x=0～2), NaMg_(2.1)Ca_(1.9-y)(VO_4)_3∶yEu~(3+)(y=0～0.19), NaMg_(2.1)Ca_(1.9-y)(VO_4)_3∶yEu~(3+),yX~-(X=Cl,F) and NaMg_(2.1)Ca_(1.9-2)_y(VO_4)_3∶yEu~(3+),yM~+(M=Li, Na, K) phosphors have been synthesized by high temperature solid phase method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and photoluminescence spectra were utilized to characterize the samples. The results show that the NaMg_2Ca_2(VO_4)_3 cubic phase phosphor can been effectly excited by UV light, and emit the blue green light of vanadate ions and the red light of europium ions simultaneously. The effect on the luminescence properties of VO■ and Eu~(3+) by adjusting matrix composition and charge compensation by F~-, Cl~-, Li~+, Na~+ and K~+ ions, the energy transfer from VO■ to Eu~(3+), and the energy transfer mechanism have been discussed. Charge compensators can increase the emission intensity of Eu~(3+ )and decrease the luminescence intensity of the substrate significantly, indicating that the charge compensators enhance the energy transfer between the substrate and activator ions. The emission intensities of the blue green and red light can be controlling, and a single base white light phosphor was obtained.
NaMg_(4-x)Ca_x(VO_4)_3∶0.01 Eu~(3+)(x=0～2), NaMg_(2.1)Ca_(1.9-y)(VO_4)_3∶yEu~(3+)(y=0～0.19), NaMg_(2.1)Ca_(1.9-y)(VO_4)_3∶yEu~(3+),yX~-(X=Cl,F) and NaMg_(2.1)Ca_(1.9-2)_y(VO_4)_3∶yEu~(3+),yM~+(M=Li, Na, K) phosphors have been synthesized by high temperature solid phase method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and photoluminescence spectra were utilized to characterize the samples. The results show that the NaMg_2Ca_2(VO_4)_3 cubic phase phosphor can been effectly excited by UV light, and emit the blue green light of vanadate ions and the red light of europium ions simultaneously. The effect on the luminescence properties of VO■ and Eu~(3+) by adjusting matrix composition and charge compensation by F~-, Cl~-, Li~+, Na~+ and K~+ ions, the energy transfer from VO■ to Eu~(3+), and the energy transfer mechanism have been discussed. Charge compensators can increase the emission intensity of Eu~(3+ )and decrease the luminescence intensity of the substrate significantly, indicating that the charge compensators enhance the energy transfer between the substrate and activator ions. The emission intensities of the blue green and red light can be controlling, and a single base white light phosphor was obtained.
引文
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[3] SONG D,GUO C F,LI T.Luminescence of the self-activated vanadate phosphors Na2LnMg2V3O12 (Ln=Y,Gd) [J].Ceram.Int.,2015,41(5):6518-6524.
[4] MIN X,HUANG Z H,FANG M H,et al..Luminescence properties of self-activated M3(VO4)2(M=Mg,Ca,Sr,and Ba) phosphors synthesized by solid-state reaction method [J].J.Nanosci.Nanotechnol.,2016,16(4):3684-3689.
[5] YANG L X,MI X Y,SU J G,et al..Tunable luminescence and energy transfer properties in Ca2-xNaMg2V3O12∶xEu3+phosphors [J].J.Mater.Sci.:Mater.Electron.,2017,28(14):9975-9982.
[6] PARK J Y,CHUNG J W,YANG H K.Synthesis and photoluminescence properties of yellow-emitting Ca5(Zn1-xMgx)4-(VO4)6 self-activated phosphors [J].Optik,2018,155:384-389.
[7] MI L Q,HUANG Y L,CAO L,et al..Modified optical properties via induced cation disorder in self-activated NaMg2V3O10 [J].Dalton Trans.,2018,47(12):4368-4376.
[8] LIANG Y J,LIU M Y,YANG F,et al..Preparation and characteristics of Ca2NaMg2V3O12∶Sm3+,single-phased white-emitting phosphors [J].J.Inorg.Organomet.Polym.Mater.,2013,23(3):684-689.
[9] KIM H,KIM J,LIM S,et al..Photoluminescence of vanadate garnet Ca2NaMg2-xV3O12∶xEu3+ phosphors synthesized by solution combustion method [J].J.Nanosci.Nanotechnol.,2016,16(2):1827-1830.
[10] DHOBALE A R,MOHAPATRA M,NATARAJAN V,et al..Synthesis and photoluminescence investigations of the white light emitting phosphor,vanadate garnet,Ca2NaMg2V3O12co-doped with Dy and Sm [J].J.Lumin.,2012,132(2):293-298.
[11] SETLUR A A,COMANZO H A,SRIVASTAVA A M,et al..Spectroscopic evaluation of a white light phosphor for UV-LEDs-Ca2NaMg2V3O12∶Eu3+ [J].J.Electrochem.Soc.,2005,152(12):H205-H208.
[12] NIE X M,WULAYIN W,SONG T T,et al..Photoluminescence enhancement of self-activated vanadate NaMg4(VO4)3 by cation substitutions [J].Mater.Lett.,2016,185:588-592.
[13] BLANZAT B,LORIERS J.Synthese et etude des proprietesspectrales de monocristaux de vanadate a structure grenat Ca2NaMg2V3O12 active par l'europiumtrivalent [J].Mater.Res.Bull.,1974,9(12):1647-1654.
[14] ZHOU Z,WANG F C,LIU S Q,et al..A single-phase phosphor Ba3LiMgV3O12∶Eu3+ for white light-emitting diodes [J].J.Electrochem.Soc.,2011,158(12):H1238-H1241.
[15] HUANG Y L,YU Y M,TSUBOI T,et al..Novel yellow-emitting phosphors of Ca5M4(VO4)6 (M=Mg,Zn) with isolated VO4 tetrahedra [J].Opt.Express,2012,20(4):4360-4368.
[16] ZHU H L,YANG H,JIN D L,et al..Hydrothermal synthesis and photoluminescent properties of YV1-xPxO4∶Eu3+(x=0-1.0) nanophosphors [J].J.Nanopart.Res.,2008,10(7):1149-1154.
[17] MI X Y,SHI H,WANG Z,et al..Luminescence properties of M3(VO4)2∶Eu3+(M=Ca,Sr,Ba) phosphors [J].J.Mater.Sci.,2016,51(7):3545-3554.
[18] MI X Y,SUN J C,ZHOU P,et al..Tunable luminescence and energy transfer properties in Ca8MgLu(PO4)7∶Ce3+,Tb3+,Mn2+ phosphors [J].J.Mater.Chem.C,2015,3(17):4471-4481.
[19] PAULOSE P I,JOSE G,THOMAS V,et al..Sensitized fluorescence of Ce3+/Mn2+system in phosphate glass [J].J.Phys.Chem.Solids,2003,64(5):841-846.
[20] 陈彩花,杨国辉,梁利芳,等.溶胶凝胶法合成CaYAlO4∶Mn4+红色荧光粉及其荧光性能研究 [J].发光学报,2017,38(5):567-573.CHEN C H,YANG G H,LIANG L F,et al..Luminescent properties of CaYAlO4∶Mn4+red phosphors prepared by sol-gel method [J].Chin.J.Lumin.,2017,38(5):567-573.(in Chinese)