溶胶-凝胶法合成Sr_3MgSi_2O_8∶Eu~(3+)红色荧光粉及其发光性能
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摘要
采用溶胶-凝胶法合成了Sr_3MgSi_2O_8∶Eu~(3+)红色荧光粉,并通过X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、扫描电镜(SEM)以及荧光光谱(PL)、X射线光电子能谱(XPS)等分析方法,对不同烧结温度(950,1 050,1 150,1 250℃)热处理4 h后得到的粉体的物相、形貌及发光性能进行了表征分析。由XRD表征结果可知,制备出的样品为正交晶系的Sr_3MgSi_2O_8;由扫描电镜及比表面积的测试结果可知,经过1 150℃热处理得到的荧光粉具有最大比表面积,可达到90.213 1 m~2/g,且粒径大小均一;由红外光谱图可知:样品中含有Si—O—Si、Mg—O和Sr—O化学键;在394 nm的激发波长下,所有样品在614 nm和702 nm处出现了强发射峰,分别对应于Eu~(3+)的~5D_0→~7F_2和~5D_0→~7F_4跃迁,属红光发射。随着热处理温度的升高,样品所对应的发射峰强度呈现出先增大后减小的变化趋势,即出现温度猝灭效应;经1 150℃热处理合成的Sr_3MgSi_2O_8∶Eu~(3+)红色荧光粉的发光性能最好,即最佳的热处理温度为1 150℃。
In this paper, Sr_3MgSi_2O_8∶Eu~(3+) red phosphor was synthesized by sol-gel method. The phase, morphology and luminescence properties of the powders obtained by calcination at different temperatures(950, 1 050, 1 150, 1 250 ℃) were characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM), fluorescence spectrum(PL) and X-ray photoelectron(XPS). According to the results of XRD, the prepared sample is orthorhombic Sr_3MgSi_2O_8. The results of scanning electron microscopy and specific surface area show that the phosphor obtained by heat treatment at 1 150 ℃ has the largest specific surface area, which can reach 90.213 1 m~2/g. In addition, the diameter is uniform; the infrared spectrum shows that the sample contains Si—O—Si, Mg—O and Sr—O chemical bonds; all samples show strong emission peaks at 614 nm and 702 nm, corresponding to the~5D_0→~7F_2 and ~5D_0→~7F_(4 )transitions of Eu~(3+) when the excitation wavelength is 394 nm, which belongs to red light emission. As the heat treatment temperature increases, the intensity of the emission peak corresponding to the sample first increases and then decreases, that is, the temperature quenching effect occurs. The Sr_3MgSi_2O_8∶Eu~(3+) red phosphor synthesized by heat treatment at 1 150 ℃ has the best luminescence performance. The optimum heat treatment temperature is 1 150 ℃.
In this paper, Sr_3MgSi_2O_8∶Eu~(3+) red phosphor was synthesized by sol-gel method. The phase, morphology and luminescence properties of the powders obtained by calcination at different temperatures(950, 1 050, 1 150, 1 250 ℃) were characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM), fluorescence spectrum(PL) and X-ray photoelectron(XPS). According to the results of XRD, the prepared sample is orthorhombic Sr_3MgSi_2O_8. The results of scanning electron microscopy and specific surface area show that the phosphor obtained by heat treatment at 1 150 ℃ has the largest specific surface area, which can reach 90.213 1 m~2/g. In addition, the diameter is uniform; the infrared spectrum shows that the sample contains Si—O—Si, Mg—O and Sr—O chemical bonds; all samples show strong emission peaks at 614 nm and 702 nm, corresponding to the~5D_0→~7F_2 and ~5D_0→~7F_(4 )transitions of Eu~(3+) when the excitation wavelength is 394 nm, which belongs to red light emission. As the heat treatment temperature increases, the intensity of the emission peak corresponding to the sample first increases and then decreases, that is, the temperature quenching effect occurs. The Sr_3MgSi_2O_8∶Eu~(3+) red phosphor synthesized by heat treatment at 1 150 ℃ has the best luminescence performance. The optimum heat treatment temperature is 1 150 ℃.
引文
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[19] SINGH D,SHEORAN S,TANWAR V.Europium doped silicate phosphors:synthetic and characterization techniques [J].Adv.Mater.Lett.,2017,8(5):656-672.
[20] FU L L,LIU G F,YANG X X,et al..Up-conversion luminescent properties and optical thermometry of LaMgAl11O19∶Yb3+/Er3+ phosphors [J].Ceram.Int.,2015,41(10):14064-14069.
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[24] CHEN Y,ZHOU B,SUN Q M,et al..Synthesis and luminescence properties of Sr3MgSi2O8∶Ce3+,Tb3+ for application in near ultraviolet excitable white light-emitting-diodes [J].Superlattice.Microst.,2016,100:158-167.
[2] 林燕美,陈国良,陈云钦,等.绿色长余辉荧光粉Sr2ZnSi2O7∶Mn2+,Tb3+的制备及性能 [J].硅酸盐学报,2011,39(9):1384-1388.LIN Y M,CHEN G L,CHEN Y Q,et al..Preparation and properties of green afterglow phosphor Sr2ZnSi2O7∶Mn2+,Tb3+ [J].J.Chin.Ceram.Soc.,2011,39(9):1384-1388.(in Chinese)
[3] DYCK N C,VAN VEGGEL F C J M,DEMOPOULOS G P,et al..Size-dependent maximization of upconversion efficiency of citrate-stabilized β-phase NaYF4∶Yb3+,Er3+ crystals via annealing [J].ACS Appl.Mater.Interfaces,2013,5(22):11661-11667.
[4] BARVE R A,SURIYAMURTHY N,PANIGRAHI B S,et al..Dosimetric investigations of Tb3+-doped strontium silicate phosphor [J].Radiat.Prot.Dosim.,2015,163(4):430-438.
[5] SINGH J,BAITHA P K,MANAM J.Influence of heat treatment on the structural and optical properties of SrGd2O4∶Eu3+ phosphor [J].J.Rare Earths,2015,33(10):1040-1050.
[6] CAO R P,CENG D,LIU P,et al..Synthesis and photoluminescence properties of LaAlO3∶Mn4+,Na+ deep red-emitting phosphor [J].Appl.Phys.A,2016,122(4):299-1-6.
[7] 山田健一.Ca(Eu1-xLax)4Si3O13红色荧光粉的研究及其在三基色白光LED上的应用 [J].姜伟,译.中国照明电器,2005(8):24-29.SHAN T J Y.Study on Ca(Eu1-xLax)4Si3O13 red phosphor and Its application in three-primary white LEDs [J].JIANG W,trans.China Light.Appl.,2005(8):24-29.(in Chinese)
[8] FENG G,JIANG W H,CHEN Y B,et al..A novel red phosphor NaLa4(SiO4)3F∶Eu3+ [J].Mater.Lett.,2011,65(1):110-112.
[9] HUANG C H,KUO T W,CHEN T M.Novel red-emitting phosphor Ca9Y(PO4)7∶Ce3+,Mn2+ with energy transfer for fluorescent lamp application [J].ACS Appl.Mater.Interfaces,2010,2(5):1395-1399.
[10] SRINIVASAN R,YOGAMALAR N R,ELANCHEZHIYAN J,et al..Structural and optical properties of europium doped yttrium oxide nanoparticles for phosphor applications [J].J.Alloys Compd.,2010,496(1-2):472-477.
[11] IN J H,LEE H C,YOON M J,et al..Synthesis of nano-sized YAG∶Eu3+ phosphor in continuous supercritical water system [J].J.Supercrit.Fluids,2007,40(3):389-396.
[12] 焦芳芳.Eu、Tb掺杂碱土多硅酸盐发光材料的研究 [D].保定:河北大学,2009.JIAO F F.Study on Eu or Tb Doped Alkaline Earth Polysilicate Phosphors [D].Baoding:Hebei University,2009.(in Chinese)
[13] DAI W B,LEI Y F,YU T,et al..Luminescence properties and a substitution defect model for self-reduction of europium ions in silicate Ba(Eu)MgSiO4 phosphors [J].Mater.Res.Bull.,2015,67:176-184.
[14] SINGH D,TANWAR V,BHAGWAN S,et al..Synthesis and optical characterization of terbium doped M2SiO4 nanophosphors [J].Adv.Sci.Lett.,2014,20(7-9):1531-1534.
[15] SAHU I P,CHANDRAKAR P,BAGHEL R N,et al..Luminescence properties of dysprosium doped calcium magnesium silicate phosphor by solid state reaction method [J].J.Alloys Compd.,2015,649:1329-1338.
[16] SINGH D,SHEORAN S,TANWAR V,et al..Optical characteristics of Eu(Ⅲ) doped MSiO3(M=Mg,Ca,Sr and Ba) nanomaterials for white light emitting applications [J].J.Mater.Sci.:Mater.Electron.,2017,28(4):3243-3253.
[17] ZHOU B,YANG W F,HAN S Y,et al..Photon upconversion through Tb3+ -mediated interfacial energy transfer [J].Adv.Mater.,2015,27(40):6208-6212.
[18] SINGH D,SHEORAN S.Synthesis and luminescent characteristics of M3Y2Si3O12∶Eu3+ (M=Ca,Mg,Sr and Ba) nanomaterials for display applications [J].J.Mater.Sci.:Mater.Electron.,2016,27(12):12707-12718.
[19] SINGH D,SHEORAN S,TANWAR V.Europium doped silicate phosphors:synthetic and characterization techniques [J].Adv.Mater.Lett.,2017,8(5):656-672.
[20] FU L L,LIU G F,YANG X X,et al..Up-conversion luminescent properties and optical thermometry of LaMgAl11O19∶Yb3+/Er3+ phosphors [J].Ceram.Int.,2015,41(10):14064-14069.
[21] HENCH L L,WEST J K.The sol-gel process [J].Chem.Rev.,1990,90(1):33-72.
[22] KESSLER V G,SPIIKSMA G I,SEISENBAEVA G A,et al..New insight in the role of modifying ligands in the sol-gel processing of metal alkoxide precursors:a possibility to approach new classes of materials [J].J.Sol-Gel Sci.Technol.,2006,40(2-3):163-179.
[23] 李玥.M3MgSi2O8∶Eu2+,Mn2+(M=Ba,Sr)荧光材料发光性能的研究 [D].北京:北京交通大学,2011.LI Y.Luminescence Properties of M3MgSi2O8∶Eu2+,Mn2+ (M=Ba,Sr) Phosphors [D].Beijing:Beijing Jiaotong University,2011.(in Chinese)
[24] CHEN Y,ZHOU B,SUN Q M,et al..Synthesis and luminescence properties of Sr3MgSi2O8∶Ce3+,Tb3+ for application in near ultraviolet excitable white light-emitting-diodes [J].Superlattice.Microst.,2016,100:158-167.