溶剂热法一步合成纳米Gd_2O_2S∶Eu~(3+)发光粉
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摘要
以六水硝酸钆、六水硝酸铕、无水乙醇、乙二胺、硫代甘油、硫脲和升华硫为主要实验原料,通过溶剂热法一步合成纳米Gd_2O_2S∶Eu~(3+)发光粉。采用X射线衍射(XRD),场发射扫描电镜(FE-SEM)和光致发光光谱(PL)等手段对合成产物进行表征。在本研究中,不同硫源影响合成产物的组成和结晶性。合适的硫源为升华硫,其较优的摩尔比为5。此工艺条件下合成的Gd_2O_2S为近球形,团聚较明显,颗粒大小约为30~50 nm。在260 nm的紫外光激发下,Gd_2O_2S∶Eu~(3+)发光粉的主发射峰位于628 nm,归属于Eu~(3+)离子的~5D_0-~7F_2跃迁。Gd_2O_2S∶Eu~(3+)的发光强度受Eu~(3+)离子掺杂浓度影响很大,Eu~(3+)离子的猝灭浓度为4%,其相应的余辉衰减时间为0.5216μs,色坐标为(0.5976,0.3153),属于红光区。
Gd_2O_2S:Eu~(3+) nanophosphor was successfully synthesized by one-step of solvothermal method using Gd(NO_3)_3·6 H_2O,Eu(NO_3)_3·6 H_2O,absolute ethyl alcohol(CH_3CH_2OH),ethyleneediamine(C_2H_8N_2),thioglycerol(C_3H_8O_2S),thiourea(CN_2H_4S)and sublimed sulfur(S)as the starting materials.The as-synthesized products were characterized by X-ray diffraction(XRD),field emission scanning electron microscopy(FE-SEM)and photoluminescence(PL)spectra.The X-ray diffraction(XRD)result shows that the phase composition and crystallinity of as-synthesized products are greatly influenced by different sources of sulfur and the molar ratios for S:Gd,where the appropriate sulfur source is sublimed sulfur and the optimal molar ratio is 5.The FE-SEM images reveal the as-synthesized Gd_2O_2S particles are in shape of quasi sphere and serious aggregation,the average particle size is about 30 ~ 50 nm.Under UV light excitation of 260 nm,the strongest emission peak for Gd_2O_2S:Eu~(3+) nanophosphor is located at 628 nm,corresponding to the ~5D_0-~7F_2 transition of Eu~(3+) ions.PL spectra shows the luminescent intensity of Gd_2O_2S:Eu~(3+) nanophosphor is greatly affected by the concentration of Eu~(3+) ions.It is found that the quenching concentration of Eu~(3+) is 4%,the calculated lifetime is 0.5216 μs and chromaticity coordinate is determined to be(0.5976,0.3153),attributing to the red emission.
Gd_2O_2S:Eu~(3+) nanophosphor was successfully synthesized by one-step of solvothermal method using Gd(NO_3)_3·6 H_2O,Eu(NO_3)_3·6 H_2O,absolute ethyl alcohol(CH_3CH_2OH),ethyleneediamine(C_2H_8N_2),thioglycerol(C_3H_8O_2S),thiourea(CN_2H_4S)and sublimed sulfur(S)as the starting materials.The as-synthesized products were characterized by X-ray diffraction(XRD),field emission scanning electron microscopy(FE-SEM)and photoluminescence(PL)spectra.The X-ray diffraction(XRD)result shows that the phase composition and crystallinity of as-synthesized products are greatly influenced by different sources of sulfur and the molar ratios for S:Gd,where the appropriate sulfur source is sublimed sulfur and the optimal molar ratio is 5.The FE-SEM images reveal the as-synthesized Gd_2O_2S particles are in shape of quasi sphere and serious aggregation,the average particle size is about 30 ~ 50 nm.Under UV light excitation of 260 nm,the strongest emission peak for Gd_2O_2S:Eu~(3+) nanophosphor is located at 628 nm,corresponding to the ~5D_0-~7F_2 transition of Eu~(3+) ions.PL spectra shows the luminescent intensity of Gd_2O_2S:Eu~(3+) nanophosphor is greatly affected by the concentration of Eu~(3+) ions.It is found that the quenching concentration of Eu~(3+) is 4%,the calculated lifetime is 0.5216 μs and chromaticity coordinate is determined to be(0.5976,0.3153),attributing to the red emission.
引文
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[22]V.Biondo,P.W.C.Sarvezuk,F.F.Ivashita,et al.Geometric magnetic frustration in RE2O2S oxysulfides(R E=Sm,Eu and Gd)[J].Mater.Res.Bull.,2014,54:41-47.
[23]田莹,曹望和,罗昔贤,等.乳状液膜法制备硫氧化物超细X射线发光粉[J].中国稀土学报,2005,23:271-276.
[24]Y.H.Song,H.P.You,Y.J.Huang,et al.HighlyUniform and Monodisperse Gd2O2S:Ln3+(Ln=Eu,Tb)Submicrospheres:Solvothermal Synthesis and LuminescenceProperties[J].Inorg.Chem.,2010,49(24):11499-11504.
[25]J.Huang,Y.H.Song,Y.Sheng,et al.Gd2O2S:Eu3+andGd2O2S:Eu3+/Gd2O2S Hollow Microspheres:SolvothermalPreparation and Luminescence Properties[J].J.Alloy.Compd,2012,532(15):34-40.
[26]J.Liu,H.D.Luo,P.J.Liu,et al.One-pot solvothermalsynthesis of uniform layer-by-layer self-assembledultrathin hexagonal Gd2O2S nanoplates and luminescentproperties from single doped Eu3+and codoped Er3+,Yb3+[J].Dalton T.,2012,41:13984-13988.
[27]邝金勇,刘应亮,张静娴,等.溶剂热合成纳米球状La2O2S:Eu3+荧光粉[J].高等学校化学学报,2005,5:41-43.
[28]J.Thirumalai,R.Chandramohan,T.A.Vijayan.Synthesis,characterization and formation mechanismof monodispersed Gd2O2S:Eu3+nanocrystals[J].J MaterSci:Mater Electron.,2011,22:936-943.
[2]T.Guo,Y.Lin,Z.Li,et al.Gadolinium Oxysulfide-Coated Gold Nanorods with Improved Stability and Dual-modal Magnetic Resonance/Photoacoustic Imaging Contrast Enhancement for Cancer Theranostics[J].Nanoscale,2017,9:56-61.
[3]罗昔贤,曹望和.稀土离子激活的稀土氧化物的蓝,绿,红上转换发光与光谱特性[J].中国科学B辑:化学,2007,37(2):148-155.
[4]S.A.Osseni,S.Lechevallier,M.Verelst,et al.Gadolinium oxysul-de nanoparticles as multimodal imaging agents for T2-weighted MR,X-ray tomography and photoluminescence[J].Nanoscale,2014,6:555-564.
[5]F.Wang,B.Yang,X.M.Chen,et al.Color-tunable and up conversion luminescence of Gd2O2S:Er,Tb phosphor[J].Mater.Chem.Phys,2016,169:113-119.
[6]X.X.Luo,W.H.Cao,Y.Tian.Characteristic and synthesis mechanism of Gd2O2S:Tb phosphors prepared by cold isostatic press pretreatment[J].Opt.Mater.,2007,30:351-356.
[7]J.B.Lian,F.Liu,X.J.Wang,et al.Hydrothermal synthesis and photoluminescence properties of Gd2O2SO4:Eu3+spherical phosphor[J].Powder Technol.,2014,253:187-192.
[8]S.Blahuta,B.Viana,A.Bessière,et al.Luminescence quenching processes in Gd2O2S:Pr3+,Ce3+scintillating ceramics[J].Opt.Mater.,2011,33:1514-1518.
[9]J.Huang,Y.H.Song,Y.Sheng,et al.Gd2O2S:Eu3+and Gd2O2S:Eu3+/Gd2O2S hollow microspheres:Solvothermal preparation and luminescence properties[J].J.Alloy.Compd.,2012,532:34-40.
[10]W.Wang,Y.S.Li,H.M.Kou,et al.Gd2O2S:Pr Scintillation Ceramics from Powder Synthesized by a Novel Carbothermal Reduction Method[J].J.Am.Ceram.Soc.,2015:1-6.
[11]王飞,刘大春,杨斌,等.掺杂离子对Gd2O2S:Eu3+磷光体结构和发光性能的影响[J].中国有色金属学报,2012,22:1107-1112.
[12]陈雨,姜国玉,王雪松.以上转换纳米颗粒和光动力疗法为基础的肿瘤联合治疗研究进展[J].影像科学与光科学,2016,34(4):297-311.
[13]S.Som,A.Choubey,S.K.Sharma.Spectral and trapping parameters of Eu3+in Gd2O2S nanophosphor[J].J.Exp.Nanosci.,2015,10:350-370.
[14]K.Zhu,W.H.Ding,W.Sun,et al.1.06μm last absorption properties of Sm2O2S prepared by flux method[J].Mater SCI:Mater Electron.,2016,27:2379-2384.
[15]黄存新,刘翠,余明清,等.固相合成Gd2O2S:Pr陶瓷闪烁体粉末[J].人工晶体学报,2005,34(1):713-716.
[16]Bang J,Abboudi M,Abrams B,et al.Combustion synthesis of Eu3+,Tb3+and Tm3+doped Ln2O2S(Ln=Y,La,Gd)phosphors[J].J.Lumin.,2004,106:177-185.
[17]Thirumalai J,Chandramohan R,Valanarasu S.Shape selective synthesis and opto-electronic properties of Eu3+doped gadolinium oxysulfide nanostructures[J].J Mater Sci.,2009,44:3889-3899.
[18]桑晓彤,雷明霞,连景宝.Gd2O2S:Eu3+发光粉的还原法合成与光致发光[J].中国陶瓷,2015,51(4):21-25.
[19]连景宝,刘凡,张静,等.Gd2O2S:Pr3+荧光粉的合成与发光性能研究[J].中国材料进展,2016,35(5):391-395.
[20]C.He,Z.G.Xia,Q.L.Liu.Microwave solid state synthesis and luminescence properties of green-emitting Gd2O2S:Tb3+phosphor[J].Opt.Mater.,2015,42:11-16.
[21]Fan W,Zhang X Y,Chen L X,et al.Preparation of Gd2O2S:Er3+,Yb3+Phosphor and Its Multi-Wavelength Sensitive Upconversion Luminescence Mechanism[J].CrystEngC omm,2015,15(17):1881-1889.
[22]V.Biondo,P.W.C.Sarvezuk,F.F.Ivashita,et al.Geometric magnetic frustration in RE2O2S oxysulfides(R E=Sm,Eu and Gd)[J].Mater.Res.Bull.,2014,54:41-47.
[23]田莹,曹望和,罗昔贤,等.乳状液膜法制备硫氧化物超细X射线发光粉[J].中国稀土学报,2005,23:271-276.
[24]Y.H.Song,H.P.You,Y.J.Huang,et al.HighlyUniform and Monodisperse Gd2O2S:Ln3+(Ln=Eu,Tb)Submicrospheres:Solvothermal Synthesis and LuminescenceProperties[J].Inorg.Chem.,2010,49(24):11499-11504.
[25]J.Huang,Y.H.Song,Y.Sheng,et al.Gd2O2S:Eu3+andGd2O2S:Eu3+/Gd2O2S Hollow Microspheres:SolvothermalPreparation and Luminescence Properties[J].J.Alloy.Compd,2012,532(15):34-40.
[26]J.Liu,H.D.Luo,P.J.Liu,et al.One-pot solvothermalsynthesis of uniform layer-by-layer self-assembledultrathin hexagonal Gd2O2S nanoplates and luminescentproperties from single doped Eu3+and codoped Er3+,Yb3+[J].Dalton T.,2012,41:13984-13988.
[27]邝金勇,刘应亮,张静娴,等.溶剂热合成纳米球状La2O2S:Eu3+荧光粉[J].高等学校化学学报,2005,5:41-43.
[28]J.Thirumalai,R.Chandramohan,T.A.Vijayan.Synthesis,characterization and formation mechanismof monodispersed Gd2O2S:Eu3+nanocrystals[J].J MaterSci:Mater Electron.,2011,22:936-943.