卤素离子掺杂对Eu~(2+)-Eu~(3+)共存Ca_(12)Al_(14)O_(33):Eu发光性能的影响
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摘要
采用高温固相法在还原气氛中合成Ca_(11.52)Al_(14)O_(33-0.5x-0.5y)F_xCl_y:0.48Eu荧光粉,对样品进行了X射线光电子能谱(XPS)、X射线粉末衍射(XRD)、扫描电镜(SEM)以及荧光光谱(PL)等表征。研究结果表明,所合成样品为立方晶体结构,样品中Eu~(2+)-Eu~(3+)共存且发光可调。在λ_(ex)=253 nm光激发下,单掺F~-与单掺Cl~-的量分别为x=0.5和y=0.5时,Eu~(2+)的蓝光强度与Eu~(3+)的红光强度比值I蓝光/I红光最大,分别为10.16和10.55。通过改变F~-与Cl~-的掺杂浓度,可以调整Eu~(2+)-Eu~(3+)的比例,进而调控荧光粉的发光,发光颜色可调整为淡紫色-深蓝色-淡蓝色-蓝白光-橙红色等变化。
Luminescent materials with the chemical formula Ca_(11.52)Al_(14)O_(33-0.5x-0.5y)F_xCl_y:0.48 Eu were synthesized by a high temperature solid-state method.Techniques such as X-ray photoelectron spectroscopy(XPS),X-ray powder diffraction(XRD),scanning electron microscope(SEM),and photoluminescence spectra(PL) were used to characterize the phosphors.The results showed that the synthesized samples occupy cubic crystal structure,Eu~(2+) and Eu~(3+) coexist in the samples,and the emission intensities of Eu~(2+) and Eu~(3+) can be adjusted by changing F-and Cl-concentration.Under the excitation of 253 nm,the intensity ratio of Iblue/Iredfor blue emission of Eu~(2+) and red emission of Eu~(3+) reaches maximum,which is 10.16 or 10.55 when the content of F-or Cl-ions is x=0.5 or y=0.5.The luminous color can vary from lavender to dark blue,light blue,and orange red by adjusting the concentration of F-and Cl-.
Luminescent materials with the chemical formula Ca_(11.52)Al_(14)O_(33-0.5x-0.5y)F_xCl_y:0.48 Eu were synthesized by a high temperature solid-state method.Techniques such as X-ray photoelectron spectroscopy(XPS),X-ray powder diffraction(XRD),scanning electron microscope(SEM),and photoluminescence spectra(PL) were used to characterize the phosphors.The results showed that the synthesized samples occupy cubic crystal structure,Eu~(2+) and Eu~(3+) coexist in the samples,and the emission intensities of Eu~(2+) and Eu~(3+) can be adjusted by changing F-and Cl-concentration.Under the excitation of 253 nm,the intensity ratio of Iblue/Iredfor blue emission of Eu~(2+) and red emission of Eu~(3+) reaches maximum,which is 10.16 or 10.55 when the content of F-or Cl-ions is x=0.5 or y=0.5.The luminous color can vary from lavender to dark blue,light blue,and orange red by adjusting the concentration of F-and Cl-.
引文
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[3]Zhang J C,Long Y Z,Zhang H D,Sun B,Han W P,Sun X Y.Eu2+/Eu3+-emission-ratio-tunable Ca Zr(PO4)2:Eu phosphors synthesized in air atmosphere for potential white light-emitting deep UV LEDs[J].J.Mater.Chem.C,2014,2(2):312.
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[5]Xu S C,Li P L,Wang Z J,Li T,Bai Q Y,Sun J,Yang Z P.Luminescence and energy transfer of Eu2+/Tb3+/Eu3+in Li Ba BO3phosphors with tunable-color emission[J].J.Mater.Chem.C,2015,3:9112.
[6]Sokolnicki J,Zych E.Synthesis and spectroscopic investigations of Sr2Y8(Si O4)6O2:Eu2+,Eu3+phosphor for white LEDs[J].J.Lumin.,2015,158:65.
[7]Dai W B.Mechanism of the reduction and energy transfer between Eu2+and Eu3+in Eu-doped Ca Al2Si2O8materials prepared in air[J].J.Mater.Chem.C,2014,2:3951.
[8]Zhang Y,Li X J,Li K,Lian H Z,Shang M M,Lin J.Crystal-site engineering control for the reduction of Eu3+to Eu2+in Ca YAl O4structure refinement and tunable emission properties[J].ACS Appl.Mater.Inter.,2015,7(4):2715.
[9]Chen W P.Eu2+and Eu3+co-activated La Al O3phosphor:synthesis and tuned luminescence[J].Dalton Trans.,2015,44(40):17730.
[10]Zhang Y,Liu X M,Li X J,Li K,Lian H Z,Shang M M,Lin J.Overcoming crystallographically imposed geometrical restrictions on the valence state of Eu in Ca Gd Al O4:realization of white light emission from singlydoped Eu phosphors[J].Dalton Trans.,2015,44(17):7743.
[11]Xia Z G,Zhuang J Q,Liao L B.Novel red-emitting Ba2Tb(BO3)2Cl:Eu phosphor with efficient energy transfer for potential application in white light-emitting diodes[J].Inorg.Chem.,2012,51(13):7202.
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[15]Peng H L,Gao Q S,Meng L L,Zhang L X,Pang Q,Liang L F.Sol-gel method and opticalproperties of Ca12Al14O32F2:Eu3+red phosphors[J].J.Rare Earths,2015,33(9):927.
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[19]Hayashi K,Ueda N,Hirano M,Hideo H.Effect of stability and diffusivity of extra-framework oxygen species on the formation of oxygen radicals in 12Ca O·7Al2O3[J].Solid State Ionics,2004,173(7):89.
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