Na_2Ca_(2.92)Si_6O_(16):0.08Eu~(3+)荧光粉的制备及其发光特性研究
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摘要
采用高温固相法制备了一系列Eu~(3+)掺杂的Na_2Ca_3Si_6O_(16)红色荧光粉.用X射线粉末衍射仪表征了荧光粉Na_2Ca_(3-x)Si_6O_(16):xEu~(3+)的结构.研究显示,Eu~(3+)的掺入并未使Na_2Ca_3Si_6O_(16)晶体产生杂相.采用荧光分光光度计分析了Na_2Ca_(3-x)Si_6O_(16):xEu~(3+)的光学性质. Na_2Ca_(3-x)Si_6O_(16):xEu~(3+)荧光粉发红光,其中以波长611 nm的发射峰强度最强.Eu~(3+)的掺杂对Na_2Ca_(3-x)Si_6O_(16):xEu~(3+)荧光粉发射光谱的峰形和峰位置无明显影响,但发光强度与Eu~(3+)的掺杂量(摩尔分数)有关,当Eu~(3+)的掺杂量为0.08时,Na_2Ca_(3-x)Si_6O_(16):xEu~(3+)荧光粉的发光强度达到最大值,掺杂量继续增大时会发生浓度淬灭现象,这可能是由多电子偶极相互作用引起的.结果表明:Na_2Ca_(2.92)Si_6O_(16):0.08Eu~(3+)荧光粉是一种潜在的可用于白光LED的红色发光材料.
A series of Na_2Ca_(3-x)Si_6O_(16):xEu~(3+)was prepared with high temperature solid-state reaction and structurally characterized with X-ray powder diffraction. The results of X-ray powder diffraction showed that Eu~(3+)-doping had no significant effect on the crystal structure of Na_2Ca_3Si_(6)O_(16):Eu~(3+). Its optical properties were checked with the spectrofluorometer. The results showed that the Na_2Ca_(3-x)Si_6O_(16):x Eu~(3+)phosphor emitted red light with the strongest emission peak at 611 nm. The doping of Eu~(3+)did not change the peak shape and position of the emission spectra of Na_2Ca_(3-x)Si_6O_(16):x Eu~(3+)phosphor. However,the doping content( mole fraction) of Eu~(3+)was related to the luminescence intensity. When the concentration of Eu~(3+)was 0.08,the Na_2Ca_(3-x)Si_6O_(16):x Eu~(3+)showed the strongest luminescence intensity. The concentration quenching was observed when Eu~(3+)concentration was over 0.08,and the concentration quenching mechanism was verified as multipole-multipole interaction. The results indicated that Na_2Ca_(2.92)Si_6O_(16):0.08Eu~(3+)phosphor was a potential red light-emitting material for white LED.
A series of Na_2Ca_(3-x)Si_6O_(16):xEu~(3+)was prepared with high temperature solid-state reaction and structurally characterized with X-ray powder diffraction. The results of X-ray powder diffraction showed that Eu~(3+)-doping had no significant effect on the crystal structure of Na_2Ca_3Si_(6)O_(16):Eu~(3+). Its optical properties were checked with the spectrofluorometer. The results showed that the Na_2Ca_(3-x)Si_6O_(16):x Eu~(3+)phosphor emitted red light with the strongest emission peak at 611 nm. The doping of Eu~(3+)did not change the peak shape and position of the emission spectra of Na_2Ca_(3-x)Si_6O_(16):x Eu~(3+)phosphor. However,the doping content( mole fraction) of Eu~(3+)was related to the luminescence intensity. When the concentration of Eu~(3+)was 0.08,the Na_2Ca_(3-x)Si_6O_(16):x Eu~(3+)showed the strongest luminescence intensity. The concentration quenching was observed when Eu~(3+)concentration was over 0.08,and the concentration quenching mechanism was verified as multipole-multipole interaction. The results indicated that Na_2Ca_(2.92)Si_6O_(16):0.08Eu~(3+)phosphor was a potential red light-emitting material for white LED.
引文
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[2] ZHOU Y,ZHU C,ZHANG M,et al. Optical properties of Eu-and Dy-doped calcium aluminoborosilicate glasses for LED applications[J]. Journal of Alloys&Compounds,2016,688:715-720.
[3] ZHANG X G,ZHOU F X,SHI J X,et al. Sr3.5Mg0.5Si3O8Cl4:Eu2+bluish-green-emitting phosphor for NUV-based LED[J]. Materials Letters,2009,63(11):852-854.
[4]王泽忠,汪克风,杜发钊,等.稀土荧光/聚碳酸酯加工可行性探讨及其荧光性能研究[J].华南师范大学学报(自然科学版),2015,47(1):32-37.WANG Z Z,WANG K F,DU F Z,et al. Study on processing feasibility and fluorescence properties of rare-earth fluorescent/polycarbonate[J]. Journal of South China Normal University(Natural Science Edition),2015,47(1):32-37.
[5] YU Q M,LIU Y F,WU S,et al. Luminescent properties of Ca2Si O4:Eu3+red phosphor trichromatic white light emitting diodes[J]. Journal of Rare Earths,2008,26(6):783-786.
[6] LI L,TANG X H,JIANG Z Q,et al. Na Ba La2(PO4)3:a novel host lattice for Sm3+-doped phosphor materials emitting reddish-orange light[J]. Journal of Alloys and Compounds,2017,701:515-523.
[7] LIAN J B,QIN H,LIANG P,et al,Co-precipitation synthesis of Y2O2SO4:Eu3+nanophosphor and comparison of photoluminescence properties with Y2O2:Eu3+and Y2O2S:Eu3+nanophosphors[J]. Solid State Sciences,2015,48:147-154.
[8] ZHAO G S,LIU W,LOU Z H,et al. Hydrothermal synthesis and photoluminescence properties of In3+co-doped YVO4:Eu3+phosphors[J]. Advanced Powder Technology,2016,27(4):1225-1232.
[9] CHEN G W,LI Y B,QI W C,et al. Morphology-tailored synthesis and luminescent properties of Y2O3:Eu3+phosphors[J]. Journal of Materials Science-Materials in Electronics,2018,29(4):2841-2847.
[10]杨洁,陈锐彬,万霞,等. Dy3+/Eu3+共掺钒酸钇荧光粉的合成及发光性质研究[J].华南师范大学学报(自然科学版),2011(2):81-86.YANG J,CHEN R B,WAN X,et al. Synthesis and luminescence properties of Dy3+/Eu3+co-doped YVO4phosphors[J]. Journal of South China Normal University(Natural Science Edition),2011(2):81-86.
[11] KIRM M,FELDBACH E,MAGI H,et al. Silicate apatite phosphors for pc-LED applications[J]. Proceedings of the Estonian Academy of Sciences,2017,66(4):383-395.
[12] CHEN H Y,WENG M H,CHANG S J,et al. Preparation of Sr2Si O4:Eu3+phosphors by microwave-assisted sintering and their luminescent properties[J]. Ceramics International,2012,38(1):125-130.
[13] WANG Z J,GUO S Q,LI Q X,et al. Luminescent properties of Ba2Si O4:Eu3+for white light emitting diodes[J].Physica B:Condensed Matter,2013,411:110-113.
[14] WU Y,WANG Y S,HE D W,et al. Synthesis of the Zn2Si O4:Eu3+red phosphor by sol-gel method[J]. Spectroscopy and Spectral Analysis,2011,31(4):890-893.
[15] KAHLENBERG V,GIRTLER D,ARROYAB E,et al.(Na2Ca3Si6O16)-structural,spectroscopic and computational investigations on a crystalline impurity phase in industrial soda-lime glasses[J]. Mineralogy and Petrology,2010,100(1/2):1-9.
[16] BARROS B S,OLIVEIRA R S D,KULESZA J,et al.Reddish-orange Ca3-xAl2O6:x Eu3+,nanophosphors:fast synthesis and photophysical properties[J]. Journal of Physics&Chemistry of Solids,2015,78:90-94.
[17] JIA C Y,HUANG Z,TIAN X Y,et al. Synthesis and photoluminescence properties of a novel Ba Ge4O9:Eu3+red emitting phosphor for warm white LEDs[J]. Dyes and Pigments,2019,160:772-778.
[18]郎集会,孙雨婷,李香兰,等.稀土Eu掺杂Zn O纳米棒的水热合成及其光学性质[J].华南师范大学学报(自然科学版),2018,50(2):25-29.LANG J H,SUN Y T,LI L X,et al. Hydrothermal synthesis and optical properties of Eu-doped Zn O nanorods[J].Journal of South China Normal University(Natural Science Edition),2018,50(2):25-29.
[19] SAKTHIVEL T,ANNADURAI G,VIJAYAKUMAR R,et al. Synthesis,luminescence properties and thermal stability of Eu3+-activated Na2Y2B2O7red phosphors excited by near-UV light for pc-WLEDs[J]. Journal of Luminescence,2019,205:129-135.
[20] van UITER L G. Characterization of energy transfer interactions between rare earth ions[J]. Journal of The Electrochemical Society,1967,114(10):1048-1053.
[21] BLASSE G,GRABMAIER B C. Luminescent Materials[M]. Berlin:Springer-Verlag,1994:91-106.
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[23] BLASSE G. Energy transfer in oxidic phosphors[J].Physics Letters A,1968,28(6):444-445.