双钙钛矿结构BaLaLiTeO_6∶Eu~(3+)红色荧光粉的光谱与LED封装特性
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摘要
采用高温固相法在1 100℃下合成出一系列不同掺杂浓度的BaLa_(1-x)LiTeO_6∶xEu~(3+)(x=0.1～1)红色荧光粉,并对其结构、形貌、光谱特性及LED光色电性能进行了系统研究。结果表明,在BaLaLiTeO_6中Eu~(3+)的最大和最佳掺杂浓度均为x=0.4,更大的掺杂量将导致杂相和浓度猝灭的产生。在465 nm光激发下,该浓度的样品发射光谱中~5D_0→~7F_2与~5D_0→~7F_2强度比值达到了7.31,色品坐标值为(0.665,0.334),色纯度为99.7%,荧光寿命为660.9μs,绝对量子效率达到71.4%。在100℃时积分发光强度是室温时的84.5%,热激活能经计算为0.434 eV。基于该样品的红光LED灯珠能够发出明亮的红光。综上所述,该类荧光粉表现出良好的发光效率、色纯度及发光热稳定性,在白光LED中具有潜在的应用价值。
A series of BaLa_(1-x)LiTeO_6∶xEu~(3+)(x=0.1-1) red-emitting phosphors were synthesized by high-temperature solid-state reaction at 1 100 ℃, and their structure, morphology, spectra and packaging performance were investigated systematically. The maximum doping content of Eu~(3+) was equal to the optimum one, i. e., x=0.4, beyond which impurities and concentration quenching were observed. The asymmetry ratio of I(~5D_0 →~7F_2)/I(~5D_0 →~7F_1) reached 7.31, resulting in high color purity of 99.7% with CIE 1931 chromaticity coordinates of(0.665, 0.334). The fluorescent lifetime and absolute quantum efficiency were measured to be 660.9 μs and 71.4%, respectively. The integrated emission intensity at 100 ℃ was as high as 84.5% of that at ambient temperature. The thermal activation energy was determined to be 0.434 eV. The prototypical LED based on it enabled to emit bright red light. In conclusion, the phosphor exhibits favorable luminous efficiency, color purity and thermal stability of luminescence, which have potential application in white LEDs.
A series of BaLa_(1-x)LiTeO_6∶xEu~(3+)(x=0.1-1) red-emitting phosphors were synthesized by high-temperature solid-state reaction at 1 100 ℃, and their structure, morphology, spectra and packaging performance were investigated systematically. The maximum doping content of Eu~(3+) was equal to the optimum one, i. e., x=0.4, beyond which impurities and concentration quenching were observed. The asymmetry ratio of I(~5D_0 →~7F_2)/I(~5D_0 →~7F_1) reached 7.31, resulting in high color purity of 99.7% with CIE 1931 chromaticity coordinates of(0.665, 0.334). The fluorescent lifetime and absolute quantum efficiency were measured to be 660.9 μs and 71.4%, respectively. The integrated emission intensity at 100 ℃ was as high as 84.5% of that at ambient temperature. The thermal activation energy was determined to be 0.434 eV. The prototypical LED based on it enabled to emit bright red light. In conclusion, the phosphor exhibits favorable luminous efficiency, color purity and thermal stability of luminescence, which have potential application in white LEDs.
引文
[1] PUST P,SCHMIDT P J,SCHNICK W.A revolution in lighting [J].Nat.Mater.,2015,14(5):454-458.
[2] LI S X,XIE R J,TAKEDA T,et al..Critical review—narrow-band nitride phosphors for wide color-gamut white LED backlighting [J].ECS J.Solid State Sci.,2018,7(1):R3064-R3078.
[3] XIE Z,ZHOU W W,ZHAO W,et al..Synthesis,electronic structure and luminescent properties of a new red-emitting phosphor GdBiW2O9∶Eu3+ [J].Chem.Phys.Lett.,2017,685:177-184.
[4] XIA Z G,XU Z H,CHEN M Y,et al..Recent developments in the new inorganic solid-state LED phosphors [J].Dalton Trans.,2016,45(28):11214-11232.
[5] 刘文全,史瑞新,段如霞,等.CaxSi合金前驱物常压氮化制备Ca1-xAlSiN3∶xEu2+红色荧光粉及发光性能研究 [J].发光学报,2017,38(10):1295-1301.LIU W Q,SHI R X,DUAN R X,et al..Preparation and luminescence properties of Ca1-xAlSiN3∶xEu2+ red phosphors by atmospheric nitriding method with CaxSi alloy precursors [J].Chin.J.Lumin.,2017,38(10):1295-1301.(in Chinese)
[6] 陈沙然,邵起越,董岩,等.K2SiF6∶Mn4+荧光粉湿热环境下的劣化行为 [J].发光学报,2018,39(6):757-763.CHEN S R,SHAO Q Y,DONG Y,et al..Degradation behavior of K2SiF6∶Mn4+ phosphors under heat-moisture conditions [J].Chin.J.Lumin.,2018,39(6):757-763.(in Chinese)
[7] TANNER P A.Some misconceptions concerning the electronic spectra of tri-positive europium and cerium [J].Chem.Soc.Rev.,2013,42(12):5090-5101.
[8] YU R J,WANG C F,CHEN J T,et al..Photoluminescence characteristics of Eu3+-doped double-perovskite phosphors [J].ECS J.Solid State Sci.,2014,3(3):R33-R37.
[9] 郑庆华,周薇薇,吕兆承,等.NaLaMgTeO6∶Eu3+新型红色荧光粉的制备与发光性能 [J].硅酸盐学报,2017,45(4):542-547.ZHENG Q H,ZHOU W W,LV Z C,et al..Preparation and luminescent properties of novel red-emitting phosphor NaLaMgTeO6∶Eu3+ [J].J.Chin.Ceram.Soc.,2017,45(4):542-547.(in Chinese)
[10] LIANG J Y,ZHAO S C,YUAN X X,et al..A novel double perovskite tellurate Eu3+-doped Sr2MgTeO6 red-emitting phosphor with high thermal stability [J].Opt.Laser Technol.,2018,101:451-456.
[11] AMRITHAKRISHNAN B,SUBODH G.Crystal structure and optical properties of B site-ordered ALaLiTeO6(A=Ba,Sr) ceramics [J].Mater.Res.Bull.,2017,93:177-182.
[12] 赖凤琴,李嘉鹏,吴有福生,等.烧结温度和掺杂浓度对Y4Zr3O12∶Eu3+荧光粉发光性质的影响 [J].发光学报,2017,38(11):1436-1442.LAI F Q,LI J P,WU Y F S,et al..Effects of calcination temperature and dopant concentration on the luminescence properties of Eu3+ doped Y4Zr3O12 phosphors [J].Chin.J.Lumin.,2017,38(11):1436-1442.(in Chinese)
[13] LóPEZ M L,JEREZ A,PICO C,et al..Synthesis,crystal structure,and magnetic susceptibility of MLnLiTeO6 (M=Ca,Sr,Ba) [J].J.Solid State Chem.,1993,105(1):19-26.
[14] LIU Q,LI X B,ZHANG B,et al..Structure evolution and delayed quenching of the double perovskite NaLaMgWO6∶Eu3+ phosphor for white LEDs [J].Ceram.Int.,2016,42(14):15294-15300.
[15] TAUC J,GRIGOROVICI R,VANCU A.Optical properties and electronic structure of amorphous germanium [J].Phys.Status Solid B,1966,15(2):627-637.
[16] PHATAK R,GUPTA S K,KRISHNAN K,et al..Crystallographic site swapping of La3+ ion in BaA′LaTeO6 (A′=Na,K,Rb) double perovskite type compounds:diffraction and photoluminescence evidence for the site swapping [J].Dalton Trans.,2013,43(8):3306-3312.
[17] KOLESNIKOV I E,POVOLOTSKIY A V,MAMONOVA D V,et al..Asymmetry ratio as a parameter of Eu3+ local environment in phosphors [J].J.Rare Earths,2018,36(5):474-481.
[18] NGUYEN H D,KIM S J,YEO I H,et al..Luminescent properties of Eu3+-doped Ba2Bi2/3TeO6 and BaBiNaTeO6 double perovskite as new orange-red emitting phosphors [J].J.Electrochem.Soc.,2012,159(3):J54-J60.
[19] DENG H J,GAO Z W,XUE N,et al..A novel Eu3+-doped garnet-type tellurate red-emitting phosphor with high thermal stability and color purity [J].J.Lumin.,2017,192:684-689.
[20] SHI Y S,QUAN B,NING Q J,et al..Photoluminescent properties and Judd-Ofelt analysis of novel Na0.5Sr0.25NbO3∶Eu3+ red phosphor with high quantum efficiency [J].Mater.Res.Bull.,2018,101:363-370.
[21] FERHI M,BOUZIDI C,HORCHANI-NAIFER K,et al..Judd-Ofelt analysis of spectroscopic properties of Eu3+ doped KLa(PO3)4 [J].J.Lumin.,2015,157:21-27.
[22] J?RGENSEN C K,REISFELD R.Judd-Ofelt parameters and chemical bonding [J].J.Less Common.Metals,1983,93(1):107-112.
[23] FONGER W H,STRUCK C W.Eu+35D resonance quenching to the charge-transfer states in Y2O2S,La2O2S,and LaOCl [J].J.Chem.Phys.,1970,52(12):6364-6372.
[2] LI S X,XIE R J,TAKEDA T,et al..Critical review—narrow-band nitride phosphors for wide color-gamut white LED backlighting [J].ECS J.Solid State Sci.,2018,7(1):R3064-R3078.
[3] XIE Z,ZHOU W W,ZHAO W,et al..Synthesis,electronic structure and luminescent properties of a new red-emitting phosphor GdBiW2O9∶Eu3+ [J].Chem.Phys.Lett.,2017,685:177-184.
[4] XIA Z G,XU Z H,CHEN M Y,et al..Recent developments in the new inorganic solid-state LED phosphors [J].Dalton Trans.,2016,45(28):11214-11232.
[5] 刘文全,史瑞新,段如霞,等.CaxSi合金前驱物常压氮化制备Ca1-xAlSiN3∶xEu2+红色荧光粉及发光性能研究 [J].发光学报,2017,38(10):1295-1301.LIU W Q,SHI R X,DUAN R X,et al..Preparation and luminescence properties of Ca1-xAlSiN3∶xEu2+ red phosphors by atmospheric nitriding method with CaxSi alloy precursors [J].Chin.J.Lumin.,2017,38(10):1295-1301.(in Chinese)
[6] 陈沙然,邵起越,董岩,等.K2SiF6∶Mn4+荧光粉湿热环境下的劣化行为 [J].发光学报,2018,39(6):757-763.CHEN S R,SHAO Q Y,DONG Y,et al..Degradation behavior of K2SiF6∶Mn4+ phosphors under heat-moisture conditions [J].Chin.J.Lumin.,2018,39(6):757-763.(in Chinese)
[7] TANNER P A.Some misconceptions concerning the electronic spectra of tri-positive europium and cerium [J].Chem.Soc.Rev.,2013,42(12):5090-5101.
[8] YU R J,WANG C F,CHEN J T,et al..Photoluminescence characteristics of Eu3+-doped double-perovskite phosphors [J].ECS J.Solid State Sci.,2014,3(3):R33-R37.
[9] 郑庆华,周薇薇,吕兆承,等.NaLaMgTeO6∶Eu3+新型红色荧光粉的制备与发光性能 [J].硅酸盐学报,2017,45(4):542-547.ZHENG Q H,ZHOU W W,LV Z C,et al..Preparation and luminescent properties of novel red-emitting phosphor NaLaMgTeO6∶Eu3+ [J].J.Chin.Ceram.Soc.,2017,45(4):542-547.(in Chinese)
[10] LIANG J Y,ZHAO S C,YUAN X X,et al..A novel double perovskite tellurate Eu3+-doped Sr2MgTeO6 red-emitting phosphor with high thermal stability [J].Opt.Laser Technol.,2018,101:451-456.
[11] AMRITHAKRISHNAN B,SUBODH G.Crystal structure and optical properties of B site-ordered ALaLiTeO6(A=Ba,Sr) ceramics [J].Mater.Res.Bull.,2017,93:177-182.
[12] 赖凤琴,李嘉鹏,吴有福生,等.烧结温度和掺杂浓度对Y4Zr3O12∶Eu3+荧光粉发光性质的影响 [J].发光学报,2017,38(11):1436-1442.LAI F Q,LI J P,WU Y F S,et al..Effects of calcination temperature and dopant concentration on the luminescence properties of Eu3+ doped Y4Zr3O12 phosphors [J].Chin.J.Lumin.,2017,38(11):1436-1442.(in Chinese)
[13] LóPEZ M L,JEREZ A,PICO C,et al..Synthesis,crystal structure,and magnetic susceptibility of MLnLiTeO6 (M=Ca,Sr,Ba) [J].J.Solid State Chem.,1993,105(1):19-26.
[14] LIU Q,LI X B,ZHANG B,et al..Structure evolution and delayed quenching of the double perovskite NaLaMgWO6∶Eu3+ phosphor for white LEDs [J].Ceram.Int.,2016,42(14):15294-15300.
[15] TAUC J,GRIGOROVICI R,VANCU A.Optical properties and electronic structure of amorphous germanium [J].Phys.Status Solid B,1966,15(2):627-637.
[16] PHATAK R,GUPTA S K,KRISHNAN K,et al..Crystallographic site swapping of La3+ ion in BaA′LaTeO6 (A′=Na,K,Rb) double perovskite type compounds:diffraction and photoluminescence evidence for the site swapping [J].Dalton Trans.,2013,43(8):3306-3312.
[17] KOLESNIKOV I E,POVOLOTSKIY A V,MAMONOVA D V,et al..Asymmetry ratio as a parameter of Eu3+ local environment in phosphors [J].J.Rare Earths,2018,36(5):474-481.
[18] NGUYEN H D,KIM S J,YEO I H,et al..Luminescent properties of Eu3+-doped Ba2Bi2/3TeO6 and BaBiNaTeO6 double perovskite as new orange-red emitting phosphors [J].J.Electrochem.Soc.,2012,159(3):J54-J60.
[19] DENG H J,GAO Z W,XUE N,et al..A novel Eu3+-doped garnet-type tellurate red-emitting phosphor with high thermal stability and color purity [J].J.Lumin.,2017,192:684-689.
[20] SHI Y S,QUAN B,NING Q J,et al..Photoluminescent properties and Judd-Ofelt analysis of novel Na0.5Sr0.25NbO3∶Eu3+ red phosphor with high quantum efficiency [J].Mater.Res.Bull.,2018,101:363-370.
[21] FERHI M,BOUZIDI C,HORCHANI-NAIFER K,et al..Judd-Ofelt analysis of spectroscopic properties of Eu3+ doped KLa(PO3)4 [J].J.Lumin.,2015,157:21-27.
[22] J?RGENSEN C K,REISFELD R.Judd-Ofelt parameters and chemical bonding [J].J.Less Common.Metals,1983,93(1):107-112.
[23] FONGER W H,STRUCK C W.Eu+35D resonance quenching to the charge-transfer states in Y2O2S,La2O2S,and LaOCl [J].J.Chem.Phys.,1970,52(12):6364-6372.