Ce~(3+),Eu~(2+)共掺Ba_3Si_6O_(12)N_2荧光粉发光特性及能量传递研究（英文）
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摘要
通过高温固相法制备了一系列Ce~(3+)/Eu~(2+)共掺杂的Ba_3Si_6O_(12)N_2,利用X射线衍射(XRD)研究了其晶体结构。研究表明,Ba_3Si_6O_(12)N_2∶Ce~(3+),Eu~(2+)荧光粉在338 nm光激发下可以发射525 nm的绿光,且具有较大的半峰宽。研究还发现,单掺Ce~(3+)的发射光谱和单掺Eu~(2+)的发射光谱存在交叠,同时Ce~(3+)的5d1最低能级能量低于Eu~(2+)的4f65d1最低能级,这二者共同证实了可能存在Ce~(3+)到Eu~(2+)的能量转移现象。同时还研究了Ce~(3+)浓度对Ba(2. 7-y)Si6O12N2∶0.3Eu~(2+),y Ce~(3+)(0≤y≤0. 1)系列荧光粉发光强度和波长的影响。热猝灭性能研究表明,Ce~(3+)引入可显著影响体系的热猝灭性能。
A series of Ce~(3+)/Eu~(2+)doped Ba_3Si_6O_(12)N_2 were prepared via conventional solid-state reactions.The structure of Ce~(3+)/Eu~(2+)doped Ba_3Si_6O_(12)N_2 was investigated by X-ray diffraction( XRD).Photoluminescence( PL) properties of Ba+3 Si6 O12 N2:Ce3,Eu~(2+)phosphor show a broad green emission band with a peak at 525 nm and under 338 nm light irradiation. The energy transfer from Ce~(3+)to Eu~(2+)was confirmed by the spectral overlap of Ba_3Si_6O_(12)N_2:Eu~(2+)PLE excitation spectra and Ba_3Si_6O_(12)N_2:Ce~(3+)emission spectrum,as well as the gap between lowest energy level of 5 d1 excited state of Ce~(3+)and 4 f65 d1 excited state of Eu~(2+). The Ce~(3+)concentration dependent of Eu~(2+)emission intensity and redshift of wavelength in Ba2 +( 2. 7-y)Si6 O12 N2:0. 3 Eu,y Ce~(3+)( 0 ≤y≤0. 1) phosphor was studied in detail. It is revealed that the co-doping of Ce~(3+)in Ba_3Si_6O_(12)N_2:Eu~(2+)phosphor has a great influence on thermal quenching property.
A series of Ce~(3+)/Eu~(2+)doped Ba_3Si_6O_(12)N_2 were prepared via conventional solid-state reactions.The structure of Ce~(3+)/Eu~(2+)doped Ba_3Si_6O_(12)N_2 was investigated by X-ray diffraction( XRD).Photoluminescence( PL) properties of Ba+3 Si6 O12 N2:Ce3,Eu~(2+)phosphor show a broad green emission band with a peak at 525 nm and under 338 nm light irradiation. The energy transfer from Ce~(3+)to Eu~(2+)was confirmed by the spectral overlap of Ba_3Si_6O_(12)N_2:Eu~(2+)PLE excitation spectra and Ba_3Si_6O_(12)N_2:Ce~(3+)emission spectrum,as well as the gap between lowest energy level of 5 d1 excited state of Ce~(3+)and 4 f65 d1 excited state of Eu~(2+). The Ce~(3+)concentration dependent of Eu~(2+)emission intensity and redshift of wavelength in Ba2 +( 2. 7-y)Si6 O12 N2:0. 3 Eu,y Ce~(3+)( 0 ≤y≤0. 1) phosphor was studied in detail. It is revealed that the co-doping of Ce~(3+)in Ba_3Si_6O_(12)N_2:Eu~(2+)phosphor has a great influence on thermal quenching property.
引文
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[29] Dexter D L. A Theory of Sensitized Luminescence in Solids[J]. J. Chem. Phys.,1953,21:836-850.
[2] Hirosaki N,Xie R J,Kimoto K,et al. Characterization and Properties of Green-emitting beta-SiAlON∶Eu2+Powder Phosphors for White lightemitting diodes[J]. Appl. Phys. Lett.,2015,86(21):211905-211907.
[3] Li W Y,Xie R J,Zhou T L,et al. Synthesis of the Phase Pure Ba3Si6O12N2∶Eu2+Green Phosphor and its Application in High Color Rendition white LEDs[J]. Dalton T.,2014,43:6132-6138.
[4] Yan C P,Liu Z N,Zhuang W D,et al. YScSi4N6C∶Ce3+-A Broad Cyan-Emitting Phosphor to Weaken the Cyan Cavity in Full-Spectrum White Light-Emitting Diodes[J]. Inorg. Chem.,2017,56(18):11087-11095.
[5] Du F,Zhuang W D,et al. Effect of Y3+on the Local Structure and Luminescent Properties of La3-xYxSi6N11∶Ce3+Phosphors for High Power LED Lighting[J]. RSC Adv.,2016,6:77059-77065.
[6] Du F,Zhuang W D,Liu R H,et al. Synthesis,Structure and Luminescent Properties of Yellow Phosphor La3Si6N11∶Ce3+for High Power whiteLEDs[J]. J. Rare Earths,2017,19:1059-1064.
[7] Uheda K,Takizawa H,Endo T,et al. Synthesis and Luminescent Property of Eu3+Doped La Si3N5Phosphor[J]. J. Lumin,2000,967:87-89.
[8] van Krevel J W H,Rutten J W T,Mandal H,et al. Luminescence Properties of Terbium-,Cerium-,or Europium-doped[alpha]-Sialon Materials[J]. J. Solid State Chem.,2002,165:19-24.
[9] Li Y Q,de With G,Hintzen H T,et al. Luminescence Properties of Eu2+and Ce3+Activated BaYSi4N7[J]. J. Alloys. Compd.,2004,385(122):1-11.
[10] Li Y Q,Hirosaki N,Xie R J,et al. Yellow-orange-emitting CaAlSiN3∶Ce3+Phosphor:Structure,Photoluminescence,and Application in White LEDs[J]. Chem Mater,2008,20:6704-6714.
[11] Chen G,Yin L,Dong J,et al. Synthesis,Crystal Structure,and Luminescence Properties of Y4Si2O7N2∶Eu2+Oxynitride Phosphors[J]. J.Am. Ceram. Soc.,2016,99(1):183-190.
[12] Xu F,Sourty E,Shi W,et al. Direct Observation of Rare-Earth Ions inα-Sialon∶Ce Phosphors[J]. Inorg. Chem.,2011,50(7):2905-10.
[13] Suehiro T,Hirosaki N,Xie R J,et al. Powder Synthesis of Ca-α-SiAlON as a Host Material for Phosphors[J]. Chem. Mater,2014,17(2):308-314.
[14] Zeuner M,Pagano S,Schnick W. Nitridosilicates and Oxonitridosilicates:From Ceramic Materials to Structural and Functional Diversity[J].Angew. Chem. Int. Edit,2011,50(34):7754-7775.
[15] Li H L,Zhou G H,Xie R J,et al. Optical Properties of Green-blue-emitting Ca-α-Sialon∶Ce3+,Li+,Phosphors for White Light-emitting Diodes(LEDs)[J]. J. Solid State Chem.,2011,184(5):1036-1042.
[16] Gan L,Mao Z Y,Wang Y F,et al. Photoluminescence Properties of Ca-α-SiAlON∶Ce3+,Phosphors as Function of Composition and Microstructure[J]. Ceram Int.,2013,39(7):8319-8326.
[17] Xie R J,Hirosaki N,Mitomo M,et al. Photoluminescence of Cerium-dopedα-SiAlON Materials[J]. J. Am. Ceram Soc.,2004,87(7):1368-1370.
[18] Maruyama Y,Watanabe T. Low-temperature Synthesis of CaAlSiN3∶Ce3+Using the Ammonothermal Method[J]. J. Ceram. Soc. Jpn.,2016,124(1):66-69.
[19] Li Y Q,de With G.,Hintzen H T. Luminescence Properties of Ce3+-activited Alkalin Earth Silicon Nitride M2Si5N8∶Ce3+(M=Ca,Sr,Ba)Materials[J]. J. Lumin,2006,116(1-2):107-116.
[20] Kuramoto D,Kim H. S,Horikawa T,et al. Luminescence Properties of M2Si5N8∶Ce3+(M Ca,Sr,Ba)Mixed Nitrides Prepared by Metal Hydrides as Starting Materials[J]. Ceram Int,2012,379(1):012015.
[21] Mikami M,Kijima N. 5d Levels of Rare-earth Ions in Oxynitride/nitride Phosphors:to What Extent is the Idea Covalency Reliable?[J]. Opt.Mater,2010,33(2):145-148.
[22] Li W,Xie R J,Zhou T,et al. Synthesis of the Phase Pure Ba3Si6O12N2∶Eu2+Green Phosphor and its Application in High Color Rendition White LEDs[J]. Dalton T.,2014,43(16):6132-6138.
[23] Kang E H,Choi S W,Hong S H. Synthesis of Ba3Si6O12N2∶Eu2+Green Phosphors Using Ba3SiO5∶Eu2+Precursor and Their Luminescent Properties[J]. Ecs. J. Solid State Sc.,2012,1(1):R11-R14.
[24] Chihiro Y,Hideki K,Masato K. Synthesis of an Oxynitride-based Green Phosphor Ba3Si6O12N2∶Eu2+via an Aqueous-solution Process,Using Propylene-glycol-modified Silane[J]. J. Soc. Inf. Display,2012,13(3):107-111.
[25] Kang H S,Hong S K,Kang Y C,et al. The Enhancement of Photoluminescence Characteristics of Eu-doped Barium Strontium Silicate Phosphor Particles by Co-doping Materials[J]. J. Alloys Comp,2005,402:246-250.
[26] Wang Z F,Xua M,Zhang W P,et al. Synthesis and Luminescent Properties of Nano-scale LuAG∶RE3+(Ce,Eu)Phosphors Prepared by Coprecipitation Method[J]. J. Lumin,2007,122-123:437-439.
[27] Liu R S,Liu Y H,Bagkar N C. Enhanced Luminescence of SrSi2O2N2∶Eu2+Phosphors by Codoping with Ce3+,Mn2+,and Dy3+ions[J].Appl. Phys. Lett.,2007,91:061119-1-3.
[28] Madej A,Zych E. Controlled Synthesis of the Monoclinic and Orthorhombic Polymorphs of Sr2SiO4Activated with Ce3+or Eu2+[J]. J.Cheminformatics,2016,47(11):104441-104450.
[29] Dexter D L. A Theory of Sensitized Luminescence in Solids[J]. J. Chem. Phys.,1953,21:836-850.