Ba_3Y(PO_4)_3∶Dy~(3+),Eu~(3+)单基质白光荧光粉的制备与发光性能
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摘要
为了探究在Dy~(3+)掺杂Ba_3Y(PO_4)_3荧光粉中共掺Eu~(3+)离子对其发光性能的影响,我们采用传统高温固相法制备了一系列Dy~(3+)、Eu~(3+)单掺杂和共掺杂Ba_3Y(PO_4)_3荧光粉。通过X射线衍射(XRD)、荧光发射光谱和荧光衰减曲线对样品进行了表征。结果表明,所制备的荧光粉呈闪铋矿立方相。在近紫外光激发下,Ba_3Y(PO_4)_3∶Dy~(3+)发射光谱在487和578 nm处有两个窄带发射峰,呈冷白光发射;Ba_3Y(PO_4)_3∶Eu~(3+)发射光谱的窄带发射位于594和616 nm处,呈发橙红光。在Ba_3Y(PO_4)_3∶Dy~(3+),Eu~(3+)中,由于Eu~(3+)离子补偿Dy~(3+)冷白光发射所缺的红色组分,从而实现了色纯度高、色温适中的暖白光发射。进一步探索了Ba_3Y(PO_4)_3∶Dy~(3+),Eu~(3+)荧光粉发光机理。所制备的Ba_3Y(PO_4)_3∶Dy~(3+),Eu~(3+)单基质白光荧光粉在白光近紫外激发白光二极管(UVWLED)领域具有潜在应用价值。
A series of Dy~(3+)and/or Eu~(3+)doped Ba_3Y(PO_4)_3 phosphors was prepared via a traditional high temperature solid state reaction to investigate how the luminescent properties of Dy~(3+)doped Ba_3Y(PO_4)_3 phosphor can be tuned by co-doping Eu~(3+)ions into the host lattice. X-ray diffraction( XRD),photoluminescence and fluorescence lifetime were used to characterize the as-prepared samples. The results show that all the samples have Ba_3Y(PO_4)_3 eulytite cubic structure. Under the excitation of near-UV light,the Ba_3Y(PO_4)_3 ∶Dy~(3+)phosphor shows cool-white emission and the Ba_3Y(PO_4)_3 ∶Eu~(3+)phosphor presents an orange-red emission. For Ba_3Y(PO_4)_3 ∶Dy~(3+),Eu~(3+)phosphor,warm-white emission with high color rendering index and appropriate correlated color temperature has been obtained by combining red emission of Eu~(3+)with cool-white emission of Dy~(3+). The luminescence mechanism of Ba_3Y(PO_4)_3 ∶Dy~(3+),Eu~(3+)phosphor has been tentatively proposed and the prepared Ba_3Y(PO_4)_3 ∶Dy~(3+),Eu~(3+)phosphor has potential application in white-light-emitting-diodes( WLEDs) filed.
A series of Dy~(3+)and/or Eu~(3+)doped Ba_3Y(PO_4)_3 phosphors was prepared via a traditional high temperature solid state reaction to investigate how the luminescent properties of Dy~(3+)doped Ba_3Y(PO_4)_3 phosphor can be tuned by co-doping Eu~(3+)ions into the host lattice. X-ray diffraction( XRD),photoluminescence and fluorescence lifetime were used to characterize the as-prepared samples. The results show that all the samples have Ba_3Y(PO_4)_3 eulytite cubic structure. Under the excitation of near-UV light,the Ba_3Y(PO_4)_3 ∶Dy~(3+)phosphor shows cool-white emission and the Ba_3Y(PO_4)_3 ∶Eu~(3+)phosphor presents an orange-red emission. For Ba_3Y(PO_4)_3 ∶Dy~(3+),Eu~(3+)phosphor,warm-white emission with high color rendering index and appropriate correlated color temperature has been obtained by combining red emission of Eu~(3+)with cool-white emission of Dy~(3+). The luminescence mechanism of Ba_3Y(PO_4)_3 ∶Dy~(3+),Eu~(3+)phosphor has been tentatively proposed and the prepared Ba_3Y(PO_4)_3 ∶Dy~(3+),Eu~(3+)phosphor has potential application in white-light-emitting-diodes( WLEDs) filed.
引文
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[11]Liu X,Lin C,Lin J.White Light Emission from Eu3+in Ca In2O4Host Lattices[J].Appl Phys Lett,2007,90(8):081904.
[12]Yang Z,Xu D,Du J,et al.Tunable Luminescence and Energy Transfer of a Eu2+/Mn2+Co-doped Sr3Na Y(PO4)3F Phosphor for White LEDs[J].RSC Adv,2016,6(90):87493-87501.
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[14]YANG Zhiping,LYU Liang,LIU Pengfei,et al.Synthesis and Luminescent Properties of the Single White Emitting Phosphor Ca9Al(PO4)7∶Ce3+,Dy3+[J].Chinese J Lumin,2013,34(4):395-399(in Chinese).杨志平,吕梁,刘鹏飞,等.单一基质白色荧光粉Ca9Al(PO4)7∶Ce3+,Dy3+的制备与发光性能[J].发光学报,2013,34(4):395-399.
[15]HUANG Jun,YI Shuangping,XIAN Jieqiang,et al.Synthesis and Luminescence Properties of Eu3+/Dy3+Co-doped Singlephased Ba2Ca WO6Phosphors for White-light Applications[J].J Guangdong Univ Technol,2016,33(2):76-80(in Chinese).黄军,易双萍,冼洁强,等.Eu3+和Dy3+共掺单基质Ba2Ca WO6白色荧光粉的合成与发光性质[J].广东工业大学学报,2016,33(2):76-80.
[16]Niu X,Xu J,Zhang Y.The Spectroscopic Properties of Dy3+and Eu3+Co-doped Y3Al5O12(YAG)Phosphors for White LED[J].Prog Nat Sci:Mater Int,2015,25(3):209-214.
[17]Pavitra E,Raju G S R,Yu J S.White Light Emission from Eu3+Co-activated Ca2Gd8Si6O26∶Dy3+Nanophosphors by Solvothermal Synthesis[J].Ceram Int,2013,39(6):6319-6324.
[18]Guan H,Liu G,Wang J,et al.Tunable Luminescence and Energy Transfer Properties of Na Gd F4∶Dy3+,Eu3+Nanophosphors[J].New J Chem,2014,38(10):4901-4907.
[19]Yang F,Liu Y,Tian X,et al.Luminescence Properties of Phosphate Phosphor Ba3Y(PO4)3∶Sm3+[J].J Solid State Chem,2015,225:19-23.
[20]Xin S,Wang Y,Wang Z,et al.An Intense Red-Emitting Phosphor YBa3(PO4)3∶Eu3+for Near-ultraviolet Light Emitting Diodes Application[J].Electrochem Solid-State Lett,2011,14(11):H438-H441.
[21]ZHOU Liya,HUANG Lijun,YI Linghong,et al.Luminescent Properties of Ba3Gd(BO3)3∶Eu3+Phosphor for White LED Applications[J].J Chinese Rare Earth Soc,2009,(1):31-35(in Chinese).周立亚,黄君丽,易灵红,等.白光LED用荧光材料Ba3Gd(BO3)3∶Eu3+的发光性能研究[J].中国稀土学报,2009,(1):31-35.
[22]Wang Z,Hu Y,Zhang S,et al.Photoluminescence Properties of a Novel Red Phosphor Sr3Ga2O5Cl2∶Eu3+[J].Appl Phys A,2016,122(2):1-6.
[23]Wu Y,Zhao F,Piao X,et al.Zn-doped Ca Ti O3∶Eu3+Red Phosphors for Enhanced Photoluminescence in White LEDs by Solid-state Reaction[J].Luminescence,2016,31(1):152-157.
[24]Yu R,Noh H M,Moon B K,et al.Synthesis and Luminescence Properties of a Novel Red-emitting Phosphor Ba3La(PO4)3∶Eu3+for Solid-state Lighting[J].J Alloys Compd,2013,576:236-241.
[25]Liu Q,Liu Y,Ding Y,et al.A White Light Emitting Luminescent Material Ba3Y(PO4)3∶Dy3+[J].Ceram Int,2014,40(7):10125-10129.
[26]Xiong F B,Lin H F,Wang L J,et al.White Light Emission in Host-sensitized Dy3+-Single-Doped Na In(WO4)2Phosphors[J].Physica B,2015,459:41-45.
[27]Guo C,Jing H,Li T.Green-emitting Phosphor Na2Gd2B2O7∶Ce3+,Tb3+for Near-UV LEDs[J].RSC Adv,2012,2(5):2119-2122.
[28]Zeng X,Im S J,Jang S H,et al.Luminescent Properties of(Y,Gd)BO3∶Bi3+,RE3+(RE=Eu,Tb)Phosphor under VUV/UV Excitation[J].J Lumin,2006,121(1):1-6.
[29]Yang Z,Xu D,Sun J,et al.Luminescence Properties and Energy Transfer Investigations of Sr3Lu(PO4)3∶Ce3+,Tb3+Phosphors[J].Mater Sci Eng B,2016,211:13-19.
[30]Ye S,Xiao F,Pan Y X,et al.Phosphors in Phosphor-converted White Light-emitting Diodes:Recent Advances in Materials,Techniques and Properties[J].Mater Sci Eng:R,2010,71(1):1-34.
[31]Zhang X,Gong M.Single-phased White-light-emitting Na Ca BO3∶Ce3+,Tb3+,Mn2+Phosphors for LED Applications[J].Dalton Trans,2014,43(6):2465-2472.
[32]Maggay I V B,Lin P C,Liu W R.Investigation of Luminescence Properties and the Energy Transfer Mechanism of Li6Lu(BO3)3∶Ce3+,Tb3+Green-emitting Phosphors[J].RSC Adv,2015,5(8):5591-5597.
[33]Zhu J,Xia Z,Liu Q.Synthesis and Energy Transfer Studies of La Mg Al11O19∶Cr3+,Nd3+Phosphors[J].Mater Res Bull,2016,74:9-14.
[34]Wang Z,Lou S,Li P.Enhanced Orange Red Emission of Sr3La(PO4)3∶Ce3+,Mn2+via Energy Transfer[J].J Lumin,2014,156:87-90.
[2]Shang M,Li G,Kang X,et al.Tunable Luminescence and Energy Transfer Properties of Sr3Al O4F∶RE3+(RE=Tm/Tb,Eu,Ce)Phosphors[J].ACS Appl Mater Interfaces,2011,3(7):2738-2746.
[3]Bandi V R,Grandhe B K,Jang K,et al.Citric Based Sol gel Synthesis and Luminescence Characteristics of Ca La2Zn O5∶Eu3+Phosphors for Blue LED Excited White LEDs[J].J Alloys Compd,2012,512(1):264-269.
[4]Sun J,Sun Y,Du H.Luminescence Properties and Energy Transfer Investigations of Sr3Gd(PO4)3∶Ce3+,Tb3+Phosphors[J].J Phys Chem Solids,2013,74(7):1007-1011.
[5]Li T,Li P,Wang Z,et al.A Series of Tunable Emission Phosphors of Sm3+,Eu3+and Mn2+Doped Ba3Tb(PO4)3:Luminescence and Energy Transfer[J].RSC Adv,2015,5(88):71735-71742.
[6]XIE Ye,YIN Yan,ZHANG Ruixi,et al.Progress in the Single Matrix White Light Emitting Phosphor for White-light LED[J].New Chem Mater,2012,40(2):24-26(in Chinese).谢晔,印琰,张瑞西,等.白光LED用单一基质白光荧光粉的研究进展[J].化工新型材料,2012,40(2):24-26.
[7]Bandi V R,Grandhe B K,Woo H J,et al.Luminescence and Energy Transfer of Eu3+or/and Dy3+Co-doped in Sr3Al O4F Phosphors with NUV Excitation for WLEDs[J].J Alloys Compd,2012,538:85-90.
[8]WU Jiang,ZHANG Ping,JIANG Chundong,et al.Single Host White Phosphors Ca3Y2Si3O12∶Dy3+Excited by Near UV Light[J].Chinese J Lumin,2014,(9):1046-1050(in Chinese).吴疆,张萍,蒋春东,等.近紫外光激发单一基质白光荧光粉Ca3Y2Si3O12∶Dy3+的制备及发光特性[J].发光学报,2014,(9):1046-1050.
[9]REN Qiang,WANG Baoxing,WU Xiulan,et al.Influence of Eu3+Doping on Luminescent Properties of Ba3La(PO4)3∶Dy3+White Phosphor and Its Luminescent Mechanism[J].J Synth Cryst,2016,45(2):350-355(in Chinese).任强,王保兴,武秀兰,等.Eu3+对Ba3La(PO4)3∶Dy3+白光荧光粉发光性能的影响及发光机理的研究[J].人工晶体学报,2016,45(2):350-355.
[10]Jeon Y I,Bharat L K,Yu J S.Eu3+Ions Co-doped CLPO∶Dy3+Single Phase White-light Emitting Phosphors for Near UVbased White LEDs[J].J Alloys Compd,2015,649:531-536.
[11]Liu X,Lin C,Lin J.White Light Emission from Eu3+in Ca In2O4Host Lattices[J].Appl Phys Lett,2007,90(8):081904.
[12]Yang Z,Xu D,Du J,et al.Tunable Luminescence and Energy Transfer of a Eu2+/Mn2+Co-doped Sr3Na Y(PO4)3F Phosphor for White LEDs[J].RSC Adv,2016,6(90):87493-87501.
[13]Shang M,Li C,Lin J.How to Produce White Light in a Single-phase Host?[J].Chem Soc Rev,2014,43(5):1372-1386.
[14]YANG Zhiping,LYU Liang,LIU Pengfei,et al.Synthesis and Luminescent Properties of the Single White Emitting Phosphor Ca9Al(PO4)7∶Ce3+,Dy3+[J].Chinese J Lumin,2013,34(4):395-399(in Chinese).杨志平,吕梁,刘鹏飞,等.单一基质白色荧光粉Ca9Al(PO4)7∶Ce3+,Dy3+的制备与发光性能[J].发光学报,2013,34(4):395-399.
[15]HUANG Jun,YI Shuangping,XIAN Jieqiang,et al.Synthesis and Luminescence Properties of Eu3+/Dy3+Co-doped Singlephased Ba2Ca WO6Phosphors for White-light Applications[J].J Guangdong Univ Technol,2016,33(2):76-80(in Chinese).黄军,易双萍,冼洁强,等.Eu3+和Dy3+共掺单基质Ba2Ca WO6白色荧光粉的合成与发光性质[J].广东工业大学学报,2016,33(2):76-80.
[16]Niu X,Xu J,Zhang Y.The Spectroscopic Properties of Dy3+and Eu3+Co-doped Y3Al5O12(YAG)Phosphors for White LED[J].Prog Nat Sci:Mater Int,2015,25(3):209-214.
[17]Pavitra E,Raju G S R,Yu J S.White Light Emission from Eu3+Co-activated Ca2Gd8Si6O26∶Dy3+Nanophosphors by Solvothermal Synthesis[J].Ceram Int,2013,39(6):6319-6324.
[18]Guan H,Liu G,Wang J,et al.Tunable Luminescence and Energy Transfer Properties of Na Gd F4∶Dy3+,Eu3+Nanophosphors[J].New J Chem,2014,38(10):4901-4907.
[19]Yang F,Liu Y,Tian X,et al.Luminescence Properties of Phosphate Phosphor Ba3Y(PO4)3∶Sm3+[J].J Solid State Chem,2015,225:19-23.
[20]Xin S,Wang Y,Wang Z,et al.An Intense Red-Emitting Phosphor YBa3(PO4)3∶Eu3+for Near-ultraviolet Light Emitting Diodes Application[J].Electrochem Solid-State Lett,2011,14(11):H438-H441.
[21]ZHOU Liya,HUANG Lijun,YI Linghong,et al.Luminescent Properties of Ba3Gd(BO3)3∶Eu3+Phosphor for White LED Applications[J].J Chinese Rare Earth Soc,2009,(1):31-35(in Chinese).周立亚,黄君丽,易灵红,等.白光LED用荧光材料Ba3Gd(BO3)3∶Eu3+的发光性能研究[J].中国稀土学报,2009,(1):31-35.
[22]Wang Z,Hu Y,Zhang S,et al.Photoluminescence Properties of a Novel Red Phosphor Sr3Ga2O5Cl2∶Eu3+[J].Appl Phys A,2016,122(2):1-6.
[23]Wu Y,Zhao F,Piao X,et al.Zn-doped Ca Ti O3∶Eu3+Red Phosphors for Enhanced Photoluminescence in White LEDs by Solid-state Reaction[J].Luminescence,2016,31(1):152-157.
[24]Yu R,Noh H M,Moon B K,et al.Synthesis and Luminescence Properties of a Novel Red-emitting Phosphor Ba3La(PO4)3∶Eu3+for Solid-state Lighting[J].J Alloys Compd,2013,576:236-241.
[25]Liu Q,Liu Y,Ding Y,et al.A White Light Emitting Luminescent Material Ba3Y(PO4)3∶Dy3+[J].Ceram Int,2014,40(7):10125-10129.
[26]Xiong F B,Lin H F,Wang L J,et al.White Light Emission in Host-sensitized Dy3+-Single-Doped Na In(WO4)2Phosphors[J].Physica B,2015,459:41-45.
[27]Guo C,Jing H,Li T.Green-emitting Phosphor Na2Gd2B2O7∶Ce3+,Tb3+for Near-UV LEDs[J].RSC Adv,2012,2(5):2119-2122.
[28]Zeng X,Im S J,Jang S H,et al.Luminescent Properties of(Y,Gd)BO3∶Bi3+,RE3+(RE=Eu,Tb)Phosphor under VUV/UV Excitation[J].J Lumin,2006,121(1):1-6.
[29]Yang Z,Xu D,Sun J,et al.Luminescence Properties and Energy Transfer Investigations of Sr3Lu(PO4)3∶Ce3+,Tb3+Phosphors[J].Mater Sci Eng B,2016,211:13-19.
[30]Ye S,Xiao F,Pan Y X,et al.Phosphors in Phosphor-converted White Light-emitting Diodes:Recent Advances in Materials,Techniques and Properties[J].Mater Sci Eng:R,2010,71(1):1-34.
[31]Zhang X,Gong M.Single-phased White-light-emitting Na Ca BO3∶Ce3+,Tb3+,Mn2+Phosphors for LED Applications[J].Dalton Trans,2014,43(6):2465-2472.
[32]Maggay I V B,Lin P C,Liu W R.Investigation of Luminescence Properties and the Energy Transfer Mechanism of Li6Lu(BO3)3∶Ce3+,Tb3+Green-emitting Phosphors[J].RSC Adv,2015,5(8):5591-5597.
[33]Zhu J,Xia Z,Liu Q.Synthesis and Energy Transfer Studies of La Mg Al11O19∶Cr3+,Nd3+Phosphors[J].Mater Res Bull,2016,74:9-14.
[34]Wang Z,Lou S,Li P.Enhanced Orange Red Emission of Sr3La(PO4)3∶Ce3+,Mn2+via Energy Transfer[J].J Lumin,2014,156:87-90.