白光LED用Eu~(2+)激活的硅（锗）酸盐荧光粉的制备与表征
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摘要
本文采用高温固相法制备了用于白光LED的Sr3SiO5:Eu2+荧光粉,研究了Sr/Si比、助熔剂BaF2用量、灼烧温度、Eu2+离子掺杂量以及Ge含量(分别为0mol、0.1mol、0.25mol、0.5mol、0.75mol、0.9mol和1 mo1)和Ba含量(分别为0mol、0.1mol、0.15mol、0.2mol、0.25mol、0.3mol、0.35mol、0.4mol、0.45mol和0.5mo1)对样品晶体结构和发光性能的影响,采用XRD和PL测定了样品的物相和光谱。对于Sr3SiO5: Eu2+荧光粉而言,确定了最佳的Sr/Si比为3,BaF2含量为1wt%,烧结温度为1380℃Eu2+离子掺杂浓度为7mo1%,发射峰位于569nm; Sr3Si1-yGeyO5:Eu2+荧光粉的发射光谱峰值位于502nm、550nm、590nm和610nm; Sr3-xBaxSiO5:Eu2+荧光粉的发射光谱范围为566 nm-576nm。在灼烧温度为1360℃～1420℃,N2/H2(90/10)的气氛条件下灼烧6小时,分别制备了纯相的Sr3-xBaxSiO5:荧光粉以及Eu2+ Eu2+荧光粉。该硅酸盐荧光粉的激发光谱是一300 nm～520nm的宽带谱,且在460nm(蓝光)处激发强度均较高,可用于紫外、近紫外和蓝光芯片激发的白光LED器件中。
The Sr3SiO5:Eu2+ phosphor for White Light Emitting Diode (WLED) is synthesized by the solid-state reaction method. The crystal structure and luminescent properties are influenced by the factors such as Sr/Si ratio, the doping concentration of the flux BaF2 and Eu2+ ion,the temperature as well as the concentration of Ge (respectively 0 mol,0.1mol,0.25 mol,0.5 mol,0.75 mol,0.9 mol and 1 mol) and Ba (respectively 0 mol,0.1 mol,0.15 mol,0.2 mol%,0.25 mol,0.3 mol,0.35 mol,0.4 mol,0.45 mol and 0.5 mol). And the phase and spectrum are analyzed by XRD and PL. To the Sr3SiO5:Eu2+ phosphor, the optimal results show that the Sr/Si ratio is 3;the doping concentration of BaF2 and Eu2+ ion is lwt% and 7mol%;and the best temperature is 1380℃.The Sr3SiO5:Eu2+ phosphor exhibits a strong yellow emission centering at about 569nm.The emission peaks of the Sr3Si1-yGeyO5:Eu2+ phosphor are 502nm,550nm,590nm and 610nm.While the range of the Sr3-xBaxSiO5:Eu2+ phosphor emission spectrum is 566nm～576nm. Under the temperature of 1360℃～1420℃,the atmosphere of N2/H2(90/10) and 6 hours, pure phases of the Sr3SiO5:Eu2+ and Sr3GeO5:Eu2+ phosphor are synthesized. And the Sr3-xBaxSi05:Eu2+ phosphor is also prepared. The range of the excitation spectrum of this kind of silicate phosphor investigated in this paper is 300nm～520nm with high exciting intensity in 460n (blue light),and it can be widely applied in the WLEDs excited by the ultraviolet, near- ultraviolet and blue chips.
The Sr3SiO5:Eu2+ phosphor for White Light Emitting Diode (WLED) is synthesized by the solid-state reaction method. The crystal structure and luminescent properties are influenced by the factors such as Sr/Si ratio, the doping concentration of the flux BaF2 and Eu2+ ion,the temperature as well as the concentration of Ge (respectively 0 mol,0.1mol,0.25 mol,0.5 mol,0.75 mol,0.9 mol and 1 mol) and Ba (respectively 0 mol,0.1 mol,0.15 mol,0.2 mol%,0.25 mol,0.3 mol,0.35 mol,0.4 mol,0.45 mol and 0.5 mol). And the phase and spectrum are analyzed by XRD and PL. To the Sr3SiO5:Eu2+ phosphor, the optimal results show that the Sr/Si ratio is 3;the doping concentration of BaF2 and Eu2+ ion is lwt% and 7mol%;and the best temperature is 1380℃.The Sr3SiO5:Eu2+ phosphor exhibits a strong yellow emission centering at about 569nm.The emission peaks of the Sr3Si1-yGeyO5:Eu2+ phosphor are 502nm,550nm,590nm and 610nm.While the range of the Sr3-xBaxSiO5:Eu2+ phosphor emission spectrum is 566nm～576nm. Under the temperature of 1360℃～1420℃,the atmosphere of N2/H2(90/10) and 6 hours, pure phases of the Sr3SiO5:Eu2+ and Sr3GeO5:Eu2+ phosphor are synthesized. And the Sr3-xBaxSi05:Eu2+ phosphor is also prepared. The range of the excitation spectrum of this kind of silicate phosphor investigated in this paper is 300nm～520nm with high exciting intensity in 460n (blue light),and it can be widely applied in the WLEDs excited by the ultraviolet, near- ultraviolet and blue chips.
引文
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[35]M.Pardha Saradh. U.V.Varadaraju.Photoluminescent Studies on Eu2+-Activated Li:SrSiO4—a Potential Orange-Yellow Phosphor for Solid-State Lighting[J]. Chemistry Material,2006,18:5267-5272
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[37]Wang Ji-lei, Wang Da-jian, Li Lan,et al. Preparation of Single Host Silicate Phosphors for White LEDs and Its Photoluminescent Properties[J]. Chinese Journal of Luminescence.2006,27 (8):463-468
[38]孙晓园,张家嬅,张霞.新一代白光LED照明用一种适于近紫外光激发的单一白荧光粉[J].发光学报.2005,26(3)：404～406
[39]Jouna Kyu Park. Kyoung Jae Choi. Kyoung Nam Kim et al.Investigation of strontium silicate yellow phosphors for White light emitting diodes from a combination chemistry[J]. Applied Physics letters.2005.87:031108
[40]陈震旻.稀土硅酸盐荧光粉制备及其性能的研究：[硕士学位论文].北京：北京交通大学光电工程系,2010
[41]张希艳,张亮亮,张云鹏等.助熔剂对Eu2+掺杂的碱十金属硅酸盐荧光粉发光性能的影响[J].硅酸盐学报.2010,38(2)：206～210
[42]孙海鹰Re3+(Nd3+,Ce3+):YA G超细粉体合成及光谱性能研究：[博士学位论文].长春：长春理工大学材料科学与工程系,2009
[43]Weijia Ding.Jing Wang, Mei Zhang et al.A novel orange phosphor of Eu2+-activated calcium chlorosilicate for white light-emitting diodes[J]. Journal of Solid State Chemistry.2006.179(7):3582-3585
[44]徐武亮,刘行仁CaZn(SiO4)4Cl2中Eu3+的发射光谱和晶体学格位[J].中国稀十学报.1993,11(2)：116～119
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[47]Park J.K, Choi K.J., Yeon J et al. Embodiment of the warm white-light-emitting diodes by using a Ba2+ codoped Sr3SiO5:Eu2+ phosphor[J]. Applied Physics Letters,2006(88):035411-1～035411-3.
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[49]廖勇.白光LED用红色荧光粉的制备与性能研究：[硕士学位论文].重庆：重庆大学化学化工学院.2007年
[50]Joung Kyu Park,Chang Hae Kim, Seung Hvok Park. Application of strontium silicate yellow phosphor for White light-emitting diodes[J]. Applied Physics Letters,2004,8(10):1647-1649
[2]Narukawa Y,Niki I,lzuno K.et al.Phosphor-conversion white light emitting diode using InGaN near-ultraviolet chip[J]. Appl.Phys.2002.41(4):L371-L373.
[3]顾铁成.大功率GaN基白光LED荧光材料与器件：[硕士学位论文].天津：天津理工大学,凝聚态物理,2008
[4]徐时清,金尚忠,王宝玲.固体照明光源-白光LED的研究进展.中国计量学院学报[J].2006,17(3)：188～191
[5]周志敏,周继海,纪爱华.LED照明技术与应用电路[M].北京：电子工业出版社,2009：25～29
[6]方志烈.半导体照明技术[M].北京：电子工业出版社,2009：315～336
[7]XIONG Chuanbing,JIANG Fengyi. Different properties of GaN-based LED grown on Si(111) and transferred onto new substrate[J]. Science in China,2006,49 (3),313-321
[8]刘洁,孙家跃,石春山.与LED匹配的白光发射荧光体的研究进展[J].化学通报.2005(6)：417～424
[9]何南玲.YAG黄色荧光粉的合成与性能研究：[硕士学位论文].重庆：重庆大学.材料系.2006
[10]王达健,许亮,顾铁成等.白光LED用宽激发带的稀十硅酸盐基质荧光粉材料[J].稀有金属材料与工程.2008,37(9)：1656～1659
[11]T.Aitasalo.P.Deren.J.holsa et al.Persistent luminescence phenomena in matetials doped with rare-earth ions[J]. Journal of Solid State Chemistry.2003.171:114-122
[12]冯仕华.白光LED用碱十金属硅酸盐荧光粉制备及光谱性质：[硕上学位论文].河北：河北大学,无机化学系,2010
[13]周明斌.近紫外光激发的白光LED用硅酸盐荧光粉的研究：[硕士学位论文].南昌：南昌大学,材料物理与化学,2008
[14]刘宗淼.Eu2+掺杂的LED用卤硅酸盐荧光粉的制备和表：[硕士学位论文].广州：中山大学.无机化学,2008
[15]SUN Xiao-yuan.ZHANG Jia-hua.ZHANG Xia et al.Long Lasting Yellow Phosphorescence in Sr,SiO5:Eu2+ and Sr3SiO5:Eu2+,Dy3+ phosphors[J].Chinese Journal of Luminescence,2008.29(4):665-669
[16]罗昔贤,曹望和,孙菲等.硅酸盐基质白光LED用宽激发带发光材料研究进展[J].科学通报.2008,53 (9)：1010～1016
[17]张中太,张俊英.无机电致发光材料及应用[M].北京：化学工业出版社,2005：57～121
[18]孙家跃,杜海燕.固体发光材料[M].北京：化学工业出版社,2003：20～80
[19]余宪恩.实用发光材料[M].河北省：中国轻工业出版社,2008.143～225
[20]肖志国,罗昔贤.蓄光型发光材料及其制品[M].北京：化学工业出版社,2005：9～23
[21]孙晓园.几种Eu2-激活的硅酸盐荧光粉的制备、发光性质及用于白光LED的研究：[硕士学位论文].长春：中国 科学院长春光学精密机械与物理研究所：凝聚态物理,2008
[22]郭宇竹.稀十掺杂白光LED荧光粉的合成及其光谱性能研究：[硕士学位论文].上海：上海师范大学：应用化学,201()
[23]Wei-Hisiang.Meng-Huei Sheng.Ming-Shyong Tsai.Preparation of Eu-activated strontium orthosilicate(Sr1.95SiO4:Eu0.05) phosphor by a sol-gel method and its luminescent properties[J]. Journal of alloys and compounds.2009.467:491-495
[24]孙晓园,张家骅,张霞等Sr2SiO4:Eu2+荧光粉的发光性质及在白光二极管中的应用[J].光电子·激光.2008.19(5)：1482-1485
[25]李盼来,杨志平,王志军等Sr3SiO5:Eu2+材料光谱特性研究[J].光子学报.2008.37(10),2001～2004
[26]杨清德,康娅.LED及其工程应用[M].北京：人民邮电出版社,2007：8～30
[27]郝金刚,梁春军,刘淡宁.LED产业分析报告[J].现代显示.2006,61(3)：8～15
[28]徐修冬.白色发光二极管用荧光材料研究进展.[硕士学位论文].广州：中山大学：无机化学,2007
[29]Li Panlai, WANG Zhijun, YANGzhiping et al. Preparation and Luminescence Characteristics of Sr3SiO5:Eu3+ Phosphor for White LEDs[J]. Journal of the Chinese Ceramic Society.2009.37(3):462-464
[30]Rosario D.,Ohara S..Mancic L.et.al.Characterisation of YAG:Ce powders thermal treated at different temperatures[J]..Applied Surface Science.2004.(238):469-474.
[31]Li Qiang.Gao Lian.Yan Dongsheng.The crystal structure and spectra of nano-scale YAG:Ce3+[J]. Materials Chemistry and Physics.2000,(64):41-44.
[32]张秋红.黄色、橙色、红色系列长波发射荧光粉发光性质研究：[博士学位论文].广州：中山大学：应用化学,2010
[33]杨翼,金尚忠,沈常宇等.白光LED用金属硅酸盐荧光粉的光谱性质[J].发光学报.2008.29(5)：800～804
[34]S.Ramanathan et al. Processing and characterization of combustion synthesized YAG powders [J]. Ceramics International,2003.29(1):477-484.
[35]M.Pardha Saradh. U.V.Varadaraju.Photoluminescent Studies on Eu2+-Activated Li:SrSiO4—a Potential Orange-Yellow Phosphor for Solid-State Lighting[J]. Chemistry Material,2006,18:5267-5272
[36]王细凤,温嘉琪,夏威等.发光二极管用荧光粉Sr2-xBaxSiO4:Eu的制备、发光性能及应用[J].硅酸盐学报.2008,36(8)：1119～1123
[37]Wang Ji-lei, Wang Da-jian, Li Lan,et al. Preparation of Single Host Silicate Phosphors for White LEDs and Its Photoluminescent Properties[J]. Chinese Journal of Luminescence.2006,27 (8):463-468
[38]孙晓园,张家嬅,张霞.新一代白光LED照明用一种适于近紫外光激发的单一白荧光粉[J].发光学报.2005,26(3)：404～406
[39]Jouna Kyu Park. Kyoung Jae Choi. Kyoung Nam Kim et al.Investigation of strontium silicate yellow phosphors for White light emitting diodes from a combination chemistry[J]. Applied Physics letters.2005.87:031108
[40]陈震旻.稀土硅酸盐荧光粉制备及其性能的研究：[硕士学位论文].北京：北京交通大学光电工程系,2010
[41]张希艳,张亮亮,张云鹏等.助熔剂对Eu2+掺杂的碱十金属硅酸盐荧光粉发光性能的影响[J].硅酸盐学报.2010,38(2)：206～210
[42]孙海鹰Re3+(Nd3+,Ce3+):YA G超细粉体合成及光谱性能研究：[博士学位论文].长春：长春理工大学材料科学与工程系,2009
[43]Weijia Ding.Jing Wang, Mei Zhang et al.A novel orange phosphor of Eu2+-activated calcium chlorosilicate for white light-emitting diodes[J]. Journal of Solid State Chemistry.2006.179(7):3582-3585
[44]徐武亮,刘行仁CaZn(SiO4)4Cl2中Eu3+的发射光谱和晶体学格位[J].中国稀十学报.1993,11(2)：116～119
[45]石春山,叶泽人.Eu2+离子在固体中的发光[J].发光与显示.1982,25(4)：1～10
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