不同结构LaBO_3:Eu~(3+)发光粉合成及其发光性能
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摘要
采用溶胶–凝胶燃烧法,在不同柠檬酸用量和热处理温度条件下合成了系列LaBO_3:Eu~(3+)发光粉。结果表明:柠檬酸与稀土离子摩尔比为1:1,700℃热处理获得单斜结构的LaBO_3:Eu~(3+)发光粉。通过提高热处理温度和增加柠檬酸用量获得正交结构的LaBO_3:Eu~(3+)发光粉。LaBO_3:Eu~(3+)发光粉的形貌受合成条件的影响。单斜结构LaBO_3:Eu~(3+)发光粉Eu~(3+)离子的~5D_0→~7F_1和~5D_0→~7F_2发射峰强度相近;正交结构LaBO_3:Eu~(3+)发光粉的主发射峰来自于Eu~(3+)的5D0→7F2跃迁。正交结构发光粉的发光强度高于单斜结构的发光粉。~5D_0→~7F_2与~5D_0→~7F_1跃迁发射的相对强度比值说明:正交结构的LaBO_3:Eu~(3+)中Eu~(3+)局域环境的对称性较低。发光强度和Eu~(3+)局域环境的对称性与柠檬酸用量及热处理温度有关。LaBO_3:Eu~(3+)发光粉的Eu~(3+)最佳掺杂量为5%。
A series of LaBO_3:Eu~(3+) phosphors were prepared by a sol-gel combustion method with different amounts of citric acid and annealing temperatures. The results show that LaBO_3:Eu~(3+) phosphors with monoclinic system can be obtained by annealing precursor of molar ratio of citric acid to rare earth ions being 1:1 at 700 ℃. The orthorhombic LaBO_3:Eu~(3+) is obtained when the annealing temperature and the amount of citric acid are increased. The morphology of LaBO_3:Eu~(3+) can be changed under different synthesis conditions. The emission intensity attributed to ~5D_0→~7F_2 transitions of Eu~(3+) is similar to that attributed to ~5D_0→~7F_1 transitions for monoclinic LaBO_3:Eu~(3+), and the main emission peaks of orthorhombic LaBO_3:Eu~(3+) originate from ~5D_0→~7F_2 transitions of Eu~(3+). The luminescence intensity of orthorhombic LaBO_3:Eu~(3+) phosphors is more intense than that of monoclinic LaBO_3:Eu~(3+). The 5D0→7F2/5D0→7F1 relative emission intensity ratios show that the local symmetry environment around Eu~(3+) ions decreases in orthorhombic LaBO_3: Eu~(3+) compared to monoclinic LaBO_3:Eu~(3+). The luminescence intensity and local symmetry environment around Eu~(3+) ions are related to the amount of citric acid and annealing temperature. The optimal Eu~(3+) doping amount of LaBO_3:Eu~(3+)phosphors is 5%.
A series of LaBO_3:Eu~(3+) phosphors were prepared by a sol-gel combustion method with different amounts of citric acid and annealing temperatures. The results show that LaBO_3:Eu~(3+) phosphors with monoclinic system can be obtained by annealing precursor of molar ratio of citric acid to rare earth ions being 1:1 at 700 ℃. The orthorhombic LaBO_3:Eu~(3+) is obtained when the annealing temperature and the amount of citric acid are increased. The morphology of LaBO_3:Eu~(3+) can be changed under different synthesis conditions. The emission intensity attributed to ~5D_0→~7F_2 transitions of Eu~(3+) is similar to that attributed to ~5D_0→~7F_1 transitions for monoclinic LaBO_3:Eu~(3+), and the main emission peaks of orthorhombic LaBO_3:Eu~(3+) originate from ~5D_0→~7F_2 transitions of Eu~(3+). The luminescence intensity of orthorhombic LaBO_3:Eu~(3+) phosphors is more intense than that of monoclinic LaBO_3:Eu~(3+). The 5D0→7F2/5D0→7F1 relative emission intensity ratios show that the local symmetry environment around Eu~(3+) ions decreases in orthorhombic LaBO_3: Eu~(3+) compared to monoclinic LaBO_3:Eu~(3+). The luminescence intensity and local symmetry environment around Eu~(3+) ions are related to the amount of citric acid and annealing temperature. The optimal Eu~(3+) doping amount of LaBO_3:Eu~(3+)phosphors is 5%.
引文
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[2]LENG Zhihua,LIU Yali,ZHANG Nannan,et al.Controlled synthesis and luminescent properties of different morphologies Gd BO3:Eu3+phosphors self-assembled of nanoparticles[J].Colloids and Surf A:Physicochem.Eng.Aspects,2015,472:109–116.
[3]朱凡,由芳田,时秋峰,等.Gd BO3:Pr3+,Yb3+中Pr3+到Yb3+的能量传递及发光性质[J].发光学报,2015,36(7):751–756.ZHU Fan,YOU Fangtian,SHI Qiufeng,et al.Chin J Lumin(in Chinese),2015,36(7):751–756.
[4]CHEN Wanping,ZHOU Ahong.Microemulsion–solvothermal synthesis and tunable emission of YBO3:Eu for white-light-emitting diodes[J].Phys Chem C,2012,116:24748–24751.
[5]高荣,张志军,赵景泰.稀土正硼酸盐的晶体结构与温(压)致相变研究[J].中国稀土学报,2014,32(4):387–396.GAO Rong,ZHANG Zhijun,ZHAO Jingtai.J Rare-Earths(in Chinese),2014,32(4):387–396.
[6]SHMYT’KO I M,KIRYAKIN I N,STRUKOVA G K.Features of La BO3 phase formation during solid_phase synthesis from the amorphous precursor state[J].Phys Solid State,2013,55(7):1468–1475.
[7]QIN Chuanxiang,QIN Lin,CHEN Guoqiang,et al.Preparation and luminescence properties of Si O2@La BO3:Eu3+nanoparticles[J].J Nanopart Res,2013,15:1827(1–10).
[8]KOPARKAR K A,BAJAJ N S,OMANWAR S K.Effect of partially replacement of Gd3+ions on fluorescence properties of YBO3:Eu3+phosphor synthesized via precipitation method[J].Opt Mater,2015,39:74–80.
[9]LI Yanping,ZHANG Jiahua,ZHANG Xia,et al.Luminescent properties in relation to controllable phase and morphology of Lu BO3:Eu3+nano/microcrystals synthesized by hydrothermal approach[J].Chem Mater,2009,21:468–475.
[10]罗文雄,黄世华,由芳田,等.YBO3:Eu3+纳米晶发光特性[J].物理学报,2007,56(3):1765–1769.LUO Wenxiong,HUANG Shihua,YOU Fangtian,et al.Acta Phys Sin(in Chinese),2007,56(3):1765–1769.
[11]郭凤瑜,刘念红,宋增福.La BO3,Gd BO3中Eu3+和Bi3+的发光特性及其相互作用[J].中国稀土学报,1991,9(4):319–323.GUO Fengyu,LIU Nianhong,SONG Zengfu.J Rare-Earths(in Chinese),1991,9(4):319–323.
[12]尹新豪,李云辉,高莹,等.水热合成花球状Y3BO6:Eu3+及其光谱性能研究[J].无机化学学报,2014,30(9):2064–2074.YIN Xinhao,LI Yunhui,GAO Ying,et al.Chin J Inorg Chem(in Chinese),2014,30(9):2064–2074.
[13]ZENGYubin,LI Zhengquan,LIANG Yingfang.A general approach to spindle-assembled lanthanide borate nanocrystals and their photoluminescence upon Eu3+/Tb3+doping[J].Inorg Chem,2013,52:9590–9596.
[14]ZHANG Xinguo,ZHOU Liya,PANG Qi,et al.A broadband-excited and narrow-line Gd BO3:Ce3+,Tb3+,Eu3+red phosphor with efficient Ce3+→(Tb3+)n→Eu3+energy transfer for NUV LEDs[J].Opt Mater,2014,36:1112–1118.
[15]SHUBHAM Srivastava,APAMA Mondal,NIROJ Kumar Sahu,et al.Borohydride synthesis strategy to fabricate YBO3:Eu3+nanophosphor with improved photoluminescence characteristics[J].RSC Adv,2015,5:11009–11012.
[16]GRZYB Tomasz,KUBASIEWICZ Konrad,SZCZESZAK Agata,et al.Synthesis and spectroscopic properties of Yb3+and Tb3+co-doped Gd BO3 materials showing down-and up-conversion luminescence[J].Dalton Trans,2015,44,4063–4069.
[17]杨志平,田晶,李旭,等.凝胶燃烧法合成Ca2Si O4:Eu2+微晶及其发光性质的研究[J].人工晶体学报,2008,37(2):368–371.YANG Zhiping,TIAN Jing,LI Xu,et al.J Synth Cryst(in Chinese),2008,37(2):368–371.
[18]XIA Guodong,ZHOU Shengming,ZHANG Junji,et al.Structural and optical properties of YAG:Ce3+phosphors by sol–gel combustion method[J].J Cryst Growth,2005,279:375–362.
[19]张鹏,张晓凡,朱建锋.柠檬酸燃烧法制备Sr3Y2(BO3)4:Eu3+荧光粉及特性研究[J].人工晶体学报,2011,40(5):1141–1149.ZHANG Peng,ZHANG Xiaofan,ZHU Jianfeng.J Synth Cryst(in Chinese),2011,40(5):1141–1149.
[20]王利剑,郑水林,田文杰.载体对Ti O2/硅藻土中Ti O2相变及晶粒生长的影响[J].硅酸盐学报,2008,36(11):1644–1648.WANG Lijian,ZHENG Shuilin,TIAN Wenjie.J Chin Ceram Soc,2008,36(11):1644–1648.
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[22]李桂芳,曹全喜,黄云霞,等.凝胶–燃烧法合成(Y,Gd)Al3(BO3)4:Tb3+荧光材料的结构及其发光性能[J].稀有金属材料与工程,2009,38(9):1638–1641.LI Guifang,CAO Quanxi,HUANG Yunxia,et al.Rare Met Mater Eng(in Chinese),2009,38(9):1638–1641.
[23]李桂芳,曹全喜,黄云霞,等.溶胶–凝胶法合成YAl3(BO3)4:Eu3+荧光粉及其发光性能[J].硅酸盐学报,2008,36(8):1114–1118.LI Guifang,CAO Quanxi,HUANG Yunxia,et al.J Chin Ceram Soc,2008,36(8):1114–1118.
[24]赵森龙,张晓婷,王焕平,等.柠檬酸络合法制备氧化镧钇亚微米粉体的研究[J].陶瓷学报,2015,36(4):397–404.ZHAO Senlong,ZHANG Xiaoting,WANG Huanping,et al.J Ceram(in Chinese),2015,36(4):397–404.