纳米Gd_2O_3:Tb~(3+)的多元醇法制备及发光特性
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摘要
以DEG为溶剂,分别配置一定比例的GdCl_3, TbCl_3作为前驱液,利用多元醇法合成可用于生物探针的Gd_2O_3:Tb~(3+)纳米晶;将一定量的APTES和TEOS加入制备好的溶液中,使得纳米晶Gd_2O_3:Tb~(3+)的表面包裹聚硅氧烷层。本实验通过马尔文粒度仪、 X射线衍射仪(XRD)、场发射扫描电镜(SEM)、透射电镜(TEM)、荧光分光光度计等检测方法研究不同煅烧温度和不同Tb~(3+)掺杂浓度对纳米晶Gd_2O_3的粒径、物相结构、和发光性能的影响。将真空干燥过的纳米晶Gd_2O_3:Tb~(3+)置于马弗炉中分别以600, 800, 1000℃进行煅烧,得到的样品经XRD表征后发现:当煅烧温度为800℃时,得到立方相结构的纳米Gd_2O_3:Tb~(3+)。通过研究不同Tb~(3+)离子掺杂浓度下纳米晶Gd_2O_3:Tb~(3+)的荧光强度表明:当Tb~(3+)离子浓度为5.0%时,纳米晶Gd_2O_3:Tb~(3+)的发射强度最强,尤其是在主发射峰545 nm附近Tb~(3+)的~5D_4→~7F_5能级跃迁峰,其峰值强度比掺杂浓度为2.5%时提高了39%; Tb~(3+)掺杂浓度升高至7.5%时,样品发生了浓度猝灭导致光谱强度下降。
Tb~(3+)-doped Gd_2O_3 nanoparticles used as biological probes were synthesized by polyol method using DEG as solvent and mixture of GdCl_3 and TbCl_3 as precursor; the polysioxane shell was encapsulated on the surface of the nanoparticle in a mixed solution of APTES and TEOS. The effects of different Tb~(3+) doping concentration and calcination temperature on the size, structure and luminescence properties of Gd_2O_3:Tb~(3+) were investigated by measurements of X-ray diffraction(XRD), scanning electron microscope(SEM), transmission electron microscope(TEM) and fluorescence spectrometer. The vacuum-dried nanocrystalline Gd_2O_3:Tb~(3+) was placed in a muffle furnace and calcined at 600, 800 and 1000 ℃ respectively, and the obtained samples were characterized by XRD. Then, the fluorescence intensity of Gd_2O_3:Tb~(3+) nanocrystals was studied at different doping concentrations of Tb~(3+) ions. The result showed that when the calcination temperature was 800 ℃, the cubic phase structure of nano-Gd_2O_3:Tb~(3+)could be obtained; the emission intensity of Gd_2O_3:Tb~(3+) nanocrystals was the strongest. When the concentration of Tb~(3+) ions was 5.0%, the emission intensity of Gd_2O_3:Tb~(3+) nanocrystals was the strongest, especially at the ~5D_4→~7F_5 transition level of Tb~(3+) near the main emission peak at 545 nm, which was increased by 39%, higher than that of the doping concentration of 2.5%; when the Tb~(3+) doping concentration increased to 7.5%, the concentration quenching of the sample led to a decrease of spectral intensity.
Tb~(3+)-doped Gd_2O_3 nanoparticles used as biological probes were synthesized by polyol method using DEG as solvent and mixture of GdCl_3 and TbCl_3 as precursor; the polysioxane shell was encapsulated on the surface of the nanoparticle in a mixed solution of APTES and TEOS. The effects of different Tb~(3+) doping concentration and calcination temperature on the size, structure and luminescence properties of Gd_2O_3:Tb~(3+) were investigated by measurements of X-ray diffraction(XRD), scanning electron microscope(SEM), transmission electron microscope(TEM) and fluorescence spectrometer. The vacuum-dried nanocrystalline Gd_2O_3:Tb~(3+) was placed in a muffle furnace and calcined at 600, 800 and 1000 ℃ respectively, and the obtained samples were characterized by XRD. Then, the fluorescence intensity of Gd_2O_3:Tb~(3+) nanocrystals was studied at different doping concentrations of Tb~(3+) ions. The result showed that when the calcination temperature was 800 ℃, the cubic phase structure of nano-Gd_2O_3:Tb~(3+)could be obtained; the emission intensity of Gd_2O_3:Tb~(3+) nanocrystals was the strongest. When the concentration of Tb~(3+) ions was 5.0%, the emission intensity of Gd_2O_3:Tb~(3+) nanocrystals was the strongest, especially at the ~5D_4→~7F_5 transition level of Tb~(3+) near the main emission peak at 545 nm, which was increased by 39%, higher than that of the doping concentration of 2.5%; when the Tb~(3+) doping concentration increased to 7.5%, the concentration quenching of the sample led to a decrease of spectral intensity.
引文
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[13] Wang Z Z, Chen X Q, Shen L J, Li B, Gao L L, Zhou Y B. Synthesis, structure and spectrum properties of Gd2O3:Er3+, Yb3+ nanometer powder coated with SiO2 [J]. Journal of the Chinese Society of Rare Earths, 2009, 27(3): 390.(王忠志, 陈向群, 沈雷军, 李波, 高乐乐, 周永勃. SiO2包覆Gd2O3:Er3+,Yb3+纳米粉的制备、 结构及发光性能 [J]. 中国稀土学报, 2009, 27(3): 390.)
[14] Ou M G, Yang C L, Zhu Q W, Qiao H N. Study on Luminescence properties of Co-doped nanoparticles Gd2O3:Tb3+, Eu3+ synthesized by polyol route [J]. Ceramics International, 2017, 43(8): 6472.
[15] Patel Sandeep K S, Dhak Prasanta, Kim Min Kwan, Lee Jae-Hyeok, Kim Miyoung, Kim Sang-Koog. Structural and magnetic properties of Co-doped Gd2O3 nanorods[J]. Journal of Magnetism & Magnetic Materials, 2016, 403(10): 155.
[16] Raunak Kumar Tamrakar, Kanchan Upadhyay, Ishwar Prasad Sahu, Durga Prasad Bisen. Tuning of photoluminescence emission properties of Eu3+ doped Gd2O3 by different excitations [J]. Optik-International Journal for Light and Electron Optics, 2017, 135: 281.
[17] Maneesha Mishra, Kuppusami P, Reddy V R, Ghosh C, Divakar R, Ramaseshan R, Akash Singh, Thirumurugesam R, Mohandas E. Influence of CeO2 layer thickness on the properties of CeO2/Gd2O3 multilayers prepared by pulsed laser deposition [J]. Vacuum, 2015, 113: 64.
[2] Hai G, Yang X D, Xiao Teng, Zhang W P, Lou L R, Mugnier Jacques. Structure and optical properties of sol-gel derived Gd2O3 waveguide films [J]. Applied Surface Science, 2004, 230(1-4): 215.
[3] Wu X F, Hu S G, Tan C B, Liu Y X. Enhanced red luminescence in Gd2O3:Eu3+,Sm3+ and its dependence on temperature [J]. Optics Communications, 2014, 328(10): 23.
[4] Xu Z H, Yang J, Hou Z Y, Li C X, Zhang C M, Huang S S, Lin J. Hydrothermal synthesis and luminescent properties of Y2O3:Tb3+ and Gd2O3:Tb3+ microrods [J]. Materials Research Bulletin, 2009, 44(9): 1850.
[5] Liu L F, Lu S C. Preparation and luminescent properties of nanocrystalline Gd2O3:Eu3+ [J]. Chinese Journal of Luminescence, 2009, 30(2): 228.(刘林峰, 吕树臣. 纳米晶Gd2O3:Eu3+的制备与发光性质 [J]. 发光学报, 2009, 30(2): 228.)
[6] Tamrakar Raunak Kumar, Bisen D P, Brahme Nameeta. Effect of Yb3+ concentration on photoluminescence properties of cubic Gd2O3 phosphor [J]. Infrared Physics & Technology, 2015, 68: 92.
[7] Liu X C, Feng X L, Zhou K X, Yang Y, Zuo T G, Du H L. Properties of nanometer TiO2 prepared by a sol-gel method [J]. Rare Metal Materials and Engineering, 2016, 45(2): 436.(刘向春, 冯雪丽, 周凯旋, 杨洋, 左探光, 杜慧玲. 纳米TiO2的溶胶凝胶法制备与性能 [J]. 稀有金属材料与工程, 2016, 45(2): 436.)
[8] Dong X T, Liu G X, Sun J, Li J L, Liu J H, Hong G Y. Preparation and properties of nanocrystall ine Yb2O3 [J]. Rare Metal Materials and Engineering, 2001, 30(1): 73.(董相廷, 刘桂霞, 孙晶, 李建利, 刘景和, 洪广言. Yb2O3纳米晶的制备及其若干性质的研究 [J]. 稀有金属材料与工程, 2001, 30(1): 73.)
[9] Liu G X, Liu S J, Dong X T, Wang J X, Hu Y F, Sun D. Hydrothermal synthesis of multi-layer core-shell structural Gd2O3:Eu3+ hollow microspheres [J]. Chinese Journal of Inorganic Chemistry, 2010, 26(1): 35.(刘桂霞, 刘姝君, 董相廷, 王进贤, 胡延芳, 孙德. 水热法制备多层核壳结构Gd2O3:Eu3+空心微球 [J]. 无机化学学报, 2010, 26(1): 35.)
[10] Cao J, Jia L W, Liu W, Yan J H, Lian H Z. Synthesis and fluorescence properties of Eu2+-doped BaYF5 nanoparticles via microemulsion [J].Chinese Journal of Lasers, 2011, 38(4): 161.(曹杰, 贾丽玮, 刘伟, 闫景辉, 连洪洲. 微乳液法制备BaYF5:Eu2+纳米粒子及光谱特性研究 [J]. 中国激光, 2011, 38(4): 161.)
[11] Peng Z W, Wang L L, Liu H Q, Huang W Q, Zou B S. Combustion synthesis and photoluminescence of nanocrystalline Gd2O3 :Eu3+ [J]. Acta Physica Sinica, 2007, 56(2): 1162.(彭智伟, 王玲玲, 刘晃清, 黄维清, 邹炳锁. Gd2O3:Eu3+纳米晶的燃烧合成及光致发光性质 [J]. 物理学报, 2007, 56(2): 1162.)
[12] Li Q H, Bi D D, Liu Z H, Liu Z Y, He F. Characteristics and application of polyol method preparing ultrafineparticles [J]. Materials Science and Engineering of Powder Metallurgy, 2008, 13(2): 79.(李启厚, 毕丹丹, 刘志宏, 刘智勇, 何峰. 多元醇法制备超微粉体材料的特点及应用 [J]. 粉末冶金材料科学与工程, 2008, 13(2): 79.)
[13] Wang Z Z, Chen X Q, Shen L J, Li B, Gao L L, Zhou Y B. Synthesis, structure and spectrum properties of Gd2O3:Er3+, Yb3+ nanometer powder coated with SiO2 [J]. Journal of the Chinese Society of Rare Earths, 2009, 27(3): 390.(王忠志, 陈向群, 沈雷军, 李波, 高乐乐, 周永勃. SiO2包覆Gd2O3:Er3+,Yb3+纳米粉的制备、 结构及发光性能 [J]. 中国稀土学报, 2009, 27(3): 390.)
[14] Ou M G, Yang C L, Zhu Q W, Qiao H N. Study on Luminescence properties of Co-doped nanoparticles Gd2O3:Tb3+, Eu3+ synthesized by polyol route [J]. Ceramics International, 2017, 43(8): 6472.
[15] Patel Sandeep K S, Dhak Prasanta, Kim Min Kwan, Lee Jae-Hyeok, Kim Miyoung, Kim Sang-Koog. Structural and magnetic properties of Co-doped Gd2O3 nanorods[J]. Journal of Magnetism & Magnetic Materials, 2016, 403(10): 155.
[16] Raunak Kumar Tamrakar, Kanchan Upadhyay, Ishwar Prasad Sahu, Durga Prasad Bisen. Tuning of photoluminescence emission properties of Eu3+ doped Gd2O3 by different excitations [J]. Optik-International Journal for Light and Electron Optics, 2017, 135: 281.
[17] Maneesha Mishra, Kuppusami P, Reddy V R, Ghosh C, Divakar R, Ramaseshan R, Akash Singh, Thirumurugesam R, Mohandas E. Influence of CeO2 layer thickness on the properties of CeO2/Gd2O3 multilayers prepared by pulsed laser deposition [J]. Vacuum, 2015, 113: 64.