Yu Shiyong, Zhi Yunxia, Su Haiquan
J Nanosci Nanotechnol. 2014 May;14(5):3380-6. doi: 10.1166/jnn.2014.7991.
A series of rare-earth ions (Er3+ and Yb3+) Co-doped CaF2 upconversion luminescent nanomaterials have been successfully prepared via a facile hydrothermal method using pluronic p123 (p123), pluronic F127 (F127) and sodium citrate as surfactants at 180 degrees C with different reaction time. The crystallographic phase, size and morphology can be controlled by simply tuning the reaction parameters such as the types of surfactants and the reaction time. It is found that reaction time and surfactant play a key role in forming the nanocrystals with different morphologies. X-ray diffraction, field-emission scanning electron microscopy FE-SEM, and photoluminescence spectra were used to characterize the structure, morphology and upconversion luminescence properties of CaF2:Er3+/Yb3+ upconversion nanomaterials, respectively. The experimental results indicate that three monodispersive and highly uniform CaF2:Er3+/Yb3+ nanocrystals with mean size of 200 nm, 3 um, and 700 nm have cubic and sphere shapes, respectively. While the possible mechanisms of upconversion luminescence are analyzed by the diagram of proposed energy transfer mechanisms, the schematic energy level diagrams showing typical upconversion processes for Er3+ also reveals that the as-synthesized CaF2:Er3+/Yb3 nanomaterials may be in the cubic structure with space group Fm-3m, in which Ln3+ cations occupy crystal lattice positions with lower point symmetry, leading to a high upconversion efficiency under the excitation of a 980 nm diode laser.
通过一种简便的水热法,以普朗尼克P123(P123)、普朗尼克F127(F127)和柠檬酸钠作为表面活性剂,在180℃下经过不同的反应时间,成功制备了一系列稀土离子(Er3+和Yb3+)共掺杂的CaF2上转换发光纳米材料。通过简单地调整反应参数,如表面活性剂的类型和反应时间,可以控制晶体相、尺寸和形态。发现反应时间和表面活性剂在形成具有不同形态的纳米晶体中起关键作用。分别使用X射线衍射、场发射扫描电子显微镜FE-SEM和光致发光光谱来表征CaF2:Er3+/Yb3+上转换纳米材料的结构、形态和上转换发光特性。实验结果表明,三种平均尺寸分别为200nm、3μm和700nm的单分散且高度均匀的CaF2:Er3+/Yb3+纳米晶体分别具有立方和球形形状。在通过提出的能量转移机制图分析上转换发光的可能机制时,显示Er3+典型上转换过程的示意性能级图还表明,所合成的CaF2:Er3+/Yb3纳米材料可能具有空间群为Fm-3m的立方结构,其中Ln3+阳离子占据具有较低点对称性的晶格位置,从而在980nm二极管激光激发下具有高上转换效率。