Chen Huan, Zhang Peipei, Cui Haining, Qin Weiping, Zhao Dan
State Key Laboratory on Integrated Optoelectronics, College of Electronic Science & Engineering, Jilin University, Changchun, 130012, China.
College of Physics, Jilin University, Changchun, 130012, China.
Nanoscale Res Lett. 2017 Sep 25;12(1):548. doi: 10.1186/s11671-017-2306-3.
Hexagonal phase (β) sodium rare earth tetrafluorides (NaREF, RE = Y, Gd, Lu, et al.) are considered the ideal matrices for lanthanide (Ln) ions doped upconversion (UC) luminescence materials, because they can provide favorable crystal lattice structures for the doped luminescent Ln ions to make intensive emissions. However, the cubic phase (α) NaREF always preferentially forms at low reaction temperature in short time as it is dynamically stable. Therefore, it is hard to obtain small sized β-NaREF via the traditional solvothermal method. In this paper, small sized β-NaYF:Yb,Er nanoparticles were synthesized by a heterogeneous-core-induced method via the solvothermal reaction. The heterogeneous α-NaGdF/β-NaYF: Yb, Er core-shell structure was confirmed by the local elemental mapping. The formation mechanism of β-NaYF:Yb,Er shell on the surface of α-NaGdF core was explained in detail. We reasoned that a hetero interface with a lower lattice symmetric structure was produced by cation exchanges between the core and shell, which caused the preferential growth of anisotropic hexagonal phase shell. The existence of this hetero interface has also been proven by observation of Gd UC emission.
六方相(β)稀土四氟酸钠(NaREF,RE = Y、Gd、Lu等)被认为是镧系(Ln)离子掺杂上转换(UC)发光材料的理想基质,因为它们可以为掺杂的发光Ln离子提供有利的晶格结构,从而实现强烈发射。然而,立方相(α)NaREF由于动力学稳定,在低温短时间反应中总是优先形成。因此,通过传统的溶剂热法很难获得小尺寸的β-NaREF。本文通过溶剂热反应采用异质核诱导法合成了小尺寸的β-NaYF:Yb,Er纳米颗粒。通过局部元素映射证实了异质α-NaGdF/β-NaYF:Yb,Er核壳结构。详细解释了α-NaGdF核表面β-NaYF:Yb,Er壳的形成机制。我们推断,核与壳之间的阳离子交换产生了具有较低晶格对称结构的异质界面,这导致了各向异性六方相壳的优先生长。通过观察Gd的UC发射也证明了这种异质界面的存在。