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中国物理学会期刊

Ho3+离子掺杂单颗粒氟化物微米核壳结构的上转换发光特性

CSTR: 32037.14.aps.71.20211719

Upconversion luminescence characteristics of Ho3+ ion doped single-particle fluoride micron core-chell structure

CSTR: 32037.14.aps.71.20211719
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  • 构建核壳结构可有效降低材料的表面缺陷及实现掺杂离子的可控区域分布, 已成为目前增强及调控材料发光特性的有效手段之一. 为此, 本文以外延生长技术, 构建了一系列NaLnF4 (Ln = Y, Yb, Ho)@ NaLnF4 (Ln = Y, Yb)核壳微米结构, 并实现了Ho3+离子上转换发光的增强及可控调节. 借助共聚焦显微光谱测试系统, 在980 nm近红外激光激发下, 研究Ho3+离子在不同单颗粒核壳结构中的上转换发光特性. 结果表明, 当包覆NaYF4惰性壳时, NaYF4:Yb3+/Ho3+及NaYbF4:Ho3+ 微米棒的上转换发射强度均得到了明显增强, 而NaHoF4@NaYF4微米核壳结构的发射强度却没有发生明显的变化. 当在其NaYF4惰性壳中引入Yb3+离子时, NaYF4:Yb3+/Ho3+, NaYbF4:Ho3+及NaHoF4 微米核壳结构的发射强度及红绿比均再次得到了明显增强. 基于对其光谱特性及动力学过程的研究, 其发射增强主要由于壳层中的Yb3+离子通过能量迁移及传递过程有效地提高Ho3+离子激发, 进而在双向协同的作用下实现其发光有效增强及色彩调控. 由此可见, 对于微米晶体而言, 构建其不同的核壳结构不仅可实现其发光有效增强, 且可根据掺杂离子的不同及其区域分布实现光谱的精准调控, 为拓展高效发光特性的微米晶体在防伪、微纳光电器件等领域的应用提供新途径.

     

    Constructing core-shell structures can effectively reduce the surface quenching effect of luminescent materials, which becomes an effective method to enhance upconversion luminescence. In this work, a series of NaLnF4@NaLnF4 (Ln = Y3+, Yb3+, Ho3+) core-shell microcrystals is successfully synthesized based on epitaxial growth technology, thereby enhancing and regulating the upconversion emission of Ho3+ ions. The results of the XRD and SEM indicate that the NaLnF4@NaLnF4 core-shell microcrystal possesses a pure hexagonal-phase crystal structure with a rod-like shape. Meanwhile, it is found that the epitaxial growth direction of the micro-shell is not affected by the crystal characteristics in the core, but determined by the crystal characteristics of the shell. Under 980 nm near-infrared laser excitation, the upconversion luminescence properties of single microrods with different core-shell structures are investigated via a confocal microscope spectroscopy. It is found that in the NaLnF4 micro-crystal, the coated NaYF4 inert shell can also effectively reduce the quenching effect on the surface of the micro-crystal for enhancing upconversion emission. When the Yb3+ ions are introduced into NaYF4 or NaYbF4 active shell that is coated, the Yb3+ ions in the shell can effectively transfer excitation energy to Yb3+ in the core through energy migration, and then establish new energy transfer channels, thereby realizing the Ho3+ ion luminescence enhancement. For NaHoF4@NaYbF4 core-shell microrods, the Yb3+ in the shell can transfer more excitation energy to Ho3+ ions at the adjacent interface for enhancing the overall luminescence intensity, and its higher red-green ratio is mainly due to the cross-relaxation process occurring between the Ho3+ ions at high doping concentration of Ho3+ in the NaHoF4 core. Meanwhile, the luminescence process of the micron core-shell system is further confirmed based on the luminescence characteristics of different structures and the dynamic luminescence process. It can be seen that constructing different micron core-shell structures and introducing sensitizing ions, can not only effectively enhance the luminous intensity of the micron materials, but also adjust the output color. Therefore, this research is an important experimental reference for enhancing the luminous intensity of the micron system and the precise adjustment of luminescence, and can effectively expand the applications of micron crystals in the fields of displays, micron lasers and anti-counterfeiting.

     

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