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上转换单分散球的 NaYF:Yb/Er:通过加热温度调控的绿光和红光发射尾,以及通过 Mn 掺杂实现的发光显著增强。

Up-conversion monodispersed spheres of NaYF:Yb/Er: green and red emission tailoring mediated by heating temperature, and greatly enhanced luminescence by Mn doping.

机构信息

Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), Northeastern University, Shenyang, Liaoning 110819, China.

出版信息

Dalton Trans. 2018 Jul 3;47(26):8646-8655. doi: 10.1039/c8dt00792f.

Abstract

Submicron sized, monodispersed spheres of Mn2+, Yb3+/Er3+ and Mn2+/Yb3+/Er3+ doped α-NaYF4 were easily autoclaved from mixed solutions of the component nitrates and ammonium fluoride (NH4F), in the presence of EDTA-2Na. Detailed characterizations of the resultant phosphors were obtained using XRD, Raman spectroscopy, FE-SEM, HR-TEM, STEM, PLE/PL spectroscopy, and fluorescence decay analysis. Finer structure and better crystal perfection was observed at a higher calcination temperature, and the spherical shape and excellent dispersion of the original particles was retained at temperatures up to 600 °C. Under the 980 nm infrared excitation, the Yb3+/Er3+-doped sample (calcined at 400 °C) exhibits a stronger green emission centered at ∼524 nm (2H11/2 → 4I15/2 transition of Er3+) and a weaker red emission centered at ∼657 nm (4F9/2 → 4I15/2 transition of Er3+). A 200 °C increase in the temperature from 400 °C to 600 °C resulted in the dominant red emission originating from the 4F9/2 → 4I15/2 transition of Er3+, instead of the previously dominant green one. Mn2+ doping induced a remarkable more enhanced intensity at ∼657 nm and ∼667 nm (red emission area) than that at ∼524 nm and ∼546 nm (green emission area), because of the non-radiative energy transfer between Mn2+ and Er3+. However, a poor thermal stability was induced by Mn2+ doping. The observed upconversion luminescence of the samples calcined at 400 °C and 600 °C followed the two photon process and the four photon process, respectively.

摘要

采用 EDTA-2Na 作为螯合剂,从混合的各组分硝酸盐和氟化铵(NH4F)溶液中,很容易水热釜合成出亚微米级、单分散的 Mn2+、Yb3+/Er3+和 Mn2+/Yb3+/Er3+掺杂的α-NaYF4 纳米球。采用 XRD、拉曼光谱、FE-SEM、HR-TEM、STEM、PLE/PL 光谱和荧光衰减分析对所得荧光粉进行了详细的表征。在较高的煅烧温度下,观察到更精细的结构和更好的晶体完整性,而在高达 600°C 的温度下,原始颗粒的球形形状和优异的分散性得以保留。在 980nm 红外激发下,Yb3+/Er3+掺杂的样品(在 400°C 下煅烧)在 ∼524nm 处(Er3+的 2H11/2→4I15/2 跃迁)显示出更强的绿光发射,在 ∼657nm 处(Er3+的 4F9/2→4I15/2 跃迁)显示出较弱的红光发射。从 400°C 到 600°C,温度升高 200°C,导致主要的红光发射源于 Er3+的 4F9/2→4I15/2 跃迁,而不是之前主要的绿光发射。由于 Mn2+和 Er3+之间的非辐射能量转移,Mn2+掺杂导致在 ∼657nm 和 ∼667nm(红光发射区域)处的强度比在 ∼524nm 和 ∼546nm(绿光发射区域)处显著增强。然而,Mn2+掺杂导致较差的热稳定性。在 400°C 和 600°C 下煅烧的样品的上转换发光分别遵循双光子过程和四光子过程。

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