NaGd(WO4)2:Yb3+/Tm3+反蛋白石光子晶体的制备与上转换发光调制研究

doi:10.15541/jim20160104

摘要/Abstract

摘要：

三维光子晶体具有长程有序的结构特点, 在可见和近红外光谱范围内有着广泛的应用。光子晶体的一个重要性质是其对嵌入其中的发光中心自发辐射具有调制作用。本研究利用自组装和模板辅助法制备高质量的三维NaGd(WO₄)₂:Yb³⁺/Tm³⁺反蛋白石光子晶体, 探究了光子带隙对Tm³⁺离子上转换荧光发射与发光动力学的调制作用。通过对比分析发现, 由于反蛋白石光子晶体独特的周期性大孔结构和光子带隙效应, 处于光子带隙内的Tm³⁺离子¹G₄-³H₆的发光强度被抑制约45%, 自发辐射速率(SDR)被抑制约30%, 同时上转换局域热效应得到有效的调制。本实验结果对探索新型高效稀土掺杂上转换发光材料和提高上转换发光效率有指导意义。

关键词: 稀土掺杂, 钨酸钆钠, 光子晶体, 自发辐射, 调制

Abstract:

Photonic crystal (PC) possesses long-scale periodicity and has been widely applied in modifying visible and near-infrared photonic band gap. One of the extraordinary properties of the PCs is the modulation on spontaneous emission of embedded luminescence centers. In this study, three-dimensional NaGd (WO₄)₂:Yb³⁺/Tm³⁺ inverse opal photonic crystals (IOPC) with highly oridered periodic structure were prepared by self-assembly method using PMMA as template. The modulation effect of PC on emission spectra and dynamics of Tm³⁺ ions were systemically studied. In NaGd (WO₄)₂:Yb³⁺/Tm³⁺ inverse opal photonic crystals, due to unique cavity structure and photonic band gap effect, the emission line of ¹G₄-³H₆transition decreases by ~45% and the spontaneous radiation rate is suppressed by ~30%. Meanwhile, the up-conversion local thermal effect is largely suppressed. This experimental analysis indicates that the IOPC structure is an effective device for improving efficiency of up-conversion luminescence.

Key words: rare earth doping, NaGd(WO₄)₂, photonic crystal, spontaneous emission, modification

中图分类号:

O614

王运锋, 宋金璠, 唐晓燕, 胡冬梅. NaGd(WO₄)₂:Yb³⁺/Tm³⁺反蛋白石光子晶体的制备与上转换发光调制研究[J]. 无机材料学报, 2016, 31(10): 1058-1062.

WANG Yun-Feng, SONG Jin-Fan, TANG Xiao-Yan, HU Dong-Mei. Preparation and Modified Upconversion Luminescence In NaGd(WO₄)₂:Yb³⁺/Tm³⁺ Inverse Opal Photonic Crystals[J]. Journal of Inorganic Materials, 2016, 31(10): 1058-1062.

图/表 4

图 1 NaGd(WO4)2: Yb3+/ Tm3+样品结构表征

Fig. 1 Structural characterization of the NaGd(WO4)2: Yb3+/Tm3+ samples (a) SEM image of the opal template sample; (b) SEM image of the inverse opal sample on NaGd(WO4)2:20%Yb3+/ 0.5%Tm3+; (c) TEM image of the inverse opal sample; (d) XRD patterns of the IOPC and reference sample

图2 不同孔径IOPC样品的透射光谱和IOPC1与IOPC5样品中Tm3+离子980 nm光激发下的上转换发射光谱

Fig. 2 Transmittance spectra of the NaGd(WO4)2:20%Yb3+/ 0.5%Tm3+IOPC and the typical upconversion luminescence of Tm3+ ions in IOPC1 and IOPC5 with the 980 nm excitation

图3 NaGd(WO4)2:Yb3+/ Tm3+IOPC的荧光衰减

Fig. 3 Characterization of luminescence decay of 1G4-3H6 transition in NaGd(WO4)2:Yb3+/ Tm3+ Luminescence decay curves of 1G4-3H6 transition in NaGd(WO4)2:Yb3+/Tm3+IOPC (a) and REF(b) sample; Dependence of decay time constants on PBG positions (c)

图4 功率依赖的上转换发射光谱

Fig. 4 Upconversion emission intensity versus excitation power (a) The upconversion emission spectra of the IOPC excited by the different powers (inset: dependence of the intergral intensity on the increased powers); (b) The upconversion emission spectra of the REF excited by the different powers (Inset: dependence of the integral intensity on the increased powers)

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NaGd(WO₄)₂:Yb³⁺/Tm³⁺反蛋白石光子晶体的制备与上转换发光调制研究

Preparation and Modified Upconversion Luminescence In NaGd(WO₄)₂:Yb³⁺/Tm³⁺ Inverse Opal Photonic Crystals

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