SiO2@Gd2O3:Yb3+, Ln3+ (Ln=Er, Tm, Ho)核壳微球的制备及上转换发光性能

陈杰; 王超; 尹玉; 刘蓉; 曾晓丹; 刘治刚

doi:10.13801/j.cnki.fhclxb.20220919.001

SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺(Ln=Er, Tm, Ho)核壳微球的制备及上转换发光性能

doi: 10.13801/j.cnki.fhclxb.20220919.001

陈杰^1, ,,
王超²,
尹玉²,
刘蓉²,
曾晓丹¹,
刘治刚¹

1.
吉林化工学院　分析测试中心，吉林 132022
2.
吉林化工学院　化学与制药工程学院，吉林 132022

基金项目: 国家自然科学基金(51902125)；吉林省科技发展计划资助项目(YDZJ202101 ZYTS029)；吉林市科技发展计划资助项目(20210103092)

详细信息

通讯作者:
陈杰，博士，副教授，硕士生导师，研究方向为功能复合材料的制备与应用　E-mail: jiechendr@163.com

中图分类号: O734；TB333
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- 被引次数: 0
出版历程
- 收稿日期: 2022-07-25
- 修回日期: 2022-08-29
- 录用日期: 2022-09-10
- 网络出版日期: 2022-09-22
- 刊出日期: 2023-07-15

Preparation and upconversion luminescence properties of SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺(Ln=Er, Tm, Ho) core-shell microspheres

1.
Characterization and Analysis Center, Jilin Institute of Chemical Technology, Jilin 132022, China
2.
School of Chemistry and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin 132022, China

Funds: National Natural Science Foundation of China (51902125); Science and Technology Development Plan of Jilin Province (YDZJ202101 ZYTS029); Science and Technology Development Plan of Jilin City (20210103092)

摘要

摘要: 为了解决稀土掺杂上转换发光材料价格昂贵且粒径可控性差的问题，采用简单的化学沉淀法以价格低廉且易制备的SiO₂微球为核，在其表面均匀包覆了Gd₂O₃:Yb³⁺, Ln³⁺(Ln=Er, Tm, Ho)壳层，成功合成了球形SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺(Ln=Er, Tm, Ho)核壳上转换发光材料。XRD结果表明，尿素作为沉淀剂优先与稀土离子反应得到SiO₂@Gd(OH)CO₃:Yb³⁺, Ln³⁺前驱体，经800℃煅烧后壳层进一步转化成结晶性良好的立方相Gd₂O₃:Yb³⁺, Ln³⁺。SEM和尺寸分布图表明，所制备样品为理想的核壳微球形貌，尺寸均匀，平均粒径约为580 nm。在980 nm激光激发下，SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺(Ln=Er, Tm, Ho)核壳微球分别表现出红光、蓝光、绿光发射，对应于Er³⁺的⁴F_9/2→⁴I_15/2跃迁、Tm³⁺的¹G₄→³H₆跃迁及Ho³⁺的⁵S₂→⁵I₈跃迁，与色度图色坐标发光颜色区域相一致，说明通过简单的调节SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺核壳微球中壳层掺杂的稀土离子种类，成功实现了三色上转换发光。
- 上转换 /
- 三色发光 /
- SiO₂@Gd₂O₃:Yb³⁺ /
- Ln³⁺ /
- 核壳微球 /
- 稀土掺杂
Abstract: In order to solve the problem of high price and poor size controllability of rare earth doped upconversion luminescent materials, spherical SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) core-shell upconversion luminescent materials were successfully synthesized by simple chemical precipitation method using low cost and easy to prepare SiO₂ microspheres as cores and uniformly coated with Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) shells. XRD results show that the SiO₂@Gd(OH)CO₃:Yb³⁺, Ln³⁺ precursor is firstly obtained by the reaction of urea with rare earth ions, then the Gd(OH)CO₃:Yb³⁺, Ln³⁺ shell is further transformed into cubic phase Gd₂O₃:Yb³⁺, Ln³⁺ with good crystallinity after calcination at 800℃. SEM and size distribution images show that the prepared samples are ideal core-shell microspheres with uniform size, and the average diameter is about 580 nm. Under the excitation of 980 nm, SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) core-shell microspheres exhibit red, blue and green emissions respectively, corresponding to the ⁴F_9/2→⁴I_15/2 transition of Er³⁺, the ¹G₄→³H₆ transition of Tm³⁺, and the ⁵S₂→⁵I₈ transition of Ho³⁺, which are consistent with the luminescence color region of chromaticity color coordinates, indicating that three color upconversion luminescence is successfully achieved by simply adjusting the doped rare-earth ion species in the shell of SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ core-shell microspheres.
- upconversion /
- three color luminescence /
- SiO₂@Gd₂O₃:Yb³⁺ /
- Ln³⁺ /
- core-shell microspheres /
- rare earth doped

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图 1 (a) SiO₂、SiO₂@Gd(OH)CO₃:Yb³⁺, Ho³⁺和SiO₂@Gd₂O₃:Yb³⁺, Ho³⁺的XRD图谱；(b) SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho)的XRD图谱

Figure 1. (a) XRD patterns of SiO₂, SiO₂@Gd(OH)CO₃:Yb³⁺, Ho³⁺ and SiO₂@Gd₂O₃:Yb³⁺, Ho³⁺; (b) XRD patterns of SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho)

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图 2 SiO₂ (a)、SiO₂@Gd(OH)CO₃:10%Yb³⁺, 1%Ho³⁺ (b)、SiO₂@Gd₂O₃:10%Yb³⁺, 1%Ho³⁺ (c)、SiO₂@Gd₂O₃:10%Yb³⁺, 1%Tm³⁺ (d)、SiO₂@Gd₂O₃:10%Yb³⁺, 1%Er³⁺ (e) 的SEM图像；SiO₂@Gd₂O₃:10%Yb³⁺, 1%Ho³⁺的尺寸分布图 (f)

Figure 2. SEM images of SiO₂ (a), SiO₂@Gd(OH)CO₃:10%Yb³⁺, 1%Ho³⁺ (b), SiO₂@Gd₂O₃:10%Yb³⁺, 1%Ho³⁺ (c), SiO₂@Gd₂O₃:10%Yb³⁺, 1%Tm³⁺ (d), SiO₂@Gd₂O₃:10%Yb³⁺, 1%Er³⁺ (e); Size distribution of SiO₂@Gd₂O₃:10%Yb³⁺, 1%Ho³⁺ (f)

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图 3 (a) SiO₂@Gd₂O₃:10%Yb³⁺, 1%Ho³⁺核壳微球的EDS图谱; (b) Si、O、Gd、Yb和Ho元素分布图

Figure 3. (a) EDS spectra of SiO₂@Gd₂O₃:10%Yb³⁺, 1%Ho³⁺ core-shell microspheres; (b) Elemental mappings of Si, O, Gd, Yb, Ho

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图 4 SiO₂、Gd₂O₃:Yb³⁺, Ho³⁺和SiO₂@Gd₂O₃:Yb³⁺, Ho³⁺核壳微球的FTIR图谱

Figure 4. FTIR spectra of SiO₂, Gd₂O₃:Yb³⁺, Ho³⁺ and SiO₂@Gd₂O₃:Yb³⁺, Ho³⁺ core-shell microspheres

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图 5 SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺核壳微球的形成示意图

Figure 5. Schematic diagram of the formation process of SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ core-shell microspheres

TEOS—Tetraethyl orthosilicate

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图 6 SiO₂@Gd₂O₃:Yb³⁺, Er³⁺ (a)、SiO₂@Gd₂O₃:Yb³⁺, Tm³⁺ (b)、SiO₂@Gd₂O₃:Yb³⁺, Ho³⁺ (c) 核壳微球的发射光谱

Figure 6. Emission spectra of SiO₂@Gd₂O₃:Yb³⁺, Er³⁺ (a), SiO₂@Gd₂O₃:Yb³⁺, Tm³⁺ (b), SiO₂@Gd₂O₃:Yb³⁺, Ho³⁺ (c) core-shell microspheres

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图 7 SiO₂@Gd₂O₃:Yb³⁺, Er³⁺ (a)、SiO₂@Gd₂O₃:Yb³⁺, Tm³⁺ (b)、SiO₂@Gd₂O₃:Yb³⁺, Ho³⁺ (c) 的相对上转换发射强度(I_UC)与激发光功率(P)关系曲线拟合图

Figure 7. Fitting diagram of the relative upconversion emission intensity (I_UC) on excitation power (P) in SiO₂@Gd₂O₃:Yb³⁺, Er³⁺ (a), SiO₂@Gd₂O₃:Yb³⁺, Tm³⁺ (b), SiO₂@Gd₂O₃:Yb³⁺, Ho³⁺ (c) samples

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图 8 SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho)的能量传递机制图

Figure 8. Energy transfer scheme of SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho)

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图 9 SiO₂@Gd₂O₃:Yb³⁺, Er³⁺和Gd₂O₃:Yb³⁺, Er³⁺样品的发射光谱对比(内插图：Gd₂O₃:Yb³⁺, Er³⁺的SEM图像)

Figure 9. Emission spectra comparison of SiO₂@Gd₂O₃:Yb³⁺, Er³⁺ and Gd₂O₃:Yb³⁺, Er³⁺ samples (Inset: SEM image of Gd₂O₃:Yb³⁺, Er³⁺)

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图 10 980 nm激发下SiO₂@Gd₂O₃:10%Yb³⁺, 1%Er³⁺ (a)、SiO₂@Gd₂O₃:10%Yb³⁺, 1%Tm³⁺ (b)、SiO₂@Gd₂O₃:10%Yb³⁺, 1%Ho³⁺ (c)的色度图(内插图：发光照片及色坐标)

Figure 10. Chromaticity diagram of SiO₂@Gd₂O₃:10%Yb³⁺, 1%Er³⁺ (a), SiO₂@Gd₂O₃:10%Yb³⁺, 1%Tm³⁺ (b) , SiO₂@Gd₂O₃:10%Yb³⁺, 1%Ho³⁺ (c) under 980 nm excitation (Inset: Luminescent photographs and color coordinates)

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