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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

陈杰, 王超, 尹玉, 等. SiO2@Gd2O3:Yb3+, Ln3+ (Ln=Er, Tm, Ho)核壳微球的制备及上转换发光性能[J]. 复合材料学报, 2023, 40(7): 4072-4081. doi: 10.13801/j.cnki.fhclxb.20220919.001
引用本文: 陈杰, 王超, 尹玉, 等. SiO2@Gd2O3:Yb3+, Ln3+ (Ln=Er, Tm, Ho)核壳微球的制备及上转换发光性能[J]. 复合材料学报, 2023, 40(7): 4072-4081. doi: 10.13801/j.cnki.fhclxb.20220919.001
CHEN Jie, WANG Chao, YIN Yu, et al. Preparation and upconversion luminescence properties of SiO2@Gd2O3:Yb3+, Ln3+ (Ln=Er, Tm, Ho) core-shell microspheres[J]. Acta Materiae Compositae Sinica, 2023, 40(7): 4072-4081. doi: 10.13801/j.cnki.fhclxb.20220919.001
Citation: CHEN Jie, WANG Chao, YIN Yu, et al. Preparation and upconversion luminescence properties of SiO2@Gd2O3:Yb3+, Ln3+ (Ln=Er, Tm, Ho) core-shell microspheres[J]. Acta Materiae Compositae Sinica, 2023, 40(7): 4072-4081. 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
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

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

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: 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+4F9/24I15/2跃迁、Tm3+1G43H6跃迁及Ho3+5S25I8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。

     

  • 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)

    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)

    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

    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

    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

    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

    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(IUC)与激发光功率(P)关系曲线拟合图

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

    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)

    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+)

    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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  • 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

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