无机材料学报 ›› 2015, Vol. 30 ›› Issue (12): 1327-1333.DOI: 10.15541/jim20150200 CSTR: 32189.14.10.15541/jim20150200
邵冲云1, 2, 许文彬2, 3, 刘力挽1, 2, 杨秋红1, 胡丽丽2, 周秦岭2, 王世凯2
收稿日期:2015-04-24
修回日期:2015-06-16
出版日期:2015-12-20
网络出版日期:2015-11-24
作者简介:邵冲云(1990–), 男, 硕士研究生. E-mail: shaochongyun@foxmail.com
基金资助:SHAO Chong-Yun1, 2, XU Wen-Bin2, 3, LIU Li-Wan1, 2, YANG Qiu-Hong1, HU Li-Li2, ZHOU Qin-Ling2, WANG Shi-Kai2
Received:2015-04-24
Revised:2015-06-16
Published:2015-12-20
Online:2015-11-24
About author:SHAO Chong-Yun. E-mail: shaochongyun@foxmail.com
Supported by:摘要:
采用溶胶-凝胶法结合高温真空烧结工艺制备了不同浓度的Al3+/Yb3+/P5+掺杂石英玻璃。研究了P5+和Al3+的引入对Yb3+掺杂石英玻璃紫外透过和紫外激发荧光光谱, 以及Yb4d电子结合能的影响, 并初步探索了其机理。研究结果表明, Al3+/Yb3+/P5+掺杂石英玻璃在190~300 nm波段的吸收主要来源于O2-→Yb3+的电荷迁移吸收, 其谱带位置和Yb4d电子结合能随Yb3+的第二配位元素(Al、Si、P)电负性增大向高能方向移动。真空烧结条件下, 引入Al3+会引发石英玻璃中Yb3+还原为Yb2+, 其典型的吸收峰位于330 nm处; 然而, 在Al3+/Yb3+共掺的基础上再引入P5+, 且P5+/Al3+摩尔比大于1时, 可以有效抑制Yb2+的形成。紫外光激发引起的近红外发光(976 nm)是电子从电荷迁移态弛豫到Yb3+激发态向基态跃迁的结果, 可见发光(525 nm)归因于Yb2+的5d→4f跃迁。本文研究结果对通过优化工艺和调整组分制备出高性能的Yb3+掺杂光纤具有一定的指导意义。
中图分类号:
邵冲云, 许文彬, 刘力挽, 杨秋红, 胡丽丽, 周秦岭, 王世凯. Al3+/Yb3+/P5+掺杂对石英玻璃紫外透过和紫外激发荧光的影响[J]. 无机材料学报, 2015, 30(12): 1327-1333.
SHAO Chong-Yun, XU Wen-Bin, LIU Li-Wan, YANG Qiu-Hong, HU Li-Li, ZHOU Qin-Ling, WANG Shi-Kai. Influence of Al3+/Yb3+/P5+-doping on UV Transmission and Fluorescence Spectra under the UV Excitation of Silica Glasses[J]. Journal of Inorganic Materials, 2015, 30(12): 1327-1333.
| Sample | Yb2O3 | Al2O3 | P2O5 | K2O | BaO | SiO2 | Al/Yb | Yb2O3(wt-ppm) | |
|---|---|---|---|---|---|---|---|---|---|
| 0#pure silica | — | — | — | — | — | 100 | — | — | |
| Al# | 1#Al-1 | — | 1.0 | — | — | — | 99.00 | — | — |
| 2#Al-4.5 | — | 4.5 | — | — | — | 95.50 | — | — | |
| 3#AY-0.5-0.05 | 0.05 | 0.5 | — | — | — | 99.45 | 10 | 3259 | |
| 4#AY-2.5-0.05 | 0.05 | 2.5 | — | — | — | 97.45 | 50 | 3214 | |
| Yb# | 5#Yb-0.05 | 0.05 | — | — | — | — | 99.95 | 0 | 3270 |
| 6#Yb-0.08 | 0.08 | — | — | — | — | 99.92 | 0 | 5324 | |
| 7#YA-0.05-1 | 0.05 | 1.0 | — | — | — | 98.95 | 20 | 3248 | |
| 8#YA-0.1-1 | 0.10 | 1.0 | — | — | — | 98.90 | 10 | 6478 | |
| 9#YA-0.15-1 | 0.15 | 1.0 | — | — | — | 98.85 | 20/3 | 9690 | |
| 10#MCVD | 0.02 | 0.2 | — | — | — | 99.78 | 10 | 1308 | |
| P# | 11#PAY-6-4-0 | — | 4.0 | 6 | — | — | 90.00 | — | — |
| 12#PAY-1-4-0.1 | 0.10 | 4.0 | 1 | — | — | 94.90 | 40 | 6264 | |
| 13#PAY-6-4-0.1 | 0.10 | 4.0 | 6 | — | — | 89.90 | 40 | 5881 | |
| 14#P-65 | 1 | 5.0 | 65 | 5 | 24 | — | 5 | 27594 | |
表1 Al3+/Yb3+/P5+掺杂石英玻璃和参照样品玻璃组分/mol%
Table1 Compositions of Yb3+/Al3+/P5+-doped silica glasses and reference samples/mol%
| Sample | Yb2O3 | Al2O3 | P2O5 | K2O | BaO | SiO2 | Al/Yb | Yb2O3(wt-ppm) | |
|---|---|---|---|---|---|---|---|---|---|
| 0#pure silica | — | — | — | — | — | 100 | — | — | |
| Al# | 1#Al-1 | — | 1.0 | — | — | — | 99.00 | — | — |
| 2#Al-4.5 | — | 4.5 | — | — | — | 95.50 | — | — | |
| 3#AY-0.5-0.05 | 0.05 | 0.5 | — | — | — | 99.45 | 10 | 3259 | |
| 4#AY-2.5-0.05 | 0.05 | 2.5 | — | — | — | 97.45 | 50 | 3214 | |
| Yb# | 5#Yb-0.05 | 0.05 | — | — | — | — | 99.95 | 0 | 3270 |
| 6#Yb-0.08 | 0.08 | — | — | — | — | 99.92 | 0 | 5324 | |
| 7#YA-0.05-1 | 0.05 | 1.0 | — | — | — | 98.95 | 20 | 3248 | |
| 8#YA-0.1-1 | 0.10 | 1.0 | — | — | — | 98.90 | 10 | 6478 | |
| 9#YA-0.15-1 | 0.15 | 1.0 | — | — | — | 98.85 | 20/3 | 9690 | |
| 10#MCVD | 0.02 | 0.2 | — | — | — | 99.78 | 10 | 1308 | |
| P# | 11#PAY-6-4-0 | — | 4.0 | 6 | — | — | 90.00 | — | — |
| 12#PAY-1-4-0.1 | 0.10 | 4.0 | 1 | — | — | 94.90 | 40 | 6264 | |
| 13#PAY-6-4-0.1 | 0.10 | 4.0 | 6 | — | — | 89.90 | 40 | 5881 | |
| 14#P-65 | 1 | 5.0 | 65 | 5 | 24 | — | 5 | 27594 | |
图1 Al3+/Yb3+/P5+掺杂对石英玻璃紫外吸收光谱的影响
Fig. 1 Influence of Al3+/Yb3+/P5+-doping on UV absorption spectra of silica glasses. (a) Al3+and Yb3+single doping; (b) Al3+/Yb3+-co-doping with Al3+ ion contents variation; (c) Al3+/Yb3+-co-doping with Yb3+ ion contents variation; (d) Al3+/Yb3+/P5+-co-doping with P5+ ion contents variation
图2 不同样品的(a)紫外吸收光谱和(b)紫外激发可见发光光谱
Fig. 2 (a) UV absorption spectra and (b) visible emission spectra under UV excitation of different samples. Al3+/Yb3+-co-doped silica glasses with Al3+ and Yb3+ion contents variation are represented by thick solid line(4#、5#、6#) and dashed line(9#、8#、7#), respectively. Al3+/Yb3+/P5+-co-doped silica glasses with P5+ ion contents variation are represented by thin solid line(12#、13#). The inset in (b) shows an enlargement of the emission intensities of sample
图3 不同样品的Yb4d电子的XPS谱
Fig. 3 XPS spectra of Yb4d in different samples. (a) Pure Yb2O3 powder, (b) 8#, (c) 6#, (d) 13#, and (e) 14# samples, Pure Yb2O3 powder and Yb3+ doped phosphate glass(14#) are used as reference samples
图4 不同样品的(a)紫外吸收和(b)紫外激发荧光光谱
Fig. 4 (a)UV absorption spectra and (b) fluorescence spectra under UV excitation of different samples. Sample 6# is Yb3+ single doping, sample 8# is Yb3+/Al3+-co-doping, sample 13# is Yb3+/Al3+/P5+-co-doping with excess P5+ contents. Coordination environment of Yb3+ of those three samples can appear Yb-O-Si, Yb-O-Al, and Yb-O-P, respectively. Sample 10# is a reference sample which is prepared in oxygen atmosphere by MCVD-system to ensure that the Yb ions are in their trivalent state
| Sample | Yb-O-M(M=) | EN* | Yb4d BE* /eV | CT band /eV |
|---|---|---|---|---|
| 8# | Al Si | 1.61 1.90 | 186.7 | 5.23 5.80 |
| 6# | Si | 1.90 | 187.1 | 5.80 |
| 13# | P | 2.19 | 187.6 | 6.50 |
表2 样品8#、6#和13#的结构和光谱对比
Table 2 Comparison of structure and spectra for samples of 8#, 6# and 13#
| Sample | Yb-O-M(M=) | EN* | Yb4d BE* /eV | CT band /eV |
|---|---|---|---|---|
| 8# | Al Si | 1.61 1.90 | 186.7 | 5.23 5.80 |
| 6# | Si | 1.90 | 187.1 | 5.80 |
| 13# | P | 2.19 | 187.6 | 6.50 |
图5 在(a)Yb3+/Al3+共掺、(b)Yb3+单掺和(c)Yb3+/P5+共掺石英玻璃中Yb3+离子CT跃迁位形坐标示意图
Fig. 5 Schematic configurational coordinate diagrams for the CT-transitions in (a) Yb3+/Al3+-co-doped, (b) Yb3+ singly doped and (c)Yb3+/P3+-co-doped silica glasses
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