无机材料学报 ›› 2015, Vol. 30 ›› Issue (12): 1327-1333.DOI: 10.15541/jim20150200 CSTR: 32189.14.10.15541/jim20150200

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Al3+/Yb3+/P5+掺杂对石英玻璃紫外透过和紫外激发荧光的影响

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   

  1. (1. 上海大学 材料科学与工程学院, 上海200436; 2. 中国科学院 上海光学机械精密研究所, 上海201800; 3. 中国科学院大学, 北京100049)
  • 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:
    国家自然科学基金(60937003)

Influence of Al3+/Yb3+/P5+-doping on UV Transmission and Fluorescence Spectra under the UV Excitation of Silica Glasses

SHAO Chong-Yun1, 2, XU Wen-Bin2, 3, LIU Li-Wan1, 2, YANG Qiu-Hong1, HU Li-Li2, ZHOU Qin-Ling2, WANG Shi-Kai2   

  1. (1. School of Materials Science and Engineering, Shanghai University, Shanghai 200436, China; 2. Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, China; 3. Graduate School of Chinese Academy of Sciences, Beijing 100049, China)
  • 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:
    National Natural Science Foundation of China (60937003)

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。

关键词: Yb3+掺杂石英玻璃, 紫外吸收带, 电荷迁移, Yb2+

Abstract:

Silica glasses containing different contents of Al2O3, Yb2O3 and P2O5 were fabricated by Sol-Gel method combined with high temperature vacuum sintering. Changes in UV transmission, fluorescence spectra under the UV excitation, and X-ray photoelectron spectra (XPS) of Yb4d caused by P5+ and Al3+ ions co-doping in Yb3+-doped silica glasses were comparatively investigated. The related mechanisms were discussed. Results show that the strong absorption bands in the range of 190 nm to 300 nm in Al3+/Yb3+/P5+-doped silica glasses are largely due to the charge-transfer (CT) from O2- to Yb3+, the positions of CT-absorption bands as well as binding energy of Yb4d are shifted to the higher energy with increasing electro-negativity of the second coordination element (Al, Si, P) of Yb3+ ions. In addition, introduction of Al3+ into Yb3+-doped silica glass leads to the reduction of Yb3+ to Yb2+ ions under vacuum sintering condition. The characteristic absorption of Yb2+ ions is located at 330 nm. Nevertheless, further incorporation P5+ into Al3+/Yb3+-co-doped silica glass with mole ratio of P5+/Al3+>1 can effectively suppress the formation of Yb2+. The IR luminescence (976 nm) under UV excitation originates from a relaxed CT transition, and the visible luminescence (525 nm) is ascribed to 5d→4f transition of Yb2+. The results provide a guidance on technology optimization and composition design for fabricating high-performance Yb3+-doped fiber.

Key words: Yb3+-doped silica glasses, UV absorption bands, charge-transfer, Yb2+

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