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硅酸盐通报 ›› 2021, Vol. 40 ›› Issue (11): 3791-3798.

• 玻璃 • 上一篇    下一篇

Co2+掺杂ZnO-MgO-Al2O3-SiO2系微晶玻璃的制备及光学性能

张涛1, 侯铮铮1, 荆涛2, 栗晟1, 郭延兴1, 焦志伟1   

  1. 1.北方工业大学机械与材料工程学院,北京 100144;
    2.甘肃省固体废物与化学品中心,兰州 730020
  • 收稿日期:2021-05-17 修回日期:2021-06-01 出版日期:2021-11-15 发布日期:2021-12-08
  • 通讯作者: 焦志伟,博士,教授。E-mail:jzwzwj@163.com
  • 作者简介:张涛(1994—),男,硕士研究生。主要从事光学功能材料方面的研究。E-mail:dogzht@163.com

Preparation and Optical Properties of Co2+-Doped ZnO-MgO-Al2O3-SiO2 System Glass-Ceramics

ZHANG Tao1, HOU Zhengzheng1, JING Tao2, LI Sheng1, GUO Yanxing1, JIAO Zhiwei1   

  1. 1. College of Mechanical and Material Engineering, North China University of Technology, Beijing 100144, China;
    2. Gansu Solid Waste and Chemicals Center, Lanzhou 730020, China
  • Received:2021-05-17 Revised:2021-06-01 Online:2021-11-15 Published:2021-12-08

摘要: 本文采用熔融法和热处理制备了Co2+掺杂的ZnO-MgO-Al2O3-SiO2(ZMAS)系透明微晶玻璃,基于X射线衍射的结果确定了微晶玻璃的主要晶相为ZnAl2O4/MgAl2O4,并且随着晶化处理时间的增加,微晶玻璃的物相构成没有发生明显变化,尖晶石相的结晶度和平均晶粒尺寸呈现先增大后减小的趋势。吸收光谱和发射光谱的结果表明Co2+进入了尖晶石相ZnAl2O4/MgAl2O4中,并取代了四面体位置(Td)的Zn2+或Mg2+。随着晶化处理时间的增加,样品的吸收光谱强度和发射光谱强度均呈现先升高后降低的趋势,这与X射线衍射结果的变化趋势一致,说明可以通过控制微晶玻璃的结晶度来调控光学性能,这对制备性能优良的微晶玻璃材料具有一定的指导意义。对比了采用不同价态Co的氧化物原料制备的微晶玻璃,结果表明无论是掺杂CoO还是Co2O3,微晶玻璃尖晶石相中的Co元素均以Co2+形式存在。此外,将所制备的微晶玻璃材料在1 540 nm处的基态吸收截面(σgas)同Co掺杂的其他基体材料进行了对比,发现它有望作为可饱和吸收体应用于调Q激光器中。

关键词: 微晶玻璃, 尖晶石, Co2+掺杂, 可饱和吸收体, 晶化行为

Abstract: In this paper, transparent glass-ceramics of the Co2+-doped ZnO-MgO-Al2O3-SiO2 (ZMAS) system were prepared via melting method and heat-treatment. Based on the X-ray diffraction results, it determine that the main crystalline phase of glass-ceramics is ZnAl2O4/MgAl2O4, and the composition of the glass-ceramics don't change significantly with the increase of the crystallization treatment time. The crystallinity and the average grain size of spinel increase first and then decrease. It shows that the broad absorption band of 4T1(4F)→4A2(4F) transitions and the emission peak of 4T1(4P)→4A2(4F) transitions of tetracoordinated Co2+ do not appear in both the absorption spectra and emission spectra of glass-ceramics. This indicates that Co2+ enter the spinel phase ZnAl2O4/MgAl2O4 and replace Zn2+ or Mg2+ in the tetrahedral (Td) sites. With the increase of crystallization treatment time, the absorption spectral intensity and emission spectral intensity of the samples increase first and then decrease. This is consistent with the changing trend of X-ray diffraction results. It shows that the optical properties can be controlled by controlling the crystallinity of glass-ceramics, which has certain guiding significance for the preparation of glass-ceramics with good properties. Comparing the glass-ceramics prepared by using raw materials with different valence states of Co oxides the result shows that the element Co exists as divalent Co2+ in the spinel phase of the final glass-ceramics, whether it is doped with CoO or Co2O3. Moreover, the prepared glass-ceramics material was compared with other Co-doped matrix materials in terms of the ground state absorption cross section (σgas) at 1 540 nm, showing that it can be used as a saturable absorber in Q-switch lasers.

Key words: glass-ceramic, spinel, Co2+-doped, saturable absorber, crystallization behavior

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