γ辐照及热退火对光热折变玻璃光学性能的影响  

Effects ofγ-Irradiation and Thermal Annealing on Photo-thermal-refractive Glass

作　　者：朱治昱 焦艳 邵冲云 何冬兵[1] 胡丽丽[1] ZHU Zhiyu;JIAO Yan;SHAO Chongyun;HE Dongbing;HU Lili(Shanghai Institute of Optics and Fine Mechanics,Chinese Academy of Sciences,Shanghai 201800,China;Center of Materials Science and Optoelectronics Engineering,University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院上海光学精密机械研究所,上海201800 [2]中国科学院大学材料与光电研究中心,北京100049

出　　处：《无机材料学报》2021年第5期521-526,共6页Journal of Inorganic Materials

摘　　要：对光热折变(Photo-thermal-refractive,PTR)玻璃在总剂量分别为0.35、1、10及100 kGy的γ射线下辐照,并进行热退火处理,采用吸收光谱、光致发光光谱及EPR电子顺磁共振谱研究了光热折变玻璃在γ射线辐照下的辐照机理。研究结果表明,γ辐照后的PTR玻璃在可见波段的吸收主要由银原子Ag^(0)、银分子簇Ag^(2)、银分子簇Ag^(3)、银纳米颗粒Agm 0及非桥氧空穴中心HC1及HC2引起;在不同剂量γ射线辐照下,玻璃基质中的变价离子(Ag^(+)、Ce^(3+))价态先发生变化,同时玻璃基质中的非桥氧键发生电离,形成了非桥氧空穴型缺陷中心HC_(1)、HC_(2)。进一步增加辐照剂量,产生了银的分子簇Ag_(2)和Ag_(3);同时玻璃基质中非桥氧空穴中心HC_(2)的浓度增大,导致在639 nm附近的吸收增强。分别在不同温度下对辐照后的PTR玻璃进行相同时间的热处理及在低于Tg(玻璃转变温度)的温度下进行不同时间的热处理,观察到250℃退火后PTR玻璃中HC_(1)及HC_(2)缺陷中心发生漂白;并在430℃退火后出现了银纳米颗粒的吸收峰,该吸收峰随退火时间的延长发生了红移及展宽。Photo-thermal-refractive(PTR)glass was irradiated withγ-ray at the total dose of 0.35,1,10 and 100 kGy,respectively,and then annealed.Irradiation mechanism of the photo-thermal-refractive glass was studied by absorption spectroscope,luminescence spectroscope and electron paramagnetic resonance.The results showed that the absorption of theγ-irradiated PTR glass in the visible light was mainly caused by the Ag0,silver molecular clusters Ag_(2),Ag_(3),silver nanoparticles Agm 0,and non-bridge oxygen hole center HC1 and HC2.Under different doses ofγ-ray irradiation,valence state of the ions(Ag^(+),Ce^(3+))in the glass matrix changed.At the same time,non-bridged oxygen bonds in the glass matrix broke,generating non-bridged oxygen hole defects HC1,HC2 and Ag0.With the increase of the radiation dose,silver molecular clusters Ag_(2)and Ag_(3)generated,and the concentration of HC2 center in the glass matrix increased,resulting in enhanced absorption near 639 nm.After being irradiated and annealed at 250℃,HC_(1)and HC_(2)defect centers was bleached.Silver molecules appeared after annealing at 430℃,of which absorption peak had a redshift and was broadened with the increase of annealing duration.

关 键 词：光热折变玻璃 Γ射线辐照 辐照缺陷 紫外–可见吸收谱 

分 类 号：TQ174[化学工程—陶瓷工业]