光谱学与光谱分析, 2009, 29 (7): 1740, 网络出版: 2010-05-26  

双叔丁基苯并噁唑噻酚在多孔二氧化硅中发光的研究

Photoluminescence from Bis-t-Butylbenzoxazolylthiophene Doped Silica Films
作者单位
1 北京交通大学光电子技术研究所, 教育部发光与光信息技术重点实验室, 北京100044
2 北京大学化学与分子工程学院, 稀土材料化学与应用国家重点实验室, 北京100871
摘要
利用溶胶凝胶法制备了用有机荧光染料2,5-双(5-叔丁基-1,3-苯并噁唑-2-基)噻酚(2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene, BBOT)的高浓度掺杂的纳米多孔二氧化硅固态薄膜, 该薄膜呈现明亮的蓝色发光。 通过紫外-可见光谱、 瞬态-稳态荧光光谱、 光学显微镜技术的研究表明: (1)在掺杂浓度低于6×10-3 mol·L-1时, 薄膜中荧光染料BBOT的光强比值随浓度呈线性增加; (2)在掺杂浓度低于6×10-3 mol·L-1时, 显微镜观察可见薄膜发光均匀、 没有相分离产生; (3)固体薄膜中分子的荧光寿命比在1,4二氧六环稀溶液中的1.957 ns延长。 在掺杂浓度为6×10-3 mol·L-1的样品中随着凝胶化程度逐渐升高荧光寿命从固化温度为50 ℃样品的2.45 ns提高到固化温度为90 ℃样品的3.04 ns。 在掺杂浓度高达6×10-3 mol·L-1时, 该体系并不产生分子荧光的浓度猝灭。 通过对比固态掺杂体系中和相同浓度下1,4二氧六环溶液中BBOT的荧光寿命随浓度和二氧化硅体系凝胶化程度变化的规律, 发现多纳米孔二氧化硅基质可以有效地抑制BBOT荧光的浓度猝灭, 获得了具有稳定荧光的有机无机杂化材料。
Abstract
Thin nano-porous silica films doped with high concentrations of fluorescent material, 2,5-bis(5-tert-butyl-2-benzoxazolyl)-thiophene (BBOT) were prepared via a sol-gel process. Uniform and bright blue fluorescence was observed. Light emission properties of these organic molecule doped inorganic silica films, i.e., hybrid films, were measured using ultraviolet-visible (UV-Vis) absorption spectroscopy, steady and time-resolved fluorescence spectroscopy as well as optical microscopy. Features of these materials were revealed in this investigation: Firstly, photoluminescence intensity from BBOT doped silica films increased linearly as the concentrations of BBOT increased if the dopant concentration was relatively low and below 6×10-3 mol·L-1; Secondly, no molecular aggregation or phase separation was observed using optical microscopy when the BBOT concentration was below 6×10-3 mol·L-1 in BBOT doped silica films. Thirdly, the fluorescence lifetimes of BBOT in the doped silica films were longer than that in a dilute dioxane solution (1.957 ns), which was contradicted to our general understanding that the fluorescence lifetime may be reduced in a condensed matter due to molecular interactions or quenching. It was further found that the fluorescence lifetime also varied with the gelation conditions. Taking a BBOT concentration of 6×10-3 mol·L-1 for an example, the lifetime of BBOT in doped silica films was about 2.45 ns for a specimen polymerized at 50 ℃; while the lifetime was increased to 3.04 ns for a specimen polymerized at 90 ℃. This work demonstrates no concentration quenching when the BBOT dopant concentrations increased to as high as 6×10-3 mol·L-1 in the silica matrix. In comparison with the changes in time-resolved photoluminescence of BBOT in dioxane solution and that of the BBOT doped nano-porous silica in relation to their concentration dependence and the gelation conditions, it was found that concentration quenching can be effectively suppressed by the nano-porous silica matrix. A stable fluorescent organic-inorganic hybrid material is thus obtained.

王俊玲, 何志群*, 王永生, 穆林平, 叶柿, 荆西平. 双叔丁基苯并噁唑噻酚在多孔二氧化硅中发光的研究[J]. 光谱学与光谱分析, 2009, 29(7): 1740. WANG Jun-ling, HE Zhi-qun, WANG Yong-sheng, MU Lin-ping1, YE Shi, JING Xi-ping. Photoluminescence from Bis-t-Butylbenzoxazolylthiophene Doped Silica Films[J]. Spectroscopy and Spectral Analysis, 2009, 29(7): 1740.

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