新型溶胶凝胶法合成激光染料掺杂AlPO4<sub>凝胶，玻璃和薄膜
文献类型：学位论文
| 作者 | 李日红 |
| 学位类别 | 博士 |
| 答辩日期 | 2010 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 张龙 |
| 关键词 | AlPO4<sub> 溶胶-凝胶 香豆素102 罗丹明6G 光学性质 |
| 其他题名 | Sol-Gel Preparation of Laser Dyes Doped AlPO4 Gel, Mesoporous Glass and Film |
| 中文摘要 | 激光染料掺杂的功能材料广泛运用在生物医学、固体染料激光器、传感器、太阳能光电池等领域，尤其运用在固体染料激光器中作为增益介质。传统的激光染料的固体载体包括聚合物、有机硅、硅干凝胶、多孔硅或多孔玻璃、以及聚合物填充的多孔无机材料等。然而，直接掺杂染料制备出硅的干凝胶，掺杂浓度不高，染料容易聚集；利用聚合物或者聚合物填充的多孔材料，这种材料激光损伤阈值低，稳定性较差，不适合高功率的激光输出；通过分相－酸腐蚀法制备的多孔玻璃由于孔径较大分布不均匀等原因，存在比较严重的光学散射而影响了激光效率、功率和光束质量等激光性能。最近，很多学者都在尝试改善材料性能，尤其是扩大多孔材料孔径分布，使材料更加稳定，透明，或者研究新型的非硅材料（如磷酸铝材料）或者以利于掺杂固体染料。 近年来，我们在多个非硅体系的溶胶－凝胶合成方面取得突破性的进展，运用溶胶-凝胶方法制备出大块AlPO4凝胶和具有较高比表面积的AlPO4介孔玻璃。这些材料具备优良的可见透过性，优良的化学稳定性和热稳定性，符合染料载体的要求。更重要的是，与介孔硅玻璃的中性Si4+相比，AlPO4材料中Al3+(及P5+)与激光染料分子中的阴性（及阳性）基团有更强的键合倾向，更有利于激光染料与AlPO4载体键合，降低染料分子团聚，很可能较介孔硅玻璃更适宜作为一些激光染料的载体材料。因此，本博士课题以磷酸铝凝胶，介孔玻璃和薄膜作为激光染料的载体材料，通过系统深入的结构研究和染料掺杂，分析了激光染料掺杂对AlPO4结构和光谱性质，探索染料分子在AlPO4中的分子状态，并结合固态核磁共振技术，研究Rh6G染料和AlPO4之间的相互作用。 通过新型溶胶凝胶方法成功制备了Rhodamine 6G (Rh6G)染料掺杂AlPO4 块状凝胶。运用吸收光谱和荧光光谱研究了染料掺杂浓度对光谱性质的影响。吸收光谱显示染料主要的吸收位于531 nm处，并随着掺杂浓度的增加吸收显著增加。发射光谱显示Rh6G染料的荧光峰位于539 nm，随着掺杂浓度的增加逐渐红移至563 nm。运用激发光谱结合Extiton Theory理论对染料分子状态的分析表明，随着浓度的增加，染料分子逐渐聚集成H-二聚体。27Al和31P的固态核磁共振数据显示染料对凝胶的主体网络的连接性并没有明显的影响。通过对比各凝胶的发光性质和染料聚集状态，可以认为掺杂Rh6G 染料摩尔比Rh6G/Al(lact)3 为 1.0×10-4时最佳。 在介孔AlPO4 玻璃中，介孔结构对染料的分离作用有利于染料高浓度的掺杂。通过系统的实验研究了近红外染料Rh6G和蓝绿波段染料香豆素102两种染料单独掺杂和共同掺杂的发光性质以及Rh6G染料单独掺杂的结构性质。实验发现： 1）Rh6G染料浸渍掺杂在介孔AlPO4 玻璃中，其主要的发射峰位于535～553 nm。通过对浸渍时间和浸渍浓度的掺杂实验研究，发现随着浸渍染料的时间和浸渍染料浓度的增加，进入介孔中染料浓度增加。27Al MAS NMR ，27Al{31P} REDOR 以及27Al{1H}REDOR揭示了染料和AlPO4玻璃基质的相互作用，当Rh6G浸渍浓度为5×10-4 mol/l，浸渍16 h左右达到平衡； Rh6G染料跟AlPO4的相互作用对染料有固定作用，即使浸析2个月后仍然比较稳定。在较小孔径和较大比表面积的介孔AlPO4玻璃中染料的聚集程度轻；2）蓝绿波段的香豆素102掺杂在AlPO4玻璃中，其主要的发射波长位于450 nm附近，表现出优秀的宽调谐能力，其可调谐宽度达111 nm，掺杂染料浓度达到5×10-4 mol/l。当掺杂浓度5×10 -3 mol/l时，激发光谱显示366 nm处激发带分裂，表明染料部分聚集成J-二聚体；3）当Rh6G染料和香豆素102同时掺杂，掺杂浓度为5×10 -5 mol/l～5×10 -6 mol/l之间时表现为双波输出，在400 nm附近和550 nm产生良好的荧光发射。较高浓度时，香豆素102的荧光很容易被Rh6G聚集体吸收，只能检测到明显的550 nm附近Rh6G的发射峰。 由于表面张力的原因，很容易在薄膜载体中实现高浓度的染料掺杂。通过浸渍提拉法制备出Rh6G染料掺杂的均匀完整不开裂的AlPO4-SiO2薄膜。吸收和激发光谱表明，随着染料浓度的增加，染料在薄膜中轻微聚集成J-二聚体，即使浓度达到10-3 mol/l时，其聚集相对10-6 mol/l时并不严重。发射光谱显示染料主要的发射带在553 nm附近，并随着浓度的增加轻微红移至556 nm。因此，可以认为AlPO4-SiO2 薄膜的表面张力对染料的聚集效应有明显的抑制作用，适合作为Rh6G染料甚至其它染料的高浓度掺杂的载体。 |
| 英文摘要 | Laser dyes doped functional materials have been widely applied in biomedicine, sensors, dye-sensitive solar cells and solid state dye laser fields, especially applied as the gain media of solid state dye laser. The conventional solid hosts for laser dyes are mostly polymers, silicate, silica gel, porous glasses and porous inorganic materials filled with polymers and so on. However, laser dyes in silica gel present more serious dyes aggregates which results in the lower laser efficiency. In the case of polymers and porous inorganic materials filled with polymers, the dyes stability is weak and the laser destroy threshold is low to encounter high power laser. Regarding in the porous glass prepared by phase-separated method, the laser efficiency and quality of light are weak ascribe to serious scattering. In the past decades, extensive research has heightened the importance to develop new highly efficient hosts for dyes by expanding the pore size, making the materials more stable, transparent and extending the framework composition toward non-siliceous systems (e.g. aluminum phosphate) Recently, we reported a simple aqueous sol-gel route yielding the transparent colorless stoichiometric AlPO4 glass possessing mesoporous structure and a surface area above 500 m2/g. Moreover, AlPO4 mesoporous glass is suitable to be a latent dyes host due to its chemical resistance, abrasion resistance and transparence in visible region. In particular, Al3+ and P5+ in AlPO4 glass behave more activity to interact with dyes which can avoid dyes aggregates and benefit the doping other than tetrahedral neutral Si4+ in silicate materials. Following the successful synthesis of AlPO4, in this thesis, a systematic study of the structure and fluorescent properties of AlPO4 gel, mesoporous glass and film doped with laser dyes were conducted, in addition, the dyes state and interaction between Rhodamine 6G (Rh6G) dye and AlPO4 were investigated by solid-state NMR companied with optical spectra. Rh6G doped AlPO4 gel was synthesized via sol-gel way. The effects on optical properties of dye loaded concentration were investigated by absorption and emission spectra. The increase of the Rh6G concentration incorporated in the AlPO4 gel gave rise to more intense absorption placed at 531 nm and a progressive red shift of the emission band from 539 nm to 563 nm. Exciton theory was applied to analyze the dyes state combined with excitation spectra, which inplied H-dimers formation as the dyes loaded concentration increased. The 27Al and 31P NMR results revealed no significant effects of Rh6G molecule on the framework of AlPO4 gel. It is therefore concluded that the optimal loaded concentration of Rh6G (molar ratio of Rh6G/Al(lact)3) is 1.0×10-4 in AlPO4 gel. AlPO4 mesoporous glass loaded dyes in high concentration is probable as the porous structure favors the separation of dyes in nano-scale. The optical properties and structure of AlPO4 mesoporous glass doped with Rh6G, as well as coumarin 102 dyes singly and co-doped were investigated. The results indicate that: 1) Emission band of Rh6G in mesoporous AlPO4 glass placed at 535 nm~553nm. The dyes concentration induced in the glass increased with the increasing of dipping time and dyes concentration. The NMR data (27Al & 31P MAS NMR, 27Al{31P}REDOR and 27Al{1H} REDOR ) revealed a strong interaction between Rh6G and AlPO4, and presented a maximum for the sample dipped for 16 h in the Rh6G solution with its concentration 5×10-4 mol/l. This interaction signified the excellent stability of Rh6G even bleached for 2 month in ethanol solution. AlPO4 glass with smaller pore size and high surface area favored the separation of dyes and less serious dye aggregates. 2) The emission band of blue-green dye coumarin 102 in mesoporous AlPO4 glass placed around 450 nm with its tunability more than 111 nm, and the highest loaded concentration in this glass was up to 5×10-4 mol/l. The splitting of excitation band placed at 366 nm suggest coumarin 102 J-dimers as the loaded concentration was 5×10-3 mol/l. 3) Double wavelength fluorescence placed at 400 nm and 550 nm were observed when Rh6G and coumarin 102 co-doped in AlPO4 mesoporous glass with the loaded concentration ranging from 5×10-5 mol/l~5×10-6 mol/l. A further increase of concentration higher than 5×10-5 mol/l should give rise to the formation of Rh6G J-dimers which absorbed the fluorescence of coumarin 102, in this case, only one obvious fluorescence band of Rh6G around 550 nm was observed. High dye concentration loaded in films hosts have been demonstrated ascribed to the surfactant effect of films. The homogeneous and non-cracking AlPO4-SiO2 film doped with Rh6G was prepared by dip-coating method. The absorption and excitation spectrum indicated no obvious aggregates existed in this film even the loaded concentration was 5×10-3 mol/l. The emission spectrum suggest a main emission band placed around 553 nm and exhibited slight red-shift to 556 nm as the dye concentration increased. In view of the surfactant effect of AlPO4-SiO2 film which can restrain the aggregating of dyes, it is therefore concluded the AlPO4-SiO2 film is probable a suitable host for Rh6G even other dyes at high loaded concentration. |
| 语种 | 中文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15643]  |
| 专题 | 上海光学精密机械研究所_学位论文 |
| 推荐引用方式 GB/T 7714 | 李日红. 新型溶胶凝胶法合成激光染料掺杂AlPO4<sub>凝胶，玻璃和薄膜[D]. 中国科学院上海光学精密机械研究所. 2010. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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