Optical Properties of Organic-Inorganic Hybrid Mesoporous Materials with Crystal-like Wall Structure

类晶壁结构有机-无机杂化介孔材料的光学性能

基本信息

批准号：
16310094
负责人：
INAGAKI Shinji
金额：
$ 6.85万
依托单位：
Toyota Central R&D Labs., Inc.
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

We have obtained mainly three results, (1)understanding of fluorescence properties and discovery of unique light harvesting antenna property of mesoporous biphenylylene-silica (BPh-HMM), (2)the synthesis of novel mesoporous organosilicas with optical function, and (3)the construction of an electrical luminescence devices and it's luminescence property, (1)Fluorescence quantum yield of BPh-HMM solid was determined as Φ=0.37-0.56(λ_<ex.>=270,λ_<em.>=370nm) by using an absolute PL Quantum Yield Measurement System (Hamamatsu Photonics). It is higher than the quantum yields of biphenyl (C_6H_5-C_6H_5,Φ=0.07) and biphenyl-disilane precursor [(EtO)_3Si-C_6H_4-C_6H_4-Si(OEt)_3,Φ=0.23]. The high quantum yield for BPh-HMM is generated by the unique arrangement of biphenylylene and silica species, which prevent the fluorescence quenching of biphenylylene species. The excitation energy of biphenylylene was effectively transferred to coumarin dye located in the mesopores. Small addition of coumarin … More dye (0.5 mol% -biphenylylene) completely quenched the biphenylylene fluorescence (λ_<em>=270nm) and in turn emitted strongly coumarin fluorescence (λ_<em>=450nm). The fluorescence quantum yield of coumarin/BP-HMM was almost Φ=1(λ_<ex.>=270,λ_<em.>=450nm). The high quantum yield indicates that mesoporous organosilicas are excellent light harvesting antenna function. (2)We have synthesized new mesoporous organosilicas from optically functional terphenyl, naphthalene, anthracene, pyrene, fluorene, and carbazole-bridged disilane precursors [(EtO)_3Si-R-Si(OEt)_3]. They had absorption bands at 270-400 nm and emission bands at 370-520 nm in visible region, which is merit for applications to visible emitted devices and solar energy conversion devices. (3)We made the electrical emitted devices using mesoporous organosilicas including biphenylylene, anthracene, carbazole as emitted layer sandwiched by electrical and hole injection layers. The devices emitted electrically, but efficiency and life time are insufficient for the actual uses. The wavelength of the emission can be tunable by selecting organic groups in the framework and dyes introduced in the mesopores. These results revealed that mesoporous organosilicas showed excellent photoluminescence and light harvesting antenna properties and have highly potential applications to solar energy conversion system. Less

我们主要获得了三项成果，（1）介孔亚联苯二氧化硅（BPh-HMM）的荧光特性的理解和独特的光捕获天线特性的发现，（2）具有光学功能的新型介孔有机二氧化硅的合成，以及（3）电致发光器件的构建及其发光性能，(1)BPh-HMM固体的荧光量子产率确定为通过使用绝对PL量子产率测量系统（Hamamatsu Photonics），Φ=0.37-0.56（λ_<ex.>=270,λ_<em.>=370nm）高于联苯（C_6H_5-C_6H_5， Φ=0.07) 和联苯基二硅烷前体[(EtO)_3Si-C_6H_4-C_6H_4-Si(OEt)_3,Φ=0.23] BPh-HMM 的高量子产率是由亚联苯和二氧化硅物质的独特排列产生的，这防止了亚联苯物质的荧光猝灭。亚联苯的激发能有效地转移到位于中孔的香豆素染料上，少量添加香豆素......更多的染料(0.5 mol%-亚联苯)完全猝灭了亚联苯荧光(λ_<em>=270nm)，进而发出强烈的香豆素荧光(λ_<em>=450nm)，香豆素/BP-HMM的荧光量子产率几乎为零。 Φ=1(λ_<ex.>=270,λ_<em.>=450nm) 高量子产率表明： (2)我们以光学功能的三联苯、萘、蒽、芘、芴和咔唑桥联的乙硅烷前驱体[(EtO)_3Si-R-Si(OEt)_3合成了新型介孔有机硅。它们的吸收带位于 270-400 nm，发射带位于 270-400 nm。可见光区域波长为370-520 nm，这对于应用于可见光发射器件和太阳能转换器件具有优势。 (3)我们使用包括亚联苯、蒽、咔唑在内的介孔有机硅作为发射层，通过电注入和空穴注入制备了电发射器件。器件发射电，但效率和寿命不足以满足实际用途。可以通过选择框架中的有机基团和引入的染料来调节发射波长。这些结果表明，介孔有机硅表现出优异的光致发光和光捕获天线性能，在太阳能转换系统中具有很高的应用潜力。