Molecular Structure Modification and Characterization of Langmuir-Blodgett Films made of Amphiphilic Polysilane through Ionizing Radiation

电离辐射对两亲性聚硅烷制成的 Langmuir-Blodgett 薄膜的分子结构改性和表征

• 批准号: 05808042
• 负责人: ASAI Keisuke
• 金额: $ 1.09万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05808042/
• 关键词: Polysilane; Amphiphilic Polysilane; Langmuir-Blodgett Film; Photoconductivity; Amphiphile; UV Spectrum; 両親媒性; LB膜; イオン励起発光; パルスラジオリシス; PMPS; 過渡吸収スペクトル

Since the last decade, polysilane derivatives have been elicited great interest as fundamental polymer materials showing lelctronic semiconductivity, nonlinear optical property, high hole drift mobility, and so on. These interesting physical properties of polysilane derivatives are essentially attributed to the delocalization of sigma-electrons of the Si backbone. However, it is hardly to say that the conjugated system is extended over the entire silicon skeleton, therefore, it is common consensus that a silicon skeleton is divided into several conjugated silicon segments. The question is which determine the hole transport phenomenon in intermolecular or interesting hopping. Then, electronic and optical characterization of highly polarized polysilane films may predict the electronic structure of silicon skeleton and inter-and intra-molecular relation.In the present work, poly (methylphenylsilane) : PMPS and poly (beta-phenethylmethylsilane) : PMbeta-PhS employed as an initial polysilane, and amphiphilic polysilanes were obtained by the salt formation between chloromethylated PMPS or PMbeta-PhS and (CH_3) _2C_nH_<2n+1>N.Chlorine anion exchanged by several kinds of counter anions and the polymer piled up to 1000 layrs. Optical spectroscopy of these piled LB films represented piezochromic shifts in their absorption spectra. High dense excitation of these amphiphilic polymers showed a deference in emission spectra of polarized and dense LB films (400-500nm broad emission) and random solvent casted films (another longer emission band at 580-600nm). These two emission bands were assigned to intramolecular exciplex formation between ammonium groups and silicon skeleton and intermolecular one, respectively. It can be condluded that energy relaxation processes are different in LB films in comparison with amorphous films, intermolecular energy transfer can be neglected in LB films of amphiphilic polysilanes.

自过去十年以来，多硅烷衍生物一直引起极大的兴趣，因为它显示了Lelctronic的半导性，非线性光学特性，高孔漂移迁移率等。多硅烷衍生物的这些有趣的物理特性基本上归因于Si主链的Sigma-电子的取消依赖性。但是，几乎不可能说共轭系统在整个硅骨架上延伸，因此，通常共识将硅骨架分为几个共轭硅节段。问题是哪个决定了分子间或有趣的跳跃中的孔传输现象。然后，高度极化的多硅烷膜的电子和光学表征可以预测硅骨骼的电子结构和层间和分子内关系的电子结构。在当前的工作中，聚（甲基苯基硅烷）：PMPS和聚（β-苯基乙基甲基硅烷）作为pMBeta-phs均具有pMBETA-PHS：PMBETA-PHS均具有pmbeta-phs polys polys phirys polysyrane，以及polysyrane sallanity，以及polysyry salltical，均硅烷硅酸盐盐，甲基硅酸盐盐，在氯甲基化的PMP或PMBETA-PHS和（CH_3）_2C_NH_ <2n+1> N.N.氯阴离子之间，由几种反阴离子交换，聚合物堆积为1000个Layrs。这些堆积的LB膜的光谱法代表了吸收光谱中的压电偏移。这些两亲性聚合物的高密集激发表现出对极化和致密LB膜的发射光谱的尊重（400-500nm宽发射）和随机的溶剂铸造膜（另一个更长的发射带，在580-600nm）。这两个发射带分别分别分配给铵基和硅骨骼和分子间的分子内一流的形成。可以舒服的是，与无定形膜相比，LB膜中的能量松弛过程是不同的，分子间的能量转移可以忽略在Amphielic Polysilanes的LB膜中。

项目成果

S.Seki,M.Ando,T.Yamaki,Y.Nakashiba,K.Asai,K.Ishigure,and S.Tagawa: "Molecular Interaction in Langmuir-Blodgett Films of Amphiphilic Polysilanes" Journal of Photopolymer Science and Technology. 5(1). 89-100 (1995)

S.Seki、M.Ando、T.Yamaki、Y.Nakashiba、K.Asai、K.Ishigure 和 S.Takawa：“两亲性聚硅烷 Langmuir-Blodgett 薄膜中的分子相互作用”光聚合物科学与技术杂志。