Photoinduced mass transport using amorphous molecular materials

本论文设计并合成了几种新型的光致变色非晶态分子材料，并研究了它们的光致变色性能和光致质量输运特性，具体如下：（1）对于N，N '-二苯基对苯二胺和N，N-双[4-（苯偶氮）-苯基]-N'，N '-二苯基对苯二胺这两种新型的偶氮苯基光致变色非晶态分子材料，发现分子结构对光致表面浮雕光栅的形成有显著的影响，其中两个偶氮苯基团在对苯二胺核中的位置不同。(2)A设计合成了一种新型偶氮苯基光致变色非晶态分子材料--三[4-（苯基偶氮）苯基]胺（TPAPA）。TPAPA的玻璃化转变温度为67℃，易形成非晶玻璃，并表现出非晶薄膜的光致变色性。用两束相干Ar^+激光辐照TPAPA非晶薄膜，形成表面浮雕光栅， ...更多信息 g，衍射效率为2.3%，调制深度为ca. 100纳米。（3）研究了偶氮苯基光致变色非晶态分子材料4-[双（9，9-二甲基芴-2-基）氨基]偶氮苯（BFlAB）在线偏振Ar^+激光辐照下的非晶态薄膜的二向色性。（4）研究了偶氮苯基光致变色非晶态分子材料BFlAB的光致变色反应。结果发现，反向顺-反热异构化的光生顺式异构体的BFlAB作为非晶膜加速相对于在溶液中，这种加速效应变得更加突出的照射时间产生的顺式异构体减少。结果表明，在偶氮苯发色团反复进行反-顺和顺-反光异构化过程中，非晶膜的局部自由体积逐渐增加。（5）利用4-二甲氨基偶氮苯，在两束相干激光照射下，在有机单晶上形成了光致表面浮雕光栅。结果表明，SRG的形成主要取决于晶体的配位和写入光的偏振态。发现使用单晶的SRG形成的写入光束的偏振的依赖性是很大的不同的非晶聚合物和光致变色非晶分子材料的报道，这表明SRG的形成机制上的有机晶体是有点不同的非晶材料。少

In the present study, we have designed and synthesized several novel photochromic amorphous molecular materials and investigated their photochromic properties and photoinduced mass transport as follows :(1)A significant effect of molecular structure on the photoinduced surface relief grating formation was found for novel azobenzene-based photochromic amorphous molecular materials, N, N'-diphenyl-p-phenylenediamine and N, N-bis[4-(phenylazo)-phenyl]-N', N'-diphenyl-p-phenylenediamine, where the positions of the two azobenzene groups in the p-phenylenediamine core are different from each othe.(2)A novel azobenzene-based photochromic amorphous molecular material, tris[4-(phenylazo)phenyl]amine (TPAPA), was designed and synthesized. TPAPA was found to readily form an amorphous glass with a glass-transition temperature of 67℃ and to exhibit photochromism as amorphous film. Irradiation of amorphous film of TPAPA with two coherent Ar^+ laser beams led to the formation of surface relief gratin … More g with a diffraction efficiency of 2〜3% and a modulation depth of ca. 100nm.(3)Dichroism of amorphous film of an azobenzene-based photochromic amorphous molecular material, 4-[bis(9,9-dimethylfluoren-2-yl)amino]-azobenzene (BFlAB), induced by irradiation with linearly polarized Ar^+ laser light has been investigated.(4)The photochromic reaction of an azobenzene-based photochromic amorphous molecular material, BFlAB, has been investigated. It was found that the backward cis-trans thermal isomerization of the photogenerated cis-isomer of BFlAB as amorphous film is accelerated relative to that in solution and that this acceleration effect becomes much more prominent as the irradiation time for generating the cis-isomer decreases. The results indicate that the local free volume of the amorphous film gradually increases during the repeated trans-cis and cis-trans photoisomerizations of the azobenzene chromophore.(5)Photoinduced surface relief grating formation on an organic single crystal by irradiation with two coherent laser beams has been demonstrated by using 4-(dimethylamino)azobenzene. It was found that the SRG formation was greatly depending upon both the coordination of the crystal and the polarization of the writing beams. The dependence of the polarization of writing beams on the SRG formation using the single crystal was found to be quite different from that reported for amorphous polymers and photochromic amorphous molecular materials, suggesting that the mechanism of the SRG formation on the organic crystal is somewhat different from that on amorphous materials. Less