Photoinduced mass transport using amorphous molecular materials

在本研究中，我们设计并合成了几种新型的光致变色非晶分子材料，并对其光致变色性能和光致质量输运进行了如下研究：(1)发现了新型偶氮基光致变色非晶分子材料N， N′-二苯基-对苯二胺和光致表面梯度光栅形成的显著影响，N， N′-双[4-（苯基）苯基]-N′，N′-对苯二胺；其中对苯二胺核中两个偶氮苯基的位置彼此不同。(2)设计并合成了一种新型的偶氮苯基光致变色非晶分子材料三[4-（苯基偶氮）苯基]胺（TPAPA）。发现TPAPA易于形成非晶玻璃，玻璃化温度为67℃，并表现出非晶薄膜的光致变色性。两束相干Ar +激光辐照TPAPA非晶膜，可形成表面凹凸光栅…More g，衍射效率为2 ~ 3%，调制深度约为100nm。(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^+激光照射下的非晶态膜的二色性。(4)研究了偶氮苯基光致变色非晶分子材料BFlAB的光致变色反应。研究发现，光生成的BFlAB非晶膜顺式异构体的反顺式-反式热异构化过程相对于溶液中加速，并且随着生成顺式异构体的辐照时间的减少，这种加速效应更加明显。结果表明，在偶氮苯发色团的反复反-顺-反光异构过程中，非晶膜的局部自由体积逐渐增大。(5)用4-（二甲氨基）偶氮苯证明了两束相干激光照射在有机单晶上形成光致表面凸出光栅。研究发现，SRG的形成对晶体的配位和书写光束的偏振都有很大的影响。在单晶中写入光束的极化对SRG形成的依赖性与在非晶态聚合物和光致变色非晶态分子材料中形成的依赖性有很大的不同，这表明SRG在有机晶体上的形成机制与在非晶态材料上的形成机制有所不同。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