标题: | 新颖感光树脂之制备与性质研究 Preparation and Characterization of Novel Photosensitive Resins |
作者: | 林和玫 Ho-May Lin 张丰志 Feng-Chih Chang 应用化学系硕博士班 |
关键字: | 感光树脂;氢键;多面体矽氧烷化合物;光聚合反应;光阻;光硬化;photosensitive resins;hydrogen bonding;polyhedral oligomeric silsesquioxane;photopolymerization;photoresist;photocurable |
公开日期: | 2007 |
摘要: | 在感光树脂研究中,已知藉由氢键作用让分子先行排列,可使感光基互相靠近而加快光聚合反应速度。在我们先前的研究中,也观察到多面体矽氧烷化合物(polyhedral oligomeric silsesquioxane,简称POSS)的siloxane基和OH基间存在氢键。因此,我们延伸之前的研究,希望开发高感度的感光树脂。本论文分为四部份研究:(1)将POSS结构导入感光性共聚高分子,再配制成负型光阻;(2)直接将单压克力官能基POSS化合物混掺入负型光阻中;(3)直接将五氟苯乙烯混掺入负型光阻中;(4)将单压克力官能基POSS化合物混掺入紫外光硬化树脂组成物中。然后探讨感光树脂的特性。 (1)在第二章研究中,制备一系列感光性共聚高分子,含有POSS结构和甲基丙烯酸酯(methacrylate)感光官能基,由甲基丙烯酸(methacrylic acid)、甲基丙烯酸甲酯(methyl methacrylate)、异丁基丙基甲基丙烯醯基多面体矽氧烷(isobutyl propylmethacryl polyhedral oligosilsesquioxanes,简称MI-POSS)经过自由基共聚合反应,再和甲基丙烯酸环氧丙酯(glycidyl methacrylate)反应而得。感光性共聚高分子化学结构以1H-NMR和FT-IR光谱确认。由微差扫描卡计(DSC)和热重分析仪(TGA)分析结果显示,感光性共聚高分子的玻璃转化温度和热安定性会随着POSS含量增加而增加。紫外光/可见光光谱仪(UV/VIS)测试结果可看到感光性共聚高分子因加入POSS而稍微降低透光性,在365nm波长透光率由99%微降至92.5%。进一步将感光性共聚高分子、压克力多官能基单体、光起始剂配制为光阻评估光阻性质。由评估结果发现,含POSS光阻的感度(sensitivity,Dn0.5)、对比(contrast, )、光硬化速率等光阻性能,都比未含POSS光阻提升许多。photo-DSC分析显示,导入POSS使反应起始时间(induction time)由0.020 min降至0.015 min。 (2)在第三章研究中,配制一系列负型光阻,固定感光性共聚高分子(不含POSS)、压克力多官能基单体、光起始剂的组成量,变化MI-POSS混掺量,并探讨其光阻特性。我们发现含POSS光阻的感度(sensitivity)、对比(contrast)、光硬化速率等光阻性能,都比未含POSS光阻提升许多。结果与第二章类似,但是提升效率稍差。 (3)在第四章研究中,延伸第三章研究,将MI-POSS改为五氟苯乙烯,并探讨其光阻特性。我们发现含五氟苯乙烯光阻的感度(sensitivity)、对比(contrast)、光硬化速率等光阻性能,都比未含五氟苯乙烯光阻提升许多。结果与第三章类似。 (4)在第五章研究中,配制二系列含POSS的紫外光硬化树脂组成物,由Bisphenol A propoxylate glycerolate diacrylate(简称PGDA)或Bisphenol A propoxylate diacrylate(简称PDA)单体加上MI-POSS单体和光起始剂Irgacure 907所组成。利用FTIR光谱和photo-DSC,探讨分子结构和分子间氢键作用对光聚合反应速率和放热量的影响。结果显示PGDA系列光聚合速度和放热量均小于PDA系列。PGDA单体的压克力官能基上含有OH官能基,因为分子结构的关系,虽然形成分子间氢键,压克力官能基容易受氢键限制无法自由运动与紧密靠近,反而不利光聚合反应。混掺MI-POSS,即使只是小量,却可以聚集压克力官能基,对光聚合速率有提升效果。PDA单体不含OH基,加入MI-POSS混掺,只是逐渐稀释压克力官能基密度,对光聚合速率没有提升效果。 由以上观察结果,可以合理的解释为hydroxyl-siloxane或hydroxyl-carbon fluorine bond间氢键交互作用,使含OH基的压克力双键聚集在POSS或pentafluorostyrene结构周围,有助于光硬化反应,因而加强光硬化反应速度、感度等感光树脂性能。我们也利用平行曝光机评估光阻的微影性质(lithographic property),发现本论文光阻适合高感度紫外光微影技术之应用。 It has been reported that the photopolymerization rates of photoresists capable of forming hydrogen bonding are significantly enhanced due to the pre-organization via hydrogen bonding to bring reactive bonds closer each other. In our previous study, we have observed the existence of hydrogen bonding interaction between the siloxane of the polyhedral oligomeric silsesquioxane (POSS) moiety and the hydroxyl groups. Accordingly, we would like to extend our previous works to develop new photosensitive resins with enhanced sensitivity, higher contrast, and better resolution. In this dissertation, POSS-containing negative-type photoresists were prepared by copolymerization and blending methods, then characterized. Fluorine-containing negative-type photoresists by blending method and POSS-containing photocurable resins were also studied. (1) In chapter 2, a series of methacrylate copolymers containing POSS were synthesized from the free radical copolymerization of methacrylic acid, methyl methacrylate, and isobutyl propylmethacryl polyhedral oligosilsesquioxanes (MI-POSS) and then were modified with glycidyl methacrylate to serve as negative-type photoresists. The UV/VIS spectroscopy reveals that the incorporation of POSS moiety into the copolymer results in slight decrease in transparency from 99% to 92.5 % (at wavelength = 365 nm). The photosensitivity in terms of resist sensitivity, contrast and photopolymerization rate are significantly increased with increasing of the POSS content. In addition, the induction time is reduced from 0.020 to 0.015 min after incorporating POSS unit based on the photo-DSC analyses. (2) In chapter 3, a series of negative type photoresists were prepared by blending different MI-POSS content and studied the photosensitive properties. The photosensitivity and photo-polymerization rate results which go up with an increase in MI-POSS content are similar to previous chapter’s study with slightly less efficiency but better processibility. (3) In chapter 4, a series of negative type photoresists were prepared by blending different pentafluorostyrene content and studied the photosensitive properties. The photosensitivity and photo- polymerization rate results which go up with an increase in pentafluorostyrene content are also similar to previous chapter’s study. (4) In chapter 5, two series of POSS-containing photocurable resin compositions were prepared and studied by FTIR spectroscopy and differential photocalorimetry. With fixed photoinitiator concentration, increasing proportions of MI-POSS were added to either bisphenol A propoxylate glycerolate diacrylate (PGDA) or bisphenol A propoxylate diacrylate (PDA). The photopolymerization rate and enthalpy of PGDA compositions are significantly smaller than PDA compositions. As POSS concentration increased, the photopolymerization reactivities of PGDA compositions increased, while the photopolymerization reactivities of PDA compositions continued decreasing with increasing POSS concentration. The strong influence of molecular structure and hydrogen-bonding interaction on photopolymerization rate and conversion was discussed. These observed results can be rationalized hydrogen bonding interaction between hydroxyl-siloxane or hydroxyl-carbon fluorine bond tends to attract the double bonds surrounding POSS or pentafluorostyrene units, thereby enhancing the photo-polymerization rate and sensitivity. We further evaluate the lithographic property of photoresists under a collimated exposure. High sensitivity photoresists made in this dissertation have potential utility for UV-lithography. |
URI: | http://140.113.39.130/cdrfb3/record/nctu/#GT008925809 http://hdl.handle.net/11536/78591 |
显示于类别: | Thesis |