单一分子量含氟嵌段共聚物的本体及薄膜自组装研究  

Investigation of Bluk and Thin-film Self-assembly Using Discrete Fluorine-containing Block Copolymers

作　　者：吴海兵 蒋胜喜 谭睿 刘雨欣 董学会 张正彪[1] Hai-bing Wu;Sheng-xi Jiang;Rui Tan;Yu-xin Liu;Xue-hui Dong;Zheng-biao Zhang(College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou 215123;South China Advanced Institute for Soft Matter Science and Technology,South China University of Technology,Guangzhou 510640)

机构地区：[1]苏州大学材料与化学化工学部,苏州215123 [2]华南理工大学前沿软物质学院,广州510640

出　　处：《高分子学报》2024年第2期142-152,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21925107);中国博士后科学基金(基金号第71批,2022M712306)资助项目。

摘　　要：嵌段共聚物导向自组装作为一种自下而上的图案化工艺,受到工业界和学术界的广泛关注.然而,导向自组装中缺陷率与分子参数之间的关系研究尚不清晰.本文工作基于模块化合成策略,利用迭代指数增长法并结合巯基-双键的点击反应成功制备了高χ低N的单一分子量含氟聚酯嵌段共聚物(oLAn-FPOSS).单一分子量特征可以排除多分散性对自组装行为的影响.本体自组装研究表明聚酯嵌段和含氟嵌段具有强相分离驱动力,可以形成特征尺寸小于10 nm的六方柱状相结构(HEX).在薄膜自组装中,嵌段共聚物经过简单的热退火可以在硅片表面形成平行基底排布的柱状纳米图案.此外,通过对比研究不同链长单一分子量嵌段共聚物的薄膜组装行为,发现随着嵌段共聚物链长的增长薄膜组装图形缺陷率明显下降,初步揭示了薄膜自组装过程中缺陷形成对嵌段共聚物链长的依赖性.Directed self-assembly of block copolymers has arouse tremendous interest from academy and industry as a bottom-up patterning process to fabricate versatile nanostructures.However,the underlying principles between molecular parameters and defectivities in directed self-assembly are still unambiguous due to the limitations of traditional polydisperse polymer models.Discrete polymer with defined molecular structure and uniform chain length are ideal candidates to reveal the fundamental principles.In this study,based on the modular synthesis strategy,discrete fluorine-containing polyester block copolymers(oLAn-FPOSS)with highχ-low N were firstly prepared by iterative exponential growth in combination with the thiol-ene click reaction.Owing to the discrete feature,the influence of polydisperse molecular parameters including composition,molecular weight and distribution on self-assembly behaviors can be completely excluded.Consequently,the impacts of molecular structures on the evolution of phase segregation can be quantitatively revealed.Due to the strong segregation strength,hexagonally packed cylindrical nanostructures(HEX)less than 10 nm can be formed in bulk and the phase stability increases with the chain length of oLA block.In thin-film self-assembly,parallelly oriented cylindrical nanopatterns on Si substrate were clearly identified after brief annealing under vacuum.In addition,through comparative studies of thin-film self-assembly behaviors of discrete block copolymers with different chain lengths,the nanopattern defectivity decreased significantly with the increase of oLA block chain length,which initially revealed the dependence of defect formation on block copolymer chain length in thin-film self-assembly.

关 键 词：单一分子量高分子 导向自组装 含氟嵌段共聚物 本体及薄膜自组装 光刻 

分 类 号：TQ316[化学工程—高聚物工业]