Quantitative understanding of phase segregation behaviors by precisely building discrete oligo-ester-b-oligo-olefin block copolymers  

作　　者：Yuxin Liu Rui Tan Haibing Wu Xue-Hui Dong Zhengbiao Zhang 

机构地区：[1]College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou 215123,China [2]State Key Laboratory of Radiation Medicine and Protection,Soochow University,Suzhou 215123,China [3]South China Advanced Institute for Soft Matter Science and Technology,School of Molecular Science and Engineering,South China University of Technology,Guangzhou 510640,China

出　　处：《Science China Chemistry》2024年第3期1008-1016,共9页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21925107,22273026);China Postdoctoral Science Foundation(71st,2022M712306);the Collaborative Innovation Center of Suzhou Nano Science and Technology;the Jiangsu Funding Program for Excellent Postdoctoral Talent。

摘　　要：Block copolymers(BCPs) with high Flory-Huggins parameter(χ) and balanced surface energy have aroused tremendous interest for ultra-small nanopatterns processing.However,high χ and balanced surface energy are generally contradicted.The fine tune of chain structure might be a useful way to achieve high χ and balanced surface energy.To realize this,the block copolymer with exactly uniform chain structure,i.e.,defined molecular structure,is highly desirable for accurately evaluating the phase behavior.Herein,two kinds of discrete oligo ester-b-oligo olefin block copolymers with different chemical structures(oligo lactic acid-boligo olefin BCP,oLA_(n)-b-C_(m);oligo phenyl lactic acid-b-oligo olefin BCP,oPL_(n)-b-C_(m)) were modularly synthesized through iterative growth methods.The effect of chain structure on segregation strength and surface properties was quantitatively investigated using the discrete BCPs as precise models.On the one hand,introducing rigid and nonpolar phenyl groups into oligo ester block has a negligible effect on the chemical incompatibility,as confirmed by the identical high χ values of oLA_(n)-b-C_(m) and oPL_(n)-b-C_(m)(χ_(oLA/C)=0.21 and χ_(oPL/C)=0.19).On the other hand,the incorporation of nonpolar phenyl groups creates balanced surface energy,that is,the high χ and balanced surface energy were simultaneously achieved by oPL_(n)-b-C_(m).Therefore,sub-10 nm perpendicular nanopatterns can be easily produced upon brief thermal treatment,demonstrating its potential application in semiconductor manufacturing with ultra-small feature size.The discrete BCP can serve as a quantitative and exquisite model to study the critical contribution of chain structures on phase separation behavior,providing insightful understanding to facilitate the potential application in the chip process.

关 键 词：discrete polymer iterative growth SELF-ASSEMBLY highχ balanced surface 

分 类 号：O631[理学—高分子化学]