Downsizing feature of microphase-separated structures via intramolecular crosslinking of block copolymers
Downsizing feature of microphase-separated structures via intramolecular crosslinking of block copolymers
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通过嵌段共聚物的分子内交联实现微相分离结构的小型化
DOI：
10.1039/c8sc05016c
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发表时间：
2019
期刊：
影响因子：
8.4
通讯作者：
Satoh Toshifumi
中科院分区：
文献类型：
--
作者：
Watanabe Kodai;Katsuhara Satoshi;Mamiya Hiroaki;Yamamoto Takuya;Tajima Kenji;Isono Takuya;Satoh Toshifumi
通过嵌段共聚物（BCP）的分子内交联反应，在不改变分子量的情况下，发展了一种减小微相分离结构特征的新策略。在高稀释条件下，对苯乙烯-苯乙烯-对丁烯基苯乙烯共聚物（SBS）和外消旋-丙交酯共聚物（SBS-LA）进行钌催化的烯烃复分解反应，制备了分子内交联的嵌段共聚物（SBS（cl）-LA）。小角X射线散射测量和透射电子显微镜观察的SBS（cl）-LAs揭示了特征尺寸减少的层状（LAM）和六方密堆积的圆柱体（HEX）结构在本体状态下，这肯定是由于限制链尺寸的分子内交联SBS嵌段。值得注意的是，尺寸减小的程度是可控的，通过改变交联密度，在LAM间距的最大减少22%。此外，我们成功地观察到缩小的HEX结构的薄膜状态，使用原子力显微镜，表明本方法的适用性，下一代光刻技术。
A novel strategy for downsizing the feature of microphase-separated structures was developed via the intramolecular crosslinking reaction of block copolymers (BCPs) without changing the molecular weight. A series of BCPs consisting of poly[styrene-st-(p-3-butenyl styrene)] and poly(rac-lactide) (SBS–LA) was subjected to Ru-catalyzed olefin metathesis under highly diluted conditions to produce intramolecularly crosslinked BCPs (SBS(cl)–LAs). Small-angle X-ray scattering measurement and transmission electron microscopy observation of the SBS(cl)–LAs revealed feature size reduction in lamellar (LAM) and hexagonally close-packed cylinder (HEX) structures in the bulk state, which was surely due to the restricted chain dimensions of the intramolecularly crosslinked SBS block. Notably, the degree of size reduction was controllable by varying the crosslink density, with a maximum decrease of 22% in the LAM spacing. In addition, we successfully observed the downsizing of the HEX structure in the thin film state using atomic force microscopy, indicating the applicability of the present methodology to next-generation lithography technology.