Watanabe Kodai, Katsuhara Satoshi, Mamiya Hiroaki, Yamamoto Takuya, Tajima Kenji, Isono Takuya, Satoh Toshifumi
Faculty of Engineering and Graduate School of Chemical Sciences and Engineering , Hokkaido University , Sapporo 060-8628 , Japan . Email:
Quantum Beam Unit , Advanced Key Technologies Division , National Institute for Materials Science , Ibaraki 305-0047 , Japan.
Chem Sci. 2019 Jan 14;10(11):3330-3339. doi: 10.1039/c8sc05016c. eCollection 2019 Mar 21.
A novel strategy for downsizing the feature of microphase-separated structures was developed the intramolecular crosslinking reaction of block copolymers (BCPs) without changing the molecular weight. A series of BCPs consisting of poly[styrene--(-3-butenyl styrene)] and poly(-lactide) (SBS-LA) was subjected to Ru-catalyzed olefin metathesis under highly diluted conditions to produce intramolecularly crosslinked BCPs (SBS()-LAs). Small-angle X-ray scattering measurement and transmission electron microscopy observation of the SBS()-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.
开发了一种在不改变分子量的情况下减小微相分离结构特征尺寸的新策略，即通过嵌段共聚物（BCP）的分子内交联反应来实现。一系列由聚[苯乙烯-（-3-丁烯基苯乙烯）]和聚（-丙交酯）（SBS-LA）组成的BCP在高度稀释的条件下进行钌催化的烯烃复分解反应，以制备分子内交联的BCP（SBS（）-LAs）。对SBS（）-LAs进行小角X射线散射测量和透射电子显微镜观察，结果表明，本体状态下的层状（LAM）和六方密堆积圆柱（HEX）结构的特征尺寸减小，这肯定是由于分子内交联的SBS嵌段的链尺寸受限所致。值得注意的是，尺寸减小程度可通过改变交联密度来控制，LAM间距最大可减小22%。此外，我们利用原子力显微镜成功观察到薄膜状态下HEX结构的尺寸减小，这表明本方法适用于下一代光刻技术。
