Dong Lei, Wylie Kevin, Nabae Yuta, Hayakawa Teruaki
School of Materials Science and Engineering, Southeast University Nanjing 211189 China.
Department of Materials Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology S8-813, 2-12-1-S8-36, Ookayama, Meguro-ku Tokyo 152-8552 Japan.
RSC Adv. 2022 Jun 17;12(28):17950-17958. doi: 10.1039/d2ra02536a. eCollection 2022 Jun 14.
A precursor diblock copolymer with a silicon backbone, polystyrene--poly(methylvinylsiloxane), was synthesized, and 1,1,2,2-perfluorodecanethiol was quantitatively introduced into the backbone a thiol-ene reaction to yield a novel coil-rod diblock copolymer, poly(styrene--poly(2-((3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)thio)ethyl)methylsiloxane). The ultra-hydrophobicity of the introduced perfluoroalkyl side chain enhanced the segregation between counter-blocks and significantly increased the value, which is essential for minimizing the size of self-assembled domains for lithographic applications. Thus, self-assembled domains with a minimal spacing of approximately 10 nm were formed. A hexagonally packed array with significant anisotropy was observed in the self-assembled morphology by small-angle X-ray scattering and transmission electron microscopy. Such an array was precisely reproduced by modified self-consistent field theory (SCFT) calculation developed for the coil-rod structure. Furthermore, the phase diagram was estimated, and the morphological dependence on the relative scale of the rod unit was investigated by SCFT prediction.
合成了一种具有硅主链的前驱体二嵌段共聚物，聚苯乙烯-聚（甲基乙烯基硅氧烷），并通过硫醇-烯反应将1,1,2,2-全氟癸硫醇定量引入主链，得到一种新型的线圈-棒状二嵌段共聚物，聚（苯乙烯-聚（2-（（3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟癸基）硫代）乙基）甲基硅氧烷）。引入的全氟烷基侧链的超疏水性增强了反嵌段之间的分离，并显著提高了χ值，这对于最小化光刻应用中自组装域的尺寸至关重要。因此，形成了间距约为10nm的最小自组装域。通过小角X射线散射和透射电子显微镜观察到自组装形态中具有明显各向异性的六边形堆积阵列。通过为线圈-棒状结构开发的改进自洽场理论（SCFT）计算精确再现了这种阵列。此外，估计了相图，并通过SCFT预测研究了形态对棒单元相对尺度的依赖性。
