A block copolymer (BCP) with specific monomer structures of fluoroacrylate polymers was designed by exploiting the inorganic superhydrophobicity and low glass transition temperature of polydimethylsiloxane (PDMS). With the use of a fluorine-containing block providing a surface tension as low as that of PDMS (19.9 < \(\gamma\) < 21.5 mN/m), PDMS-b-poly(2,2,3,3,3-pentafluoropropyl acrylate) (PDMS-b-PPeFPA) copolymer was synthesized to create a volume-symmetric lamellar structure. The compositional randomness of the BCP chains adsorbed onto the substrates provided well-balanced interfacial interactions toward the overlaid PDMS-b-PPeFPA (\(\gamma\)_PDMS-ads ≈ \(\gamma\)_PPeFPA-ads). Under this symmetric confinement with simultaneous dual neutral interfaces, lamellar microdomains with a sub-10 nm half-pitch feature size were successfully oriented perpendicular to the interfaces at room temperature. We showed the response of the BCP films to a lateral electric field, demonstrating that the perpendicular lamellae were adaptively aligned along the electric vector within a short treatment period. Furthermore, the PDMS-b-PPeFPA system exhibited a remarkable etch contrast for O₂ reactive ion etching, yielding unidirectionally aligned air–inorganic nanoarrays emanating from the perpendicular lamellae between the electrodes. This study reports a system engineering approach for conceiving highly immiscible, silicon- and fluorine-containing BCP whose components exhibit identical surface tensions (\(\gamma\)_PDMS ≈ \(\gamma\)_PPeFPA) and for generating perpendicularly oriented lamellar microdomains due to substrate neutrality.

利用聚二甲基硅氧烷（PDMS）的无机超疏水性和低玻璃化转变温度，设计了具有特定氟代丙烯酸酯聚合物单体结构的嵌段共聚物（BCP）。使用含氟嵌段提供与 PDMS 一样低的表面张力 (19.9 < \(\gamma\)  < 21.5 mN/m)，PDMS- b -poly(2,2,3,3,3合成了丙烯酸-五氟丙酯）（PDMS- b -PPeFPA）共聚物，以形成体积对称的层状结构。吸附在基材上的 BCP 链的组成随机性为覆盖的 PDMS- b -PPeFPA（\(\gamma\) _PDMS-ads  ≈  \(\gamma\) _PPeFPA-ads）提供了良好平衡的界面相互作用。在这种具有同时双中性界面的对称限制下，具有亚10 nm半节距特征尺寸的层状微域在室温下成功地垂直于界面定向。我们展示了 BCP 薄膜对横向电场的响应，证明垂直片层在短时间内沿着电矢量自适应排列。此外，PDMS- b -PPeFPA系统在O ₂反应离子蚀刻中表现出显着的蚀刻对比度，产生从电极之间的垂直片层发出的单向排列的空气-无机纳米阵列。这项研究报告了一种系统工程方法，用于构想高度不混溶的含硅和氟 BCP，其组件表现出相同的表面张力（\(\gamma\) _PDMS  ≈  \(\gamma\) _PPeFPA），并生成垂直取向的层状微域，因为至底物中性。