The self-assembly of thin films of block copolymers (BCPs) with perpendicular domain orientation offers a promising approach for nanopatterning on a variety of substrates, which is required by advanced applications such as ultrasmall transistors in integrated circuits, nanopatterned materials for tissue engineering, and electrocatalysts for fuel cell applications. In this study, we created BCPs with an A-b-(B-r-C) architecture that have blocks with equal surface energy (γ_air) and that can bind to the substrate, effectively creating a non-preferential substrate coating via self-brushing that enables the formation of through-film perpendicular domains in thin films of BCPs. We employed a thiol–epoxy click reaction to functionalize polystyrene-block-poly(glycidyl methacrylate) with a pair of thiols to generate an A-b-(B-r-C) BCP and tune γ_air of the B-r-C block. The secondary hydroxyl and thiol ether functionality generated by the click reaction was utilized to bind the BCP to the substrates. Scanning electron microscopy revealed that perpendicular orientation was achieved by simply annealing a thin film of the BCP on the bare substrate without the usual extra step of coating a random copolymer brush on the substrate. The self-brushing capability of the BCP was also examined on gold, platinum, titanium, aluminum nitride, and silicon nitride surfaces. These results demonstrate that self-brushing is a promising approach for achieving perpendicular domain orientation in thin films of BCP for nanopatterning on a variety of useful surfaces.

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用于纳米图案的自刷：在嵌段共聚物薄膜中实现垂直域取向

具有垂直域取向的嵌段共聚物（BCP）薄膜的自组装为在各种基材上进行纳米图案化提供了一种有前途的方法，这是集成电路中的超小型晶体管、用于组织工程的纳米图案材料和用于燃料电池应用的电催化剂。在这项研究中，我们创建了具有 A- b -(B- r -C) 结构的 BCP，该结构具有相同表面能（γ_空气）的块体，并且可以与基材结合，通过自身有效地形成非优先基材涂层。 -刷涂能够在 BCP 薄膜中形成穿膜垂直域。我们采用硫醇-环氧点击反应，用一对硫醇对聚苯乙烯嵌段聚（甲基丙烯酸缩水甘油酯）进行功能化，生成 A- b -(B- r -C) BCP 并调整B- r -C的γ_空气堵塞。利用点击反应产生的仲羟基和硫醇醚官能团将 BCP 与底物结合。扫描电子显微镜显示，通过简单地在裸基板上退火 BCP 薄膜即可实现垂直取向，而无需在基板上涂覆无规共聚物刷的通常额外步骤。还在金、铂、钛、氮化铝和氮化硅表面上检验了 BCP 的自刷能力。这些结果表明，自刷是一种在 BCP 薄膜中实现垂直域取向以在各种有用表面上进行纳米图案化的有前途的方法。