Poly(2-vinylpyridine)-b-poly(fluorinated methacrylate) Block Copolymers Forming 5 nm Domains Containing Metallocene,ACS Applied Energy Materials

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Poly(2-vinylpyridine)-b-poly(fluorinated methacrylate) Block Copolymers Forming 5 nm Domains Containing Metallocene
ACS Applied Energy Materials ( IF 5.4 ) Pub Date : 2020-07-17 00:00:00 , DOI: 10.1021/acsapm.0c00608
Xuemiao Li ₁ , Hai Deng ₁

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Directed self-assembly (DSA) of thin films of a block copolymer (BCP) is a promising approach for sub-10 nm lithographic patterning. In this paper, a series of poly(2-vinylpyridine)-block-poly(pentadecafluorooctyl methacrylate) (P2VP-b-PPDFMA) and poly(2-vinylpyridine)-block-poly(heptafluorobutyl methacrylate) (P2VP-b-PHFBMA) BCPs are synthesized by living anionic polymerization. The molar ratio of the two blocks and the degree of polymerization enable precise control of the morphology and size of the microdomains of the BCPs. The resulting materials form sub-5 nm scale microphase-separated structures, as seen with small-angle X-ray scattering and transmission electron microscopy. The introduction of the fluorine-containing blocks leads to a significant increase in the Flory–Huggins interaction parameter (χ) between the two blocks, as determined with the mean-field theory. The temperature dependence of χ_2VP/PDFMA is χ = 48.79/T + 0.272 (0.387 at 150 °C) and of χ_2VP/HFMBA is χ = 2.29/T + 0.342 (0.347 at 150 °C). χ of each of these BCPs is 4 times higher than that of polystyrene-block-poly(2-vinylpyridine) (0.083 at 150 °C). The resulting smallest domain spacing of these BCPs is 8.3 nm in a lamellar morphology. The BCPs self-assemble into straight lines in a silicon trench template and the doping of the P2VP block with metal atoms can enhance their etch resistance, demonstrating the potential of these BCPs for advanced lithographic applications.

中文翻译：

聚（2-乙烯基吡啶）-b-聚（氟化甲基丙烯酸酯）嵌段共聚物形成含茂金属的5 nm域

嵌段共聚物（BCP）薄膜的直接自组装（DSA）是用于10纳米以下光刻图案的有前途的方法。在本文中，一个系列的聚（2-乙烯基吡啶）的-嵌段-聚（pentadecafluorooctyl丙烯酸甲酯）（P2VP- b -PPDFMA）和聚（2-乙烯基吡啶） -嵌段-聚（七氟丁基甲基丙烯酸酯）（P2VP- b-PHFBMA）BCP通过活性阴离子聚合合成。两个嵌段的摩尔比和聚合度能够精确控制BCP的微区的形态和大小。所得材料形成亚5纳米尺度的微相分离结构，如小角度X射线散射和透射电子显微镜所见。用均场理论确定，引入含氟嵌段会导致两个嵌段之间的Flory-Huggins相互作用参数（χ）显着增加。_{χ2VP / PDFMA}的温度依赖性为χ= 48.79 / T + 0.272（150°C时为0.387），而_{χ2VP / HFMBA的温度依赖性}为χ= 2.29 / T+ 0.342（150°C时为0.347）。这些BCP中的每一个的χ均比聚苯乙烯嵌段-聚（2-乙烯基吡啶）的χ高（在150°C时为0.083）4倍。在层状形态中，这些BCP的最终最小域间距为8.3 nm。BCP在硅沟槽模板中自组装成直线，并且用金属原子掺杂P2VP块可以增强其抗蚀刻性，这证明了这些BCP在高级光刻应用中的潜力。

更新日期：2020-07-17

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