如何有效控制大規模定向且有序的薄膜型態(特別是垂直定向的柱狀或板狀結構)為嵌段共聚物微影蝕刻術有效應用的關鍵。對於廣泛被使用之聚苯乙烯-聚二甲基矽氧烷嵌段共聚物自組裝薄膜而言，由於聚二甲基矽氧烷的低表面自由能，將導致含聚二甲基矽氧烷嵌段共聚物於自組裝時形成聚二甲基矽氧烷表面層，進而造成自組裝薄膜表層具平行排列的奈米微結構。本研究藉由熵-驅使定向方式，利用具有星狀結構的嵌段共聚物系統，平衡基材界面由於焓的效應對於嵌段共聚物組成成份的親合力，進而獲得垂直定向的奈米結構，並結合空氣電漿處理對星狀結構之嵌段共聚物自組裝薄膜表面，由交聯反應形成中性層，達到中和嵌段共聚物組成成份在空氣介面能的差異，以製備具高深寬比、垂直定向的奈米微結構薄膜。換言之，可結合高分子鏈的構型效應(熵-驅使)以及表面電漿處理(焓-驅使)，達到含聚二甲基矽氧烷嵌段共聚物自組裝之有效控制，製備大規模定向且有序的薄膜型態。
此外，藉由調整熱退火處理的時間之不同，首度觀察到由基材表面以及交聯的中性層同步成核成長之垂直定向柱狀結構，具有自我校準的行為。初時在成長至薄膜的中間時會產生錯位，形成螺旋與彎曲的柱狀結構，最終則可達到大規模定向且有序的垂直定向柱狀結構之薄膜型態。本研究主要為觀察薄膜形成垂直柱狀結構的成核成長及自我校準的過程，利用低掠角小角度X光散射實驗以及三維穿透式電子顯微鏡的影像重建技術探討其可能之自組裝行為，了解柱狀結構如何經過彎曲且自我校準後，形成垂直定向的奈米微結構。

Controlling the orientation of nanostructured block copolymer (BCP) thin films is essential for next-generation lithography. However, obtaining BCP with perpendicular orientation remains a challenge because of the surface selectivity to the different blocks. This challenge is especially severe for silicon-containing BCPs which is notorious for its high surface energy difference between constituted blocks. Here, we demonstrate a new approach to achieve perpendicular orientation with high aspect ratio using a combination of architecture effect (entropy effect) and surface air plasma treatment (enthalpy effect). Specifically, perpendicular cylinders of star-block copolymers composed of polystyrene and poly(dimethylsiloxane) blocks span-thru from the bottom substrate to the top surface of the thin film can be formed after thermal annealing.
Owing to the nucleation sites of the perpendicular nanostructure are fabricated from both interfaces of the thin film, the growth of the nanostructures would lead to a mismatch in the middle of the thin film, resulting in the formation of the spiral-like morphology and bended cylinders. Herein, we aim to examine and understand the nucleation and growth of the nanostructures nucleated from the SiO2 substrate and the air plasma-treated surfaces. Interestingly, the deformed nanostructures would be eliminated through a self-alignment process during the thermal annealing.

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