Surface Structure of Spin-Coated Fluorinated Polymers Films Dominated by Corresponding Film-Formation Solution/Air Interface Structure

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• 作者：Huagang Ni ; XueHua Li ; YanYan Hu ; Biao Zuo ; ZeLiang Zhao ; JuPing Yang ; DaXiang Yuan ; XiuYun Ye ; XinPing Wang
• 刊名：The Journal of Physical Chemistry C
• 出版年：2012
• 出版时间：November 15, 2012
• 年：2012
• 卷：116
• 期：45
• 页码：24151-24160
• 全文大小：524K
• 年卷期：v.116,no.45(November 15, 2012)
• ISSN：1932-7455

文摘

In this paper, the relationship between the surface structures of spin-coated fluorinated polymer films and their corresponding film-formation solution/air interface structures was investigated. Film-forming poly(n-alkyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate (FMA; PFMA_y-ec-PnAMA_x-ec-PFMA_y) was synthesized via a controlled/living atom-transfer radical polymerization (ATRP) technique. The structures both at solution interface and on the spin-coated film surface for these polymers were studied by X-ray photoelectron spectroscopy (XPS), sum frequency spectroscopy (SFG), and surface tension measurements. The results showed that, with increasing polymerization degree of PnAMA, the fluorinated moieties in PFMA_y-ec-PnAMA_x-ec-PFMA_y adsorbed at the solution/air interface were gradually completely replaced by PnAMA segments, resulting in an increase in corresponding solution surface tension until it was equal to that of poly(n-alkyl methacrylate) solution. Additionally, it was observed for the first time that the surface F/C ratios of spin-coated films decreased linearly with increasing surface tension of the corresponding film-formation polymer solution. Overall, the results indicate that the ultimate surface composition of spin-coated films of these fluorinated methacrylates was mainly dominated by their corresponding film-formation solution/air interfacial structure. This work provides a fundamental understanding of the formation of film surface structures from fluorinated polymer solution to the resulting solid film.