奈米碳管薄膜表面改質之製備與應用及其特性分析

Study on the Preparation and Characterization of Surface Treatment on Transparent Carbon Nanotubes Thin films

廖宏倫

奈米碳管 ； 官能基化 ； 共軛高分子 ； 拉曼 ； 疊氮苯氨 ； 分散性 ； carbon nanotubes ； functionalized ； conjugated polymer ； Raman ； azidoaniline ； dispersibility

清華大學工程與系統科學系學位論文

2016年

碩士

王本誠

英文

本研究分別以(i)非共價改質法和(ii)共價改質法，兩個方向對我們奈米碳管進行表面改質。 在非共價改質法中，我們使碳管表面改質上羧基，和基材上修飾氨基，設計簡易自組裝流程，欲使基材與碳管薄膜間產生共價鍵結，進而達到提升薄膜附著力與均勻性之目的，我們藉由SEM、AFM分析奈米碳管薄膜之形貌，並利用水槍噴灑的方式測試薄膜的附著性，其中方均跟粗糙度由原本未處理前的211nm降至21.3nm，造成薄膜樣品粗糙度與附著力的改善，我們推測是因為碳管與基材間產生共價鍵結，使樣品在成膜時，產生的形貌差異。本研究也討論改質碳管在有機太陽能電池元件上的應用潛力，利用Raman、 AFM與SEM等儀器量測結果，對改質奈米碳管做更深入的物化特性分析。 而在共價改質法中，我們使用4-叠氮苯氨在紫外光照射時產生的自由基，與我們碳管管壁反應，得到管壁官能基化具苯氨的奈米碳管，再藉由表面的官能基去與2-氨基苯磺酸、2-氨基-1,4-苯二磺酸以及(3-氨基苯基)磷酸做後續接枝聚合反應，期待導入共軛高分子優異的導電特性至碳管結構中，藉此改善碳管整體之電性。此外碳管管壁修飾上具親水的官能基團(如氨基、磷酸、磺酸等)，使得共價改質後的碳管，在酒精溶劑中靜置一個月，仍然表現相當優異的分散性質，這樣的結果也說明了，搭配適當的表面改質技術，能使奈米碳管有更多元的應用空間。本研究利用FTIR、XPS與Raman對改質後的碳管做結構上的分析，以及利用TGA以及四點探針，討論改質後碳管薄膜之熱性質與導電特性及其應用潛力分析。

Abstract This study is working on the two-parts modification of carbon nanotubes(CNTs). (I) Non-covalent (II) Covalent modification (I) Pyrene derivatives attach to the surface of CNTs via physisorption, which is the result of a π-π stacking interaction between the pyrene moiety and the CNTs sidewall. We present a simple self-assembly technique to fabricate robust CNTs thin films on glass surface. By employing a cross-linking reagent such as DIC, between the CNT-pyrene complex and the APTES-modified glass substrate with amino groups, it leads to the formation of a strong bonding between CNTs thin films and glass substrate. Characterization by AFM and SEM reveal the morphology of the thin films. The best RMS roughness of our sample is 21.3 nm, which has significant difference compared to the one without APTES-treatment (211nm). We also used water jet to test the interfacial adhesion of the sample and found that the films treated with APTES were robust. Our results on smooth and robust CNTs thin films that show promising potential in industrial applications. (II) We obtained sidewall functionalized CNTs after radical reacted with 4-azidoaniline hydrochloride by UV source. Modified CNTs were prepared by in situ oxidative polymerization with three different monomers. It was found that the dispersion stability of modified CNTs were significantly improved compared to those of the raw SWCNTs. We used FTIR, XPS and Raman spectra to explain the bonding and quality of modified CNTs. Characterized by TGA and four-point probe to discuss the thermal and electrical properties of modified CNTs.

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