自組裝單分子膜(Self-Assembled Monolayer, SAM)於基板表面的修飾可控制鍍膜的成長行為及薄膜的特性，而薄膜成長模式及薄膜結構的控制是決定薄膜材料特性的重要因素，且在金屬鍍膜機制中，鍍膜與基板間的界面性質往往是決定薄膜結構的關鍵因素。本實驗利用掃描式電子穿隧顯微鏡(Scanning Tunneling Microscopy, STM)與表面增強紅外線光譜(Surface-Enhanced Infrared Spectroscopy, SEIRAS)結合電化學系統，即時觀測含磺酸根之二烷基硫化物(3,3-Thiobis(1-propanesulfonic acid, sodium salt), TBPS)在金(111)電極表面的自組裝行為以及其作為電化學鍍銅添加劑時的銅薄膜成長的機制。與一般二烷基硫化物相同的是，TBPS以平躺的方式吸附電極表面，形成低覆蓋率的單分子膜，然而與金原子產生化學鍵結而形成規則結構的現象卻是與有機硫醇分子較為相似。實驗結果顯示，TBPS分子在金(111)表面表現出一複雜、受電位影響的自組裝行為，電極電位改變了分子-分子、分子-載體間的作用力。在鍍銅行為的影響方面，本研究發現在TBPS分子存在的環境下，有效地加速銅的沉積於金表面，且在過程中分子轉置於鍍膜之上。銅overpotential deposition (OPD)的沉積型態則是形成與未含TBPS分子的3D成長有所不同之光滑、低粗糙度的銅膜。
由於有機半導體電子元件的表現受到有機半導體分子膜排列及導電度的影響，然而有機半導體分子常因與金屬表面間的強吸引力而無法形成規則排列，因此本實驗亦將在小分子的自組裝行為的研究延伸至有機半導體高分子的自組裝薄膜，期望能夠製備出具有大範圍高規則度的有機半導體薄膜於金屬表面。我們成功地利用修飾鹵素原子於金(111)表面的方法，製備出具有大範圍規則結構的poly(3-hexylthiophene) (P3HT)分子膜，且利用bottom-up的方式組裝C60於P3HT分子膜之上，形成具有良好導電度、雙連續面單分子膜的奈米結構。在未經修飾的金(111)表面上，P3HT僅能形成彎曲、不規則的吸附型態，為改善此問題，我們預先於金(111)表面修飾溴/碘原子層，降低P3HT與載體的作用力後，使高分子鏈能夠形成規則排列。並藉由調控電極電位將碘原子層脫附，脫附同時由P3HT得到電子進行p-dope，使P3HT單分子膜除具有高規則度外亦有較高的導電度。將C60分子分別組裝於P3HT與p-dope P3HT修飾後的金(111)表面，因p-dope P3HT與C60有較強的donor-acceptor作用力，可得到穩定性、導電度佳的混合分子膜。STS的研究結果顯示碘原子層脫附所引起的p-dope現象會使P3HT單分子膜及混合膜的Fermi level偏移~0.1 eV。本研究提供一簡易、快速的方法來製備具有高規則度奈米結構之有機半導體分子膜。

The interfacial properties between the substrate and the deposited film are the major determinants of film construction. By forming a self-assembled monolayer (SAM) on a substrate surface, one can control the film characteristics and the metal-deposition process. This study reveals the self-assembly process and the effects on metal-deposition process of 3,3-Thiobis(1-propanesulfonic acid, sodium salt) (TBPS) via scanning tunneling microscopy (STM) and surface-enhanced infrared spectroscopy (SEIRAS). TBPS exhibits an adsorption behavior typically observed for dialkyl sulfides including intact adsorption and low coverage phases with molecules predominantly lying flat on the surface. On the other hand, an untypical chemical bond and well-ordered domains were determined which resemble the characteristics of alkenethiol SAMs. In situ STM studies in TBPS-containing electrolyte reveal a very complex, potential-dependent adsorption behavior. This behavior is attributed to the influence of the electrode potential on intermolecular and molecule-substrate interactions as well as on the TBPS coverage. The results also shows that Cu growth on Au(111) - which is known to be strongly kinetically hindered in additive-free, aqueous perchloric acid solutions - proceeds significantly faster in the presence of TBPS. The TBPS molecules either “float” on top of the growing film. Cu growth in the overpotential deposition (OPD) regime results in a smooth Cu film with low surface roughness, in contrast to defect-mediated 3D island growth in additive-free electrolytes.
The performance of organic semiconductor devices depends to a great extent on the arrangement and conductivity of molecules adsorbed on metal substrate surfaces. A central challenge in the creation of well-ordered, supramolecular nanostructures are strong interactions between adsorbent and metal which often lead to poorly ordered adlayer phases. It, therefore, is very important to develop new techniques to produce organic semiconductor films with desired properties. We could succeed to fabricate well-ordered, supramolecular C60/poly(3-hexylthiophene) (P3HT) nanostructures on I-modified Au(111) surfaces. A bottom-up strategy to halide-pretreated single-crystal electrodes in the solution phase has been used because it is a simple and effective approach to fabricate defect-free, nanostructured, and bicontinuous composite-monolayers with exceptional conductivity. The p-type semiconductive polymer, P3HT, has widely been studied, but it has a problem to form randomly oriented and/or curvy-wire morphology on a bare Au(111) electrode. To overcome these problems, we have used iodine-modified Au(111) substrates to let the polymer chains stack and fold into well-organized arrays of two-dimensional, linear architectures with large, ordered domains. At sufficiently negative electrode potentials, electrons transfer from P3HT to iodine leading to iodine desorption and p-doping of the P3HT adlayer. As a consequence, the Fermi level shifts ~0.1 eV toward the HOMO position. This p-doped P3HT monolayer exhibits strong donor-acceptor interactions with n-type materials, like C60. Therefore, a stable C60/P3HT supramolecular nanostructure could be fabricated on Au(111) surfaces. It exhibits high conductivity which can resist a comparatively large potential change from 1 to 0 V. In contrast to previous studies, the nanostructures produced by the present method have a high degree of ordering. Furthermore, the preparation from the solution phase is cost-effective, easy to perform and fast compared to the UHV technique commonly employed in the literature.

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