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研究生： 李雅雯
Li, Ya-Wen
論文名稱： 含磺酸根硫醚分子在Au(111)電極上的自組裝行為及其對電化學鍍銅的影響
Self-Assembled Behavior of a Sulfonate Thioether and Its Effect on Electrochemical Deposition of Copper on Au(111) Surface
指導教授： 李玉郎
Lee, Yuh-Lang
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 137
中文關鍵詞： 自組裝單分子膜 、掃描式電子穿隧顯微鏡 、電化學鍍銅
外文關鍵詞： Self-assembly monolayer, scanning tunneling microscopy, electrochemical copper deposition, DPS
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    • 本研究利用循環伏安儀(cyclic voltammetry, CV)及電化學式掃描電子穿隧顯微鏡(electrochemical scanning tunneling microscopy, EC-STM)來探討3-(dimethylcarbamothioyl thio) propane-1-sulfonic acid (DPS)分子於金(111)電極表面上的吸附行為及其對於電化學鍍銅之效應。實驗結果顯示吸附在金(111)表面的DPS分子，在高電位(1.1V)時會進行氧化反應，並產生氧化態之DPS(DPSo)。若溶液中不含有DPS分子，氧化後的DPS分子在電位0.8 V會形成(√13×√31)及2種具有不同分子構型的(√13×6)之規則結構。但若溶液中含有DPS，氧化後，因大量DPSo分子的吸附，分子膜會形成聚集的分子團，無法觀察到規則的結構。此外，吸附的DPS分子膜(DPS或DPSo)會在0~0.2 V電位區間進行脫附。
    在電化學鍍銅上的實驗發現，氧化後的DPS分子對銅的低電位沉積(UPD)及過電位沉積(OPD)皆有促進的效果。由STM的觀察發現，UPD銅膜會形成單層的二維島嶼型態，而OPD銅傾向於三維的成長模式。在高電位(1.25V)停留30分鐘後使溶液中的DPSo分子數量增加，其對銅沉積量及銅島狀物的高度皆有增加的趨勢。此外，本研究亦發現，在DPS氧化的程序中若有銅離子的存在，則會形成DPSo-Cu2+複合物，此一複合物可增加銅在UPD電位區間的沉積量，並改變UPD銅膜表層銅原子的排列。而在OPD電位區間，硫酸根離子會吸附於載體表面，佔據銅離子可反應的位置，使銅的沉積量下降，改變OPD的沉積型態。

    Cyclic voltammetry (CV) and electrochemical scanning tunneling microscopy (EC-STM) were used to study the self-assembly behavior of 3-(dimethylcarbamothioyl thio) propane-1-sulfonic acid (DPS) on Au(111), as well as its effects on the Cu deposition. The results show that the adsorbed DPS will be oxidized to be an oxidized state (DPSo) at ca. 1.1 V. The adsorbed DPSo self-organizes into ordered structures, (√13 × √31) and (√13 × 6), at 0.8 V when the solution is free of DPS. However, when DPS molecules are contained in the solution, a larger amount of DPS will be oxidized and adsorb on the surface, leading to the formation of aggregate islands. Ordered adlayer cannot be observed in this case. Besides, the adsorbed DPS and DPSo will desorb when the potential is cathodically swept to about 0-0.2 V.
    The results on the electrochemical Cu deposition reveal that the oxidized DPS can enhance the Cu deposition in both the UPD and OPD stages. Under the observation of an in-situ STM, the UPD Cu film demonstrates as monolayer islands, while the OPD Cu film exhibits a 3-dimentional morphology. When a larger amount of DPSo was formed by prolonging the oxidization time at 1.25 V, the Cu deposition will be enhanced. This study also find that, if the DPS oxidization is performed at the presence of Cu ions, a (DPSo-Cu2+) complex will form. This complex demonstrates a distinct effect to the Cu deposition. In the Cu UPD region, the complex will increase the deposition amount of Cu and, meanwhile, leads to a different arrangement of top-most Cu atoms. In the OPD stage, less Cu islands was deposited. This result is ascribed to the weaker interaction of DPSo-Cu2+ complex to the Cu substrate. Parts of the active sites were occupied by the adsorbed SO42- ions which decreases the deposition rate of Cu.

    摘要 I Abstract III 誌謝 V 表目錄 X 圖目錄 XI 第一章 緒論 1 1.1 前言 1 1.2 研究動機 4 第二章 文獻回顧 5 2.1 自組裝單分子膜 (self-assembled monolayers, SAMs)的介紹 5 2.1.1 自組裝單分子膜系統的發展及起源 5 2.1.2 自組裝單分子膜系統的分類 6 2.1.3 自組裝現象及分子的特性 8 2.1.4 有機硫化物自組裝於金(111)電極之相關研究 9 2.1.4.1 烷基硫醇及二烷基二硫化物 9 2.1.4.2 硫醚 10 2.1.5 自組裝分子薄膜的應用 21 2.2 銅製程技術簡介 23 2.2.1 電鍍銅填充盲孔之技術發展 23 2.2.2 電鍍銅添加劑的種類及其作用原理 27 2.2.2.1 氫離子(H+) 27 2.2.2.2 氯離子(Cl-) 28 2.2.2.3 抑制劑(Suppressor) 30 2.2.2.4 平整劑(Leveler) 31 2.2.2.5 加速劑(Accelerator)或光澤劑(Brightener) 32 2.2.3 低電位沉積(UPD)文獻回顧 42 第三章 實驗部分 51 3.1 氣體及耗材 51 3.2 藥品 51 3.3 儀器設備 52 3.3.1 循環伏安儀 (Cyclic Voltammogram, CV) 52 3.3.2 掃描式電子穿隧顯微鏡(Scanning Tunneling Microscopy, STM) 55 3.3.2.1 儀器操作原理 55 3.3.2.2 取像方法 58 3.3.2.3 儀器裝置介紹 60 3.4 實驗步驟 65 3.4.1 金屬單晶電極的製備 65 3.4.2 STM的前處理 65 3.4.3 循環伏安儀的前處理 67 3.4.4 DPS自組裝單分子膜的製備與鍍銅效應實驗程序 69 第四章 結果與討論 71 4.1 DPS分子於金(111)上自組裝行為的探討 71 4.1.1 利用循環伏安儀檢測DPS單分子膜的電化學特性 71 4.1.2 利用STM觀察DPS單分子膜於金(111)電極的自組裝行為 75 4.2 銅於金(111)表面的沉積行為 86 4.2.1 電化學鍍銅於金(111)之循環伏安圖 86 4.2.2 STM觀察電化學鍍銅於金(111)電極 88 4.3 DPS分子對電鍍銅於金(111)上之影響 91 4.3.1 利用循環伏安儀檢測DPS分子對電化學鍍銅於金(111)電極之影響 91 4.3.2 利用STM觀察銅於DPS修飾之金(111)電極的沉積行為 98 4.4 DPSo-Cu2+複合物對電化學鍍銅於金(111)表面的影響 112 4.4.1 利用循環伏安儀檢測DPSo-Cu2+複合物於金(111)電極 112 4.4.2 利用STM觀察DPSo-Cu2+複合物於金(111)電極 115 第五章 結論 129 第六章 參考文獻 131

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