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研究生：	林品均 Lin, Pin-Chun
論文名稱：	含磺酸根硫醚之自組裝單分子膜在Au(111)電極上的吸附及其對電化學鍍銅的效應 Self-Assembled Monolayer of Thioether with Sulfonate Adsorbed on Au(111) Surface and Its Effect on Electrochemical Deposition of Copper
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：	2010
畢業學年度：	98
語文別：	中文
論文頁數：	111
中文關鍵詞：	自組裝單分子膜、磺酸根、掃描式電子穿隧顯微鏡、循環伏安法、電化學鍍銅、氯
外文關鍵詞：	SAMs, TBPS, sulfonic, STM, CV, copper deposition, chloride
相關次數：	點閱：119 下載：0
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本研究的主要工作可分為二部份，第一部份是藉由循環伏安法 (cyclic voltammetry, CV) 以及電化學掃描式電子穿隧顯微鏡 ( electrochemical scanning tunneling microscopy, EC-STM) 來分析有機硫醚分子3,3’-thiobis(1-propanesulfonic acid, sodium salt) (TBPS) 自組裝單分子膜於金(111)上的吸附結構及電化學行為。在STM觀察之下，TBPS單分子膜於0.8 V (vs. RHE) 會形成 (6 × 3√3) 的規則結構 ; 然而當電位低於0.7 V時，TBPS吸附層呈現不規則的排列，而在0.06 V時產生脫附的行為。從CV實驗中得知，0.3 V ~ 1.0 V為TBPS單分子膜穩定存在的區間，TBPS要到1.2 V之後才會完全氧化。

本研究的第二部份是利用電化學的方式將銅電鍍於TBPS單分子膜修飾後的金(111)電極上，觀察鍍銅過程中的電化學行為及表面銅層的成長模式。由CV實驗中得知， TBPS單分子膜的修飾對銅的低電位沉積 (underpotential deposition, UPD) 有稍微促進的效果，過電位沉積 (overpotential deposition, OPD) 則是沿載體方向進行特殊的二維條狀成長。當溶液中有氯離子存在時，對於銅的UPD及OPD皆有明顯的促進效果，銅沉積的方式在UPD電位下呈片狀成長，在OPD電位區間則產生顆粒狀的形態。當氯離子濃度較高時，有助於銅成長為平台狀的表面形式。此外，本研究亦發現，TBPS自組裝膜製備後，基板的潤洗與否對後續的鍍銅程序有明顯的差異，未經潤洗的修飾基板，對於銅在UPD及OPD電位區間的成長有較明顯的促進效果。

This research includes two parts. In the first part, the adsorption behavior and electrochemical features of an organic thioether— 3,3’-thiobis(1-propanesulfonic acid, sodium salt) (TBPS) on Au(111) electrode were investigated by using cyclic voltammetry (CV) and in-situ scanning tunneling microscopy (STM). Under the investigation of STM, an ordered TBPS adlattice can be observed at 0.8 V (vs. RHE) and the structure is identified to be (6 × 3√3). When the potential was negatively shifted, the TBPS adlayer becomes disorder at ca. 0.7 V and desorbed from the Au(111) surface at ca. 0.06 V. The CV spectrum reveals that the TBPS monolayer adsorbs stably at the potential range between 0.3 V ~ 1.0 V, and oxidizes when the potential was elevated up above 1.2 V.

For the second part of this study, electrochemical deposition of copper was performed on the TBPS-modified Au(111) surface. The CV results indicate that the TBPS adlayer has a slightly enhancement effect to the underpotential deposition (UPD) of copper. For the overpotential deposition (OPD), the modification of TBPS triggers a one dimensional growth mode of copper, formation of copper clusters with rode-like morphology. The presence of the chloride ions has an enhancement effect to the copper deposition both in the UPD and OPD regions. It’s also found that the deposition rate was also affected by the chloride concentration and the rinsing conditions of the TBPS-modified Au(111) substrates after the self-assembling process.

摘要.......................................................I
Abstract..................................................II
誌謝.....................................................III
目錄......................................................IV
表目錄...................................................VIII
圖目錄.....................................................IX
第1章 緒論..................................................1
1 前言...................................................1
2 研究動機與目的...........................................3
第2章 文獻回顧...............................................4
1 自組裝單分子膜 (self-assembled monolayers, SAMs) 的介紹...4
1.1 自組裝單分子膜系統的發展及起源............................4
1.2 自組裝單分子膜系統的分類.................................4
1.3 自組裝現象及分子的特性...................................6
1.4 自組裝分子薄膜的應用....................................7
1.5 有機硫化物自組裝於金屬基材之相關研究.......................9
1.5.1 烷基硫醇及二烷基二硫化物...............................9
1.5.2 硫醚..............................................10
2 金屬基材對SAMs排列之影響.................................16
3 銅製程技術簡介..........................................17
3.1 電鍍銅填充盲孔之技術發展................................17
3.2 電鍍銅添加劑的種類及其作用原理...........................22
3.2.1 氫離子(H+).........................................22
3.2.2 氯離子(Cl-)........................................22
3.2.3 抑制劑(Suppressor).................................23
3.2.4 平整劑(Leveler)....................................24
3.2.5 加速劑(Accelerator)或光澤劑(Brightener).............26
3.3 低電位沉積(UPD)文獻回顧................................28
第3章 實驗部份..............................................36
1 氣體及耗材.............................................36
2 藥品..................................................36
3 儀器設備...............................................37
3.1 循環伏安儀 (Cyclic Voltammogram, CV).................37
3.2 掃描式電子穿隧顯微鏡(Scanning Tunneling Microscopy, STM)	  .........................................................40
3.2.1 儀器操作原理........................................40
3.2.2 取像方法...........................................42
3.2.3 儀器架構...........................................43
4 實驗步驟...............................................48
4.1  STM 部分...........................................48
4.2 循環伏安儀掃描的前處理..................................50
4.3 自組裝單分子膜的製備...................................51
4.4 銅電化學沉積流程......................................51
第4章 結果與討論............................................52
1 金(111)電極的重排現象....................................52
1.1 金(111)電極在0.1 M過氯酸中之循環伏安圖...................52
1.2  STM觀察金(111)電極重排現象............................54
2  TBPS於金(111)上的自組裝單分子膜之電性與結構的探討...........58
2.1 利用循環伏安儀檢測TPBS單分子膜的電化學特性.................58
2.1.1 循環伏安圖.........................................58
2.1.2 脫附實驗...........................................62
2.1.3 電流對時間關係圖.....................................64
2.2 利用STM觀察TPBS單分子膜吸附於金(111)上的行為..............66
3  TBPS單分子膜於金(111)上之電化學鍍銅效應的探討..............72
3.1 以循環伏安法分析銅於金(111)表面之沉積行為.................72
3.2 以循環伏安法分析TBPS單分子膜於金(111)電極之電化學鍍銅特性....75
3.3 利用STM觀察TBPS單分子膜於金(111)電極之電化學鍍銅特性.......77
4 氯離子效應對TBPS單分子膜於金(111)上之電化學鍍銅的影響.........82
4.1 利用循環伏安儀測試氯離子濃度的差異對TBPS單分子膜於金(111)電極上電化學鍍銅的影響............................................82
4.2 STM觀察低濃度氯離子 (77 μM) 對TBPS單分子膜於金(111)電極上電化學鍍銅的影響...............................................85
4.3 STM觀察高濃度氯離子 (0.77 mM) 對TBPS單分子膜於金(111)電極上電化學鍍銅的影響..............................................91
5  TBPS在未潤洗情況下自組裝於金(111)上之電化學特性及銅沉積行為的探討	.........................................................96
5.1 未潤洗之TBPS自組裝分子膜於金(111)上的電化學特性...........96
5.2 未潤洗之TBPS自組裝分子膜於金(111)上的電化學鍍銅效應........98
第5章 結論................................................104
1  TBPS自組裝單分子膜於金(111)上電性及分子結構的探討..........104
2  TBPS自組裝單分子膜於金(111)上電化學鍍銅的探討.............104
第6章 參考文獻.............................................106

                                    

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