具咪唑(imidazole)官能基硫醇分子於金(111)上之吸附及對電鍍銅的影響

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劉芸圻(Yun-Chi Liu) 查詢紙本館藏

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化學學系

論文名稱

具咪唑(imidazole)官能基硫醇分子於金(111)上之吸附及對電鍍銅的影響

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摘要(中)

在這項研究中透過循環伏安法（CV）和掃描式穿隧電子顯微鏡（STM）於硫酸、過氯酸和鹽酸中研究了2-巰基-5-苯並咪唑磺酸（MBIS）與2-巰基苯并咪唑（MBI）吸附在金（111）上的空間結構，揭示了電位控制和分子濃度對吸附構型和表面排列的巨大影響。同時也探討了MBI分子和MBIS分子吸附在金（111）電極上對於電鍍銅的影響。
首先，透過STM觀察MBIS分子和MBI分子可形成有序分子膜，其單位晶格分別為（3√3 × 3√3）和（√3 × 5）。 MBIS分子和MBI分子的覆蓋度分別是0.11和0.23。MBIS分子比MBI分子更鬆散地組裝在金（111）上，這是由於磺酸根基團的排斥力，使分子間的相互作用更大。
其次，MBIS分子和MBI分子在硫酸和過氯酸中形成相同的有序結構，但在鹽酸中卻呈現無序。這種現象表明，陰離子深刻影響著MBIS分子和MBI分子的吸附。在另一項實驗結果中發現，當電解質中MBIS分子的濃度逐漸增加，MBIS分子的結構從有序變為無序。相反地，MBI分子結構並不受影響，在越來越高的分子濃度中（√3 × 5）的結構依然存在。
最後，MBIS分子和MBI分子都在低分子濃度下加速了銅在金（111）上的電沉積，但在高濃度下卻減緩了沉積速度。

摘要(英)

In this study, the spatial structures of 2-Mercapto-5-benzimidazolesulfonic acid (MBIS) and 2-Benzimidazolethiol (MBI) adsorbed on Au(111) have been investigated by cyclic voltammetry (CV) and scanning tunneling microscopy (STM) in sulfuric, perchloric and hydrochloric acids, revealing the immense effects of potential controlled and molecular concentration on the adsorption configuration and surface arrangement. The effects of MBI and MBIS adsorbed on a Au(111) electrode on copper electroplating are exaamined.
First, MBIS and MBI form order molecular films, whose unit cells are (3√3 × 3√3) and (√3 × 5), as characterized by STM. The coverage of MBIS and MBI is 0.11 and 0.23. MBIS is more loosely packed on Au(111) than MBI, suggesting a greater repulsive intermolecular interaction due to the sulfonate group.
Secondly, both MBIS and MBI form the same ordered structure in sulfuric and perchloric acids, but they are disordered in hydrochloric acid. This phenomenon indicates a profound effect of anion is the adsorption of MBIS and MBI. In one experiment, where the concentration of MBIS is gradually increased in the electrolyte, the MBIS structure changes from ordered to disordered. In contrast, but the MBI structure is not affect and the structure of (√3 × 5) stays with increasingly higher concentration.
Finally, both MBIS and MBI accelerate the electrodeposition of copper on Au(111) at low molecular concentration, but slow down at high concentration.

關鍵字(中)

★ 穿隧式掃描電子顯微鏡
★ 咪唑衍生物
★ 金(111)

關鍵字(英)

論文目次

摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 vii
表目錄 x
第一章緒論 1
1–1 硫醇分子自組裝分子膜 1
1–1–1 有機硫醇分子自組裝單層膜於金（111）上 1
1–1–2 含芳香環硫醇分子研究 2
1–2 超級填孔（Super–filling） 5
1–2–1 有機硫醇添加劑 5
1–2–2 相關研究 6
1–3 研究動機 6
第二章實驗部分 7
2–1 實驗藥品 7
2–2 實驗耗材 8
2–2–1 氣體 8
2–2–2 金屬線材 8
2–3 儀器設備 9
2–3–1 循環伏安儀（Cyclic Voltammetry, CV) 9
2–3–2 掃描式穿隧電子顯微鏡(Scanning Tunneling Microscope, STM) 9
2–4 實驗步驟 10
2–4–1 CV電極製備與實驗操作步驟 10
2–4–2 STM探針的製備 11
2–4–3 STM電極製備與實驗操作步驟 11
第三章 MBIS於金（111）電極吸附的結果與討論 14
3–1 電位控制對於MBIS分子吸附結構之影響 14
3–1–1 添加1μM MBIS於0.1M硫酸溶液中之CV圖 14
3–1–2 電位控制對於MBIS分子結構的影響及可逆性 16
3–2 不同溶液對MBIS分子結構之影響 27
3–2–1 添加1?M MBIS於0.1M過氯酸溶液中之CV圖及STM圖 27
3–2–2 添加1?M MBIS於0.1M鹽酸溶液中之CV及STM圖 32
3-2-3 添加1mM MBIS於0.1M過氯酸鉀溶液中之CV及STM 36
3–3 濃度變化對MBIS分子結構之影響 39
3–3–1 添加100mM MBIS於0.1M硫酸溶液中之STM及CV圖 39
3–4 第三章小結 42
第四章 MBI於金（111）電極吸附的結果與討論 44
4–1 電位控制對於MBI分子吸附結構之影響 44
4–1–1 添加1?M MBI於0.1M硫酸溶液中之CV圖及STM圖 44
4–1–2 電位控制對於MBI分子結構的影響及可逆性 51
4–2 改變PH值對MBI分子結構之影響 56
4–2–1 添加1 μM MBI於0.1M過氯酸溶液中之CV圖及STM圖 56
4–2–2 添加1 μM MBI於0.1M過氯酸鉀溶液中之CV及STM圖 60
4–3 濃度變化對MBI分子結構之影響 63
4–3–1 添加100mM MBI於0.1M過氯酸溶液中之STM及CV圖 63
4–4 第四章小結 66
第五章 MBIS∕MBI對電沉積銅之影響 68
5–1 添加MBIS∕MBI分子電沉積銅之CV圖 68
5–1–1 添加不同濃度MBIS於0.1M硫酸銅溶液中之CV圖 68
5–1–2 添加不同濃度MBI於0.1M硫酸銅溶液中之CV圖 70
5–2 添加1 μM MBIS分子電沉積銅之STM圖 73
第六章結論 76
第七章參考文獻 77

參考文獻

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指導教授

姚學麟

審核日期

2020-8-17

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