A. 有機分子(Chloride, MPS, SPS )自組裝於金 (111) 上所形成的單分子層電性與結構的探討
本研究藉由循環伏安法(cyclic voltammetry, CV)來分析有機分子：氯離子(Chloride anion)、3-Mercaptopropylsulfonic acid (MPS)、bis(3-sulfopropyl)-disulfide (SPS)及混合系統(MPS/Chloride與 SPS/Chloride)下，在電極表面上的電化學行為，並且於電化學系統下利用即時掃瞄式穿隧電子顯微術(in-situ scanning tunneling microscopy, in-situ STM)，可即時記錄分子自組裝方式吸附於金(111)的表面上的過程與分析分子的吸附方式。觀察氯離子在自組裝過程時，經EC-STM的研究之下，可成功的發現到兩種不同的規則結構；(√19 ×√31)與(√21 ×3√7)分別在0.45 V和0.77 V之下。然而，經MPS有機分子修飾過的金(111)電極大約在0.7 V時可觀察到分子的規則吸附，其結構為(9 ×√13)。同樣地，SPS有機分子在金(111)電極表面具有規則吸附，分別為(√7 ×√7)、(7 ×3√3)及(2√3 ×√31)的結構。最後將氯離子與有機分子混合並修飾於金(111)電極上，發現在電位0.2 V下有規則結構產生，其結構為(√19 ×2√13) ，推測此結構是氯離子與有機分子混合後所產生的複合規則結構。

B. 有機分子(Chloride, MPS, SPS )吸附層對於電化學鍍銅的影響
利用電化學的方式將銅電鍍於有機分子修飾後的金(111)電極上，觀察其鍍銅所產生的電化學行為及表面銅層的成長模式，在電化學系統下經由循環伏安法(CV)得知，發現將銅電鍍於MPS或SPS吸附層，對於銅的低電位沉積(UPD)具有抑制的作用。而在任何系統中只要含有氯離子，將會對銅的低電位沉積具有加速的效應。由掃瞄式穿隧電子顯微鏡(in-situ STM)即時觀察銅成長模式，在有機分子SPS與MPS吸附層，其低電位沉積(underpotential deposition, UPD)的成長方式為顆粒狀的成長，過電位沉積(overpotential deposition, OPD)則呈現二維與三維方向成長，而且發現不同的有機分子會影響銅的沉積速率。單純氯離子修飾於電極上，在UPD的電位下則呈現片狀成長；然而在OPD的電位下，經循環伏安法觀察到，其銅會產生兩階段的沉積。最後即時觀察混合系統下銅成長模式，UPD電位下呈現片狀成長而且在第一層銅的成長過程中，會再長第二層銅層於第一層銅層上面。然而在OPD電位區間，經SPS修飾後的電極產生樹枝狀成長且部分位置有大顆粒的銅沉積；而經MPS修飾後的電極則產生顆粒狀成長。

A. Electronic Properties and Adlayer Structures of Organic Molecules (Chloride, MPS, SPS) Self-Assembled Monolayer onto Au(111)
We have used cyclic voltammetry (CV) to study electrochemical features of organic molecules modified Au(111) electrode. In-situ scanning tunneling microscopy (In-situ STM) can study the Self-Assembled Monolayer on Au(111) electrode. The adsorption behavior of Chloride ions was investigated by In-situ STM. The results show that Chloride forms two ordered structures on the electrode surface. At 0.45 V, the structure is (√19 ×√31), and when the potential was elevated to 0.77 V, the structure is (√21 ×3√7). At 0.7 V, MPS modified Au(111) electrode exhibits the ordered monolayer with the structure of (9 ×√13). On the other hand, SPS has the same condition, but the structures are different: (√7 ×√7), (7 ×3√3), and (2√3 ×√31), separately. Finally, in the mixed system (SPS/Chloride and MPS/Chloride) exhibits ordered structure (√19 ×2√13) at 0.2 V.

B. Electrochemical Deposition of Copper onto Organic molecules modified Au(111) electrode
The electronic properties of copper electrodeposition onto molecules- modified electrode is studied by using cyclic voltammetry (CV). Inhibition effect was found as Au(111) covered with MPS or SPS at underpotential deposition (UPD) region. The presence of the Chloride adlayer has an effect on enhancement of the copper deposition, so the UPD peak right shifts slightly in the presence of Chloride. In-situ STM images exhibit that electrodeposition of copper on MPS or SPS modified Au(111) electrode is two-dimensional growth like grain shape when potential sweeps to the UPD region, and three-dimensional growth at OPD region. Copper deposition from Chloride containing solutions, STM images reveals thin film growth mode at UPD region, and three-dimensional random growth at OPD region. Finally, for Chloride ions onto MPS or SPS modified Au(111) electrode, STM images reveals that copper UPD is like the thin film growth, and copper deposition becomes three-dimensional growth in the OPD region, like branches of a plant.

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