臺灣博碩士論文加值系統

中文摘要
本研究中，以三組兩種成份的自組裝混合單層薄膜為研究題材，分別為12-(4-啶)十二烷硫醇 / 十二烷基硫醇、16-硫醇基-1-十六烷醇 / 16-硫醇基十六酸甲酯、15-炔十六烷硫醇 / 十二烷基硫醇，置備不同比例的共同吸附薄膜，以及以其中一種成分置換另一種成分的分子薄膜，利用反射-吸收紅外光譜（FT-IR）的特徵吸收變化，間接觀察比對兩種成分在表面的組成與分布情形。結果顯示表面比例是由溶液中的比例所控制的，16-硫醇基-1-十六烷醇 / 16-硫醇基十六酸甲酯、15-炔十六烷硫醇 / 十二烷基硫醇兩組為分散型的分布，12-(4-啶)十二烷硫醇 / 十二烷基硫醇則較難從中判斷。另外，以12-(4-啶)十二烷硫醇 / 十二烷基硫醇直紋模紋為模板，五銀螺旋錯合物(([Ag5(Bpy-(HC2H-Bpy)2)2])n(CF3SO3)5n))為單元衍生的分子導線系統，利用掃描式電子顯微鏡（SEM）觀察到整齊鏈狀區域呈島狀站立的分布，及原子力顯微鏡（AFM）可觀察到零星突起於其中一列模紋，顯示下方模紋影響五銀錯合物的排列方式。而我們以15-炔十六烷硫醇自組裝薄膜為模板，成功地在末端炔基產生硫化銀（Ag2S）奈米粒子，X光光電子能譜（XPS）可證明其生成，以穿透式電子顯微鏡（TEM）觀察其平均大小約為4.96奈米，原子力顯微鏡可觀察到粒子於表面生成的形貌，同時利用漸進式膜紋及多次處理步驟，嘗試控制成核的大小。

Abstract
Three kinds of binary mixed self-assembled monolayers on gold were prepared: 12-(4-pyridyl) dodecanethiol / dodecanethiol, methyl 16-mercaptohexadecanoate / 16-mercapto-1-hexadecanol, and hexadec-15-yne-1-thiol / dodecanethiol in different ratios. The compositions of these mixed-monolayers were measured by means of infrared reflection spectroscopy (IRS). The structure of the mixed monolayers formed by co-adsorption was compared with that formed by exchange experiment, through analysis of the characteristic absorption frequencies. The results of current study indicated that the ratio of the different components on the gold surface is related to the composition of solutions.
Among the different combinations studied, the mixed layer of methyl 16-mercaptohexadecanoate / 16-mercapto-1-hexadecanol, and hexadec-15-yne-1-thiol / dodecanethiol displayed homogeneous distribution of the two component on the gold surface, while the distribution of 12-(4-pyridyl) dodecanethiol / dodecanethiol was ambiguous.
On a surface patternized with 12-(4-pyridyl) dodecanethiol and dodecanethiol as a template for the growth of (([Ag5(Bpy-(HC2H-Bpy)2)2])n(CF3SO3)5n)) complex, the silver helical complex grew selectively on the pyridyl-bearing SAM surface.
Growth of Ag2S nanoparticles on a SAM of hexadec-15-yne-1-thiol was carried out by derivatizing the terminal acetylene group with silver ion and followed by H2S exposure. The presence of silver sulfide was evidenced by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and transmittance electron microscopy (TEM) imaging. Attempts to vary the size of the nanoparticles by chemical or thermal process were also carried out.

總目錄
總目錄…………………………………………………………………….I
中文摘要………………………………………………………………..IV
英文摘要………………………………………………………………..VI
圖目錄………………………………………………………………...VIII
表目錄…………………………………………………………………..XI
壹、緒論…………………………………………………………………1
1-1 Langmur─Blodgett薄膜………………………………………….…1
1-2 自組裝單層分子薄膜………………………………………………..3
1-3 烷基硫醇自組裝分子薄膜…………………………………………..7
1-4 混合單層分子薄膜…………………………………………………10
1-4-1混合單層分子薄膜的製備與結構………………………………11
1-4-2混合單層分子薄膜的鑑定………………………………………12
1-5混合單層分子薄膜的應用…………………………………………15
1-5-1分子導線的建構………………………………………………….15
1-5-2控制硫化銀粒子的大小………………………………………….17
1-5-2.1硫化銀奈米粒子的合成………………………………………..17
1-5-2.2奈米粒子的組裝技術…………………………………………..19
貳、研究動機與方法…………………………………………………...21
參、實驗部分…………………………………………………………...23
3-1實驗用藥品…………………………………………………………23
3-2合成部分……………………………………………………………25
3-2-1 12-(4-啶)十二烷硫醇的合成………………………………….25
3-3樣品的製備…………………………………………………………27
3-3-1實驗用基材的製備……………………………………………….27
3-3-2混合單層薄膜的製備……………………………………………28
3-3-3以模紋方式製備分子薄膜………………………………………32
3-3-4穿透式電子顯微鏡試樣的製備………………………………….33
3-4實驗用儀器與技術…………………………………………………34
肆、結果與討論………………………………………………………...44
4-1混合單層薄膜之反射-吸收紅外光譜觀察結果…………………...44
4-1-1 12-(4-啶)十二烷硫醇 / 十二烷基硫醇混合單層薄膜（第1組）……………………………………………………………………..45
4-1-1.1共同吸附分子薄膜…………………………………………….45
4-1-1.2置換分子薄膜………………………………………………….46
4-1-1.3分子導線……………………………………………………….47
4-1-2 16-硫醇基-1-十六烷醇 / 16-硫醇基十六酸甲酯混合單層薄膜（第2組）……………………………………………………………..48
4-1-2.1共同吸附分子薄膜……………………………………………..48
4-1-2.2置換分子薄膜…………………………………………………..51
4-1-3 15-炔十六烷硫醇 / 十二烷基硫醇混合單層薄膜（第3組）...51
4-1-3.1共同吸附分子薄膜……………………………………………..51
4-1-3.2置換分子薄膜…………………………………………………..55
4-2分子導線的建構……………………………………………………56
4-2-1掃描式電子顯微鏡觀察結果…………………………………….57
4-2-2原子力顯微鏡觀察結果………………………………………….58
4-3控制硫化銀粒子的大小……………………………………………59
4-3-1 X光光電子能譜觀察結果……………………………………….59
4-3-2原子力顯微鏡觀察結果………………………………………….60
4-3-3掃描式電子顯微鏡觀察結果…………………………………….61
4-3-4掃描式光電子能譜顯微儀觀察結果…………………………….61
4-3-5穿透式電子顯微鏡觀察結果…………………………………….62
伍、結論與未來展望…………………………………………………...64
陸、參考文獻………………………………………………………….101

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