臺灣博碩士論文加值系統

我們的研究主要目標在於開發二維奈米粒子LB緻密薄膜製造技術。所提出的新方法，其精神在於結合傳統的LB技術以及疏水性奈米粒子於高極性環境上自發性地自組裝趨勢。在我們的研究當中，我們利用油酸長碳鏈的性質的界面活性劑，來穩定5~6 nm的銀奈米粒子並且將其分散於低極性的正己烷中成LB分散液，而使顆粒呈現疏水的性質並能浮在空氣與水的交界面，當應用在LB的技術上則因為具有自組裝的效果，因此我們提出恆壓自組裝（Constant-Pressure Self-Asembly, CPSA）的新方式得以順利製備由奈米粒子所組成之薄膜材料。CPSA包含兩個步驟：（i）傳統的LB阻隔棒移動方式，由氣相的分散狀態推擠到過渡相狀態；（ii）固定表面壓使奈米粒子在空氣與水的交界面進行自組裝。第二步即我們所謂恆壓自組裝的過程，我們利用LB儀器可控制表面壓恆定的特點，當機器在固定表面壓力下，經由阻隔棒的來回壓縮動作，減少氣液界面的面積，推動銀奈米粒子進行自組裝。藉由CPSA的過程，我們成左漣Q用阻隔棒將疏水性的奈米粒子推擠成緻密的二維單層薄膜。而所得到的緻密單層薄膜，是將銀奈米粒子組裝成奈米粒子間彼此所能達最小可靠近的間隔，即奈米粒子外層包覆的界面活性劑相接觸的長度大約是2~3 nm的緻密，並且是均勻大片面積的單層薄膜。
因此在本篇論文中，第一章節主要著重於LB儀器的介紹，並且詳細的說明，表面壓偵測原理，與等溫線所表現的意義；第二章節則是探討銀奈米粒子LB分散液的製備以及純化過程，首重獲得粒徑均勻奈米粒子的製備方法，使其適於LB二維奈米粒子緻密薄膜製造技術。第三章節則詳細描述我們發展出的等壓自組裝（CPSA）技術，改善傳統LB技術以及達成上述目標。第四章則是對於這整各技術所寄予的未來展望。

The main theme of my thesis is of the development of a suitable technique in the preparation of a dense film composed of 0D nanoparticles. We have chosen silver nanoparticles synthesized in hexane, with capping (stabilizing) molecules of oleic acid and the average diameters in 5-6 nm, as a model system in our entire studies. The niche of my approach is to combine both conventional Langmuir-Blodgett (LB) technique and the spontaneous self-assembly of hydrophobic nanoparticles at the water-air interface. The method we have been developed called the Constant-Pressure Self-Assembly (CPSA) procedure for fabricating such film. The CPSA comprises of two steps: (i) the conventional LB barrier movement from a dispersed “gas” state to the “transition” state and (ii) self-assembly of nanoparticles at the water/air interface at a constant surface pressure. The second stage of the CPSA process proceeds along with the automatic barriers’ movement to maintain the constant surface pressure. Generally, the reduction of the amount of empty areas on the surface due to the self-assembly leads to the barriers moving towards each other and a decrease of the total surface area. We can then successfully obtain a two-dimensional dense film composed of hydrophobic nanoparticles from such CPSA process, dense monolayer LB film that were pushed by two barriers to compress. The resulting dense monolayer film indicates the interparticle distances are as closed as 2~3 nm which is in accordance with the total length of the capping molecules at the nanoparticle surfaces.
I have arranged the content of my thesis in such a way that the readers can get a clear pictures of the CPSA technique in detail, including Chapter 1: the introduction of the LB technique, isotherm, model derivation of surface pressure detection, Chapter 2: the preparation of a suitable silver nanoparticles LB solution and its characterization, Chapter 3: the detail description and discussion of our CPSA technique, and Chapter 4: the conclusion and prospect of this new LB-CPSA technology.

中文摘要 ii
英文摘要 iii
總目錄 v
圖目錄 vii
表目錄 xii
謝誌 xiii
第一章 序 論 1
1.1 奈米材料物性研究 1
1.2 奈米材料的製備方法簡介 5
1.3 Langmuir-Blodgett（LB）薄膜技術 6
1.3.1 Langmuir薄膜平衡表面壓原理入門 7
1.3.2 Langmuir單層奈米粒子薄膜導論 12
1.3.3 Langmuir-Blodgett（LB）沉積技術 14
1.3.4 Langmuir-Schaefer（LS）沉積技術 16
1.4 研究動機及目標 17
第二章 零維銀奈米粒子LB分散液之製備 19
2.1零維銀奈米粒子之合成策略 19
2.1.1反應物、製備實驗流程及鑑定儀器 21
2.1.2材料鑑定與討論 22
2.2合成後處理及LB分散液的製備 26
2.2.1後處理之目標與流程 26
2.2.2 LB分散液的製備 30
第三章 單層、緻密、大面積分佈的LB薄膜 33
3.1 LB薄膜序言 33
3.2傳統LB薄膜製備流程 34
3.2.1實驗裝置、藥品及檢測設備 34
3.2.2傳統LB技術於奈米粒子組裝薄膜之極限 37
3.3等壓自組裝之構思 45
3.4等壓自組裝薄膜製備條件選擇：起始壓力 47
3.4.1第一轉折點的定義 48
3.4.2通過第一轉折表面壓之等壓自組裝 49
3.4.3未達第一轉折表面壓之等壓自組裝 53
3.4.4於第一轉折表面壓之等壓自組裝 58
3.4.5不同表面壓下的等壓自組裝差異討論 67
3.5等壓自組裝薄膜製備條件選擇：自組裝時間 69
3.5.1短時間等壓自組裝 70
3.5.2長時間等壓自組裝 75
3.6薄膜轉移至固體基材上的技術探討 80
3.6.1 LB膜製備 80
3.6.2 LS膜製備 81
3.6.3 LB膜與LS膜差異討論 81
3.7 LB薄膜物性的檢測與討論 84
第四章 結論與未來展望 90
參考文獻 92

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