臺灣博碩士論文加值系統

本研究運用靜電逐層組裝技術在玻璃基板上交替地進行聚電解質與SiO2奈米粒子的雙面多層沉積，經鍛燒去除聚電解質並燒結後，形成SiO2奈米粒子薄膜。首先在玻璃基板上沉積帶正、負電的聚電解質建構接著層(adhesion layers)，然後再沉積聚電解質與雙尺寸(22nm 及 7nm) SiO2混合奈米粒子建構本體層(body layers) ，最後沉積聚電解質與單尺寸(7nm) SiO2奈米粒子建構上表層(top layers) 。本體層雙尺寸SiO2奈米粒子溶液，是以不同體積比例混合而成，分別為22nm : 7 nm = 4：1，2：1，1：1，1：2，1：3，1：4，1：5，1：6。另外，亦以個別的單一尺寸SiO2奈米粒子做為本體層當做比較基準。實驗結果顯示，在20個雙層本體層22nm : 7 nm = 1：4，1：5，1：6的條件下，奈米粒子薄膜皆具有透明且超親水的性質，水滴前進接觸角均小於10°，可見光區(400-800 nm)平均穿透度為91.8~92.4％若再植入矽烷自組裝單分子層(self-assembled monolayer, SAMs)，可得到一透明且超疏水表面，水滴前進接觸角可達169~171°，接觸角遲滯只有7~9°，平均穿透度為90.2~91％。這種奈米粒子薄膜的表面在進行矽烷自組裝單分子層處理前後，分別具有超親水與超疏水的極端潤濕性質，提供了表面圖案化與梯度化的絕佳機會。因此，本研究進一步將透明超疏水表面以濕式(聚電解質溶液)法及乾式(雷射雕刻)法進行點、線、面的表面圖案化，可成功得到透明超疏水/超親水圖案化表面﹔此外，亦將透明超親水表面以濕式(前進溶液)法，控制矽烷的反應時間及濃度，亦可成功得到透明超疏水-超親水梯度化表面。

Surfaces patterned with high contrast of wettability and surfaces with continuous wettability gradients may find
many potential allications. Superhydrophilic/superhydrophobicpatterning and superhydrophilic/superhydrophobic gradient on a surface are, therefore, most desirable. In the first part of this work, an electrostatic layer-by-layer (ELbL) assembly process, by which adhesion, body, and top layers were sequentially deposited on glass substrate, was utilized
to fabricate nanoparticulate thin films[PAH (4.0) / PAA (4.0)]5＋ [PAH ( 7.5 ) / ( 22+7nm ) SiO2 ( 9.18 )]20 ＋ [PAH ( 7.5 )/ 7nm SiO2 ( 9.18 )]3 by using SiO2 nanoparticles and polyelectrolytes. The effects of differently sized nanoparticles in body layers on transmittance in visible light region and surface superhydrophobicity were especially emphasized. Actually,
ten compositions in the binary mixture solution of 22 nm and 7 nm silica nanoparticles for body layer deposition were systematically studied. After high temperature sintering and silanization, the as-fabricated nanoparticulate thin films were subjected to characterization. The experimental results revealed that nanoparticulate thin films with average transmittance
higher than that of plain glass, advancing contact angle around 170 o, and contact angle hysteresis around 10 o can be realized by depositing the body layers with mixed 22/7 nm colloidal silica nanoparticle solution with volume ratios of 1：4, 1：5, and 1：6. In the second part of this work, the ensuing transparent and superhydrophobic thin film that was fabricated with volume ratio of 1：4 was chosen for further study of surface patterning. By tuning power and scanning speed of the laser inscriber and
number of scanning, superhydrophilic patterns of dot arrays with minimum 100 μm dot diameter, canals with minimum
100 μm width, and areas of different shapes with 2 mm characteristic length were successfully inscribed by using stainless steel photomask on the superhydrophobic background. In the third part of this work, the nanoparticulate thin film, which was fabricated with volume ratio of 1：4, without silanization was chosen for further study of surface gradients. By controlling the concentration and advancing speed of alkylsilanes solution over the surface of the nanoparticulate thin film, superhydrophobic-superhydrophilic gradient surfaces were successfully created.

摘 要 I
ABSTRACT III
致 謝 V
目 錄 VI
表目錄 X
圖目錄 XI
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 2
第二章 文獻回顧 4
2.1 超疏水表面-蓮花效應 4
2.2 超疏水理論 7
2.2-1 楊氏(Yang)方程式 8
2.2-2溫佐(Wenzel)方程式 8
2.2-3卡西-巴斯特(Cassie and Baxter)方程式 9
2.3 抗反射光學原理 10
2.3.1 破壞性干涉機制 11
2.3.2 漸變折射率機制 12
2.3.3 抗反射膜之製備 13
2.4抗反射超疏水表面 15
2.5表面疏水改質 18
2.6 超疏水/超親水：表面圖案化(patterning) 20
2.7 超疏水 – 超親水：表面梯度化(gradient) 26
第三章 實驗 33
3.1 藥品 33
3.2 儀器設備及裝置 35
3.2.1 浸鍍機(機械手臂) 35
3.2.2超音波洗淨機 36
3.2.3 雷射光散射法粒徑測定儀 36
3.2.4 掃瞄式電子顯微鏡 37
3.2.5 動態接觸角分析儀 38
3.2.6 靜態接觸角測量儀 40
3.2.7 紫外光-可見光光譜儀 40
3.2.8 高溫爐 41
3.2.9 Mili-Q超純水系統 42
3.2.10 CO2 Laser 雕刻機 42
3.3 實驗方法 43
3.3.1玻璃基板的前置清洗流程 43
3.3.2 聚電解質溶液的配製 43
3.3.2.1 SiO2粒子溶液配製 44
3.3.2.2多層膜之製備：靜電逐層組裝技術 44
3.3.3 SiO2奈米粒子薄膜鍛燒 46
3.3.4 SiO2奈米粒子薄膜的疏水改質 46
3.3.5 SiO2奈米粒子薄膜表面圖案化製備 47
3.3.6 SiO2奈米粒子薄膜表面梯度化製備 48
第四章 結果與討論 50
4.1 透明超親水/超疏水SiO2奈米粒子薄膜 50
4.1-1疏水改質前本體層SiO2奈米粒子以不同混合體積比例對二氧化矽奈米粒子薄膜穿透度與潤濕性之分析 50
4.1-2疏水改質後本體層SiO2奈米粒子以不同混合體積比例對二氧化矽奈米粒子薄膜穿透度與潤濕性之分析 54
4.1-3有無上表層對SiO2奈米粒子薄膜穿透度與潤濕性之分析影響 71
4.1-4單一尺寸與雙尺寸的SiO2奈米粒子薄膜之特性比較 74
4.1-5 SiO2奈米粒子薄膜之最適化組裝條件 75
4.2 SiO2奈米粒子薄膜的表面圖案化 75
4.2-1 點、線、面的超疏水/超親水圖案化表面 77
4.2-2 圖案化表面潤濕性分析 81
4.2-3 圖案化表面的潤濕性反差(wettability contrast) 82
4.3 梯度化表面 83
4.3-1 不同液面上升速率對潤濕性梯度的影響 83
4.3-2 不同矽烷濃度對潤濕性梯度的影響 85
4.3-3 超疏水-超親水梯度化表面 86
第五章 結論與建議 89
5.1 結論 89
5.2 建議 90
參考文獻 91
附錄 99
濕式(聚電解質溶液)法製備超親水╱超疏水表面圖案化 99
自述 105

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