[[alternative]]Manufacturing and wettability of dual-dimension micro/nano-structure

碩士[[abstract]]本研究已成功製得三種斥水之漣漪結構，並使用垂直取向角度量測儀量測液滴與連漪結構垂直之平均接觸角：1.將俱漣漪結構之聚二甲基矽氧烷，以微電鑄法翻製俱漣漪結構之鎳模仁，並使用霧狀鎳電鑄法製作粗化之漣漪結構，其中波長4.0μm連漪結構之平均最大接觸角為130°；(二) 將非離子界面活性劑沾附在波長2.6μm漣漪結構之波峰，可得到平均最大接觸角為140°；(三)用PDMS溶膠翻製波長2.0μm漣漪結構之PDMS薄膜，可得到平均最大接觸角為154°。[[abstract]]The present study has been proposed three manufacturing methodology to fabricate the hydrophobic ripple structure , and measured the contact angle between a distilled water and these ripple structure which droplets vertically on hydrophobic ripple structure using by the contact angle analysis system : (1) used the micro-electroforming and particle-nickel technology to fabricate the roughen ripple structure with 4.0μm in wavelength can be obtained average contact angle approximately 130 degree ; (2) adhered the nonionic surfactant on the peaks of the ripple structure with 4.0μm in wavelength can be obtained an average contact angle approximately 140 degree (3) used the replicating method to copy the PDMS ripple structure with 2.0μm in wavelength from a PDMS ripple structure has same wavelength and a gold film sputtered on the ripple structure can be obtained average contact angle approximately 154 degree。[[tableofcontents]]總目錄 中文摘要...........................................................................................I 英文摘要................................... ............................................. .........II 總目錄......................................... ....................................................III 壹、導論............. ... .........................................................................1 1-1 前言... .................................. ....................................................1 1-2文獻回顧.......... .................................. .......................................3 1-2-1 表面潤濕性............................. ...............................................3 1-2-1.1 接觸角(Contact angle；CA)............. .... ...........................3 1-2-1.2 Wenzel’s model............................... ....................................4 1-2-1.3 Cassie and Baxter’s model........... .......................................4 1-2-1.4 接觸角的遲滯性............................... ....................................4 1-2-1.5 表面自由能............... ...........................................................5 1-2-2 粗糙表面之潤濕機制........... ....................................................6 1-2-2.1 微結構表面之潤濕............................. ...................................6 1-2-2.2 疏水性與粗糙表面吸附之關係...............................................7 1-2-3 疏水性基材製程............................... ........................................8 1-2-3.1 微機電製程與微結構壓印.......................................................8 1-2-3.2 溶膠－凝膠合成法(Sol-Gel)...................................................10 1-2-3.3 陽極處理(Anodizing threatment)...........................................11 1-2-3.4 奈米球模板(Nanosphere lithography)...................................12 1-2-3.5 微電鑄法...............................................................................14 1-3 研究範疇........................ .............................................................16 貳、實驗設計................. ....................................................................26 2-1 實驗材料與設備......... .................................................................26 2-1.1 實驗材料................. .................................................................26 2-1.2 實驗設備.............................. ....................................................26 2-2 俱漣漪結構薄膜製作.............. .....................................................27 2-2.1 矽晶圓準備工作................. ......................................................27 2-2.2 PDMS溶膠配製.................... ...................................................28 2-2.3 PDMS溶膠旋轉塗佈與真空烘乾...............................................28 2-2.4 薄膜拉伸.................. ................................................................28 2-2.5 真空濺鍍.............. ....................................................................29 2-3 不飽和聚脂樹脂對PDMS漣漪結構翻製.. ...................................29 2-4 PDMS溶膠對PDMS俱漣漪結構薄膜之翻模...............................29 2-5 微電鑄製程................................ .................................................30 2-5.1 霧狀鎳製程.................................... ..........................................32 2-6 俱非離子界面活性劑之PDMS薄膜.............................................32 2-7 表面形貌之觀察............................ .............................................33 2-7.1 光學顯微鏡(Optical Microscopy；OM)....................................33 2-7.2 掃描式電子顯微鏡(Scanning Electron Microscopy ；SEM)….33 2-7.3 原子力顯微鏡(Atomic Force Microscope；AFM).....................33 2-8 接觸角之量測..................................... ........................................33 参、結果與討論....................................... .........................................37 3-1 拉伸應變對PDMS漣漪結構之影響............... ............................37 3-2 不飽和聚脂樹脂翻製漣漪結構.....................................................38 3-3 使用PDMS溶膠翻製漣漪結構...................................................38 3-4 俱漣漪結構之PDMS模塊以微電鑄翻製鎳模..............................38 3-5 接觸角量測.................................................................................39 肆、結論............................................................................................66 伍、參考文獻.....................................................................................68 圖目錄 圖1-1 水珠在蓮花表面之疏水性微結構帶走污垢微粒之示意圖，此種微 結構之特性能讓水珠輕易在表面滾動【2】。...........................................................17 圖1-2 超疏水性塗裝在現今已非常普遍，如房屋外牆之油漆塗裝，利用 奈米技術使得髒汙不易殘留牆面，維持乾淨美觀【3】。.........................................18 圖1-3 左圖為親水性表面示意圖，液體容易附著於表面且髒汙不易帶走； 右圖為疏水性表面示意圖，液體不易附著於表面，並且輕易帶走髒污【5】。..........19 圖1-4 Wenzel’s model示意圖，液體在結構表面部分潤濕【7】。... ......................20 圖1-5 Cassie’s model之示意圖，液體在理想表面無潤濕之情形，表示 為疏水性表面【9】。. ........................................................... ..................................20 圖1-6 (a)前進接觸角之示意圖，當液滴往下時接觸角增加為θa；(b)後 退接觸角，當液滴網上時接觸角減少為θb【10】。................. ................................21 圖1-7 Shibuichi等人對平面及粗糙面之接觸角量測結果(黑圓點)， 及 Bico等人推導之理論方程式(黑實線)【11】。................................ ..........................22 圖1-8 微機電製程(MEMS)之示意圖，係以結構模仁在光阻上壓印出相 同之結構【16】。.................... .................... .................... ......................................23 圖1-9顯示不同粒徑之球陣列板及其接觸角：經ODT表面改性之平整 金層接觸角為114°，俱奈米半球形結構且經ODT表面改性之基材其接 觸角可大於130°，甚至可達168°；其接觸角隨著奈米球面直徑縮小而 增加【19】。.. .................................. ......................................................................24 圖1-10 微電鑄架構示意圖，陽極為擬鍍物鎳材，陰極為欲鍍物，電鍍 液必須帶有擬鍍物之金屬離子【20】。... ................................................................25 圖2-1 PDMS薄膜拉伸治具之照片。................ ........................ ............................34 圖2-2 PDMS薄膜經固定拉伸應變及鍍金後，薄膜回放之照片。...........................35 圖2-3 微電鑄前置作業，照片中表示各部位置。.......... ........................................36 圖3-1 厚度2.5mm、楊式模數0.604MPa之PDMS以三種拉伸應變 分別為(a)10%；(b)20%；(c)30%，鍍金20秒後應力回復產生不同波 長漣漪結構之OM照片。......................... .............................................................45 圖3-2 PDMS模塊以三種拉伸應變分別為(a)10%；(b)20%；(c)30%， 鍍金20秒後應力回復產生不同波長漣漪結構之SEM照片。.................................46 圖3-3 不飽和聚脂樹脂對俱有漣漪結構之PDMS薄膜表面翻模之OM照片。........47 圖3-4 不飽和聚脂樹脂翻製PDMS薄膜之漣漪結構OM照片：(a)翻模前之 PDMS漣漪結構；(b)減少硬化劑比例、延長硬化時間所得到之無殘膠表面 ，但仍可發現因保力膠與金鍍層介面壓縮應力產生之裂紋。..................................48 圖3-5 PDMS溶膠對表面具漣漪結構之PDMS薄膜翻製之OM照片：……...........49 (A)翻模較為完整之漣漪結構；(b)拔模時，將波谷部分拔起形成相互成 對之漣漪差排。圖3-6 拉伸率30%，鍍金10A俱漣漪結構之PDMS模 塊翻製微電鑄鎳模仁：(a)鎳模仁及(b)PDMS溶膠翻製鎳模仁之漣漪結 構OM照片。... ..................................................... ................................................50 圖3-7 拉伸率30%之PDMS翻製微電鑄霧面處理鎳膜仁之SEM照片。...............51 圖3-8 伸長率0%至110%之PDMS薄膜液滴於平形漣漪方向之平均 接觸角：(a) 92°(b) 95°(c) 125°(d) 132°(e) 134°(f) 140°(g)126° (h) 134°(i) 129 (j) 130 (k)128°(l)137°。…………………..........................................52 圖3-9伸長率10%至110%之PDMS薄膜液滴於垂直漣漪方向之 平均接觸角：(a) 89°(b) 127° (c) 132°(d) 141 (e) 143°(f) 136°(g) 145° (h) 153°(i) 139°(j) 137°(k) 144°。...........................................................................53 圖3-10 漣漪差排之OM照片。.......................... ...................................................54 圖3-11 漣漪生成時無法迅速釋放應力產生之裂痕。........ ....................................55 圖3-12 漣漪結構中產生之排向表面裂縫。............. .............................................56 圖3-13 非離子界面活性劑噴覆於不同伸長率PDMS薄膜之OM照片 ，由上而下分別為10%至110%。圖3-14 非離子界面活性劑噴覆於伸 長率0%至110%具漣漪結構薄膜表面，液滴與漣漪結構垂直之平均接 觸角，分別為(a)112°(b)101°(c) 105° (d) 139°(e) 130°(f) 138°(g) 141°(h) 124°(i) 123°(j) 130°(k) 128°(l)128。...................... ...............................................58 圖3-15 非等離子界面活性劑噴覆於載玻片上，再將伸長率10%至110% 具漣漪結構之PDMS薄膜覆蓋於載玻片，乾燥後得到之OM照片。 圖3-16 非離子界面活性劑噴覆於伸長率10%至110%具漣漪結構薄膜表面 ，液滴與漣漪結構平行之平均接觸角，分別為(a) 98°(b) 99°(c) 135° (d)127°(e) 128°(f) 134°(g) 116°(h) 106°(i) 114°(j) 124° (k) 120°。.......................60 圖3-17 將伸長率10%至110%具漣漪結構之PDMS薄膜，覆蓋於表面 俱非離子界面活性劑之載玻片，乾燥後量測液滴與漣漪結構垂直之接觸 角分別為(a) 133°(b) 138°(c) 136°(d) 137°(e) 138°(f) 137 °(g) 140°(h) 128° (i) 128°(j) 134°(k) 132°。......................................................................................61 圖3-18 將伸長率10%至110%具漣漪結構之PDMS薄膜，覆蓋於表面 俱非離子界面活性劑之載玻片，乾燥後量測液滴與漣漪結構平行之接觸 角分別為(a) 109°(b) 129°(c) 131°(d) 127°(e) 128°(f) 130° (g) 133°(h) 136°(i) 138°(j) 137° (k)132°。................................................................................62 圖3-19 以PDMS溶膠翻製伸長率10%至110%具漣漪結構之PDMS 薄膜OM照片。..... .................... .................... .................... ................................ 63 圖3-20 PDMS溶膠翻製伸長率10%至110%具漣漪結構之PDMS薄膜， 液滴垂直於漣漪結構之接觸角分別為(a)134°(b)140°(c)115°(d)135° (e)148°(f)148°(g)145°(h)154°(i)139°(j)149°(k)144°。………………………………..64 圖3-21 PDMS溶膠翻製伸長率10%至110%具漣漪結構之PDMS薄膜 ，液滴平行於漣漪結構之接觸角分別為(a)124°(b)132°(c)118°(d)121° (e)119°(f)118° (g)126°(h)123°(i)120°(j)123°(k)118°。............................................65[[note]]學號: 699370168, 學年度: 10