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研究生:張瑀翔
研究生(外文):Chang,Yu-Hsiang
論文名稱:圖案化智能高分子刷製備繞射光柵感應器於矽晶圓表面
論文名稱(外文):Fabrication of the Light-induced Polymer/Gold Composite Brushes on Silicon Wafer as Diffractive Grating Sensor
指導教授:陳建光陳建光引用關係
口試委員:陳建光
口試日期:2014-07-23
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:材料科學與工程系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:中文
論文頁數:170
中文關鍵詞:智慧型高分子原子轉移自由基聚合法高分子光柵光柵EDC/NHS微影製程
外文關鍵詞:Smart polymersatom transfer radical polymerizationpolymer gratinggratingEDC / NHSlithography
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本實驗使用原子轉移自由基聚合法(Atom transfer radical polymerization, ATRP)於圖案化矽晶圓表面進行表面起始聚合(Surface-initiated polymerization)製備出聚(氮-異丙基丙烯醯胺-嵌段-[PMMA聚甲基丙烯酸])(PNIPAAM-b-PMAA)高分子刷再藉由PMAA之carboxylic acid進行EDC/NHS反應改質末端為硫醇後使得奈米金粒子固定於高分子刷末端製備出具有光感應光柵。
結果顯示可在線/間距比率為1:1.5的圖案化光阻晶圓表面長出線寬為1、1.5、2、3 um的一維光柵,而在空氣中高度依序為469.20、542.89、553.16、422.84 nm的結構。由於高分子刷一端固定於表面,另一端可隨環境的改變而呈現不同樣貌,將一維光柵置於25°C水(< LCST)中,發現高度依序變為756.92、1033.05、1189.12、1084.28 nm,而置於50°C水中,高度依序變為640.24、684.37、841.723、790.56 nm,可知高分子受不同環境溫度時影響會有500nm高度上的差異,並在肉眼觀察顏色上有明顯的差異, 1 um的一維光柵在冷水中則呈綠現色,而於熱水中變為藍色,接者利用橢圓測厚儀分析其繞射光譜,證實了光柵之顏色變化,可應用於環境檢測器。進一步為模仿人工功能,在500 nm洞陣列(二維光柵)上接枝高分子刷,利用雷射掃描共軛焦分光光譜顯微鏡(SCMS)即時雷射加熱分析高分子伸展與收縮所造成的孔洞變化,證明光感應型高分子伸展是可產生與虹膜相似的變化,並具有良好回復性,具備製造人工虹膜之潛力。
In this study, we grafted Poly(N-isopropylacrylamide) block Poly(methacrylic acid) (PNIPAAM-b-PMAA) brushes from the initiator-modified surface of patterned silicon wafer by atom transfer radical polymerization (ATRP) to fabricate the Sequentially, we immobilized gold nanoparticles (AuNPs) on the PMAA side chain to generate light-induced polymer grating.
One-dimensional grating of the polymer brushes on the silicon wafer with the different widths are 1 , 1.5 , 2 , 3 ?慆 and thickness is 469.20,542.89,553.16,422.84 nm. Polymer brush is Stimuli-responsive; that is,they dehydrate and collapse when Environment is change .When the temperature is, Thicknesses were changed to 756.92, 1033.05, 1189.12, 1084.28 nm at 25°C (<LCST) due to the thermoresponsive behavior of PNIPAAm. the thicknesses were switched to 640.24 , 684.37 , 841.72 ,790.56 nm at 50 ?aC. Because of significant thickness change, the color changed from green to blue for 1um width grating when the temperature increased from 25 to 50 ?aC. Ellipsometer is exploited to analyze diffractive grating to confirm the results of color change.In addition, we also grafted polymer brush on 500nm ordered hole array to mimic behavior of human iris. The results exhibit the holes could be closed under a laser illumination according to the observation of Spectral confocal and multiphoton system (SCMS).. The close and open behavior of hole array could be reversibly for several cycles. The light-induced polymer grating possessing good recoverability posses high potential to apply in VOC sensor or artificial human iris.
摘要 I
Abstract III
致謝 V
目錄 VIII
圖目錄 XIII
表目錄 XX
1. 緒論 1
1.1. 研究背景 1
1.2. 研究目的 2
2. 理論與文獻回顧 3
2.1. 高分子刷簡介 3
2.2. 自組裝單分子層 6
2.3. 原子轉移自由基聚合法 8
2.4. 液態除氣法 12
2.5. 智能型高分子 13
2.6. 微影製成[26] 18
2.7. 晶圓蝕刻 25
2.8. 金奈米粒子光熱效應 29
2.9. 光柵效應 31
3. 儀器簡介 34
3.1. 原子力顯微鏡(AFM) 34
3.2. 掃描式電子顯微鏡(SEM) 38
3.3. X光光電能譜儀 (XPS) 40
3.4. 共軛焦顯微鏡 (CLSM) 42
4. 實驗流程與方法 45
4.1. 實驗流程圖 45
4.2. 實驗藥品 46
4.3. 實驗儀器 49
4.4. 實驗步驟 52
4.4.1. 矽晶片表面起始高分子刷製作 52
4.4.2. 微影製程製備聚圖案化光阻層 55
4.4.3. 蝕刻製成製作圖案化矽晶圓 58
4.4.4. 矽晶片表面起始聚合圖案化高分子刷 59
4.4.5. 孔洞型矽晶圓表面起始聚合高分子刷 63
4.4.6. EDC/NHS修飾高分子 67
4.4.7. 奈米金粒子製作 68
5. 結果與討論 69
5.1. 矽晶圓表面高分子刷分析 69
5.1.1. FTIR光譜 69
5.1.2. ESCA化學能譜分析 71
5.1.3. 接觸角親疏水測定 78
5.2. 高分子刷表面分析 80
5.2.1. 矽晶圓表面分析 80
5.2.2. APTES自組裝層表面分析 81
5.2.3. ATRP起始劑層表面分析 82
5.2.4. PNIPAAM-b-PMAA高分子刷層 82
5.3. 圖案化高分子刷表面分析 84
5.3.1. 微影製程光阻圖案 84
5.3.2. 圖案化APTES自組裝層 87
5.3.3. 圖案化ATRP起始劑層 88
5.3.4. 圖案化PNIPAAM高分子刷 89
5.3.5. 共聚物PNIPAAM-b-PMAA 96
5.4. 奈米高分子孔洞列陣表面分析 98
5.4.1. 孔洞型矽晶圓表面分析 98
5.4.2. 奈米高分子孔洞列陣 100
5.4.3. 奈米共聚高分子孔洞列陣 103
5.5. 高分子溫度敏感性 104
5.5.1. 高分子溫感形貌測試 104
5.5.2. 高分子回復性測試 108
5.6. 奈米金高分子微結構 111
5.6.1. 奈米金粒子ESCA化學能譜分析 111
5.6.2. 奈米金粒子TEM檢測 115
5.6.3. 金奈米粒子接枝SEM型態測定 116
5.6.4. 圖案化金奈米粒子SEM型態測定 118
5.7. 高分子刷螢光檢測 119
5.7.1. PNIPAAM螢光測試 119
5.7.2. 奈米金熱效應 120
5.7.3. SCMS螢光顯示測定 121
5.8. 光學性質 129
5.8.1. 各圖案化光柵繞射光測定 129
6. 結論 136
參考文獻 137
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