臺灣博碩士論文加值系統

本實驗分為兩個部分，第一部份利用原子轉移自由基聚合(Atom Transfer Radical Polymerization, ATRP)於圖案化矽晶圓製備表面起始聚甲基丙烯酸N,N-二甲氨基乙酯(Poly(2-(dimethylamino)ethyl methacrylate), PDMAEMA)的高分子刷，反應完以傅立葉轉換紅外線光譜儀(FT-IR)、X射線光電子能譜儀(XPS)、高解析場發射掃描式顯微鏡(FE-SEM)、接觸角(CA)分析表面組成。
結果顯示可在線/間距比率為1:1.5的圖案化光阻矽晶圓表面長出現寬為1、1.5、2、3μm的一維光柵，利用原子力顯微鏡(AFM)探討聚合時間與高度的關係，由於高分子刷一端固定於表面，另一端可隨著環境的改變而呈現不同樣貌，在空氣中測得最高高度為457 nm，在pH=4水中高度因正電排斥關係變為1323nm，而在pH=7水中高度因膨潤(swelling)關係變為831nm，最後pH=10水中高度因捲曲(collapsing)關係變為783nm，可推得高分子刷會受到不同酸鹼度環境下影響，高度會有2~3倍的變化，未來可應用於環境檢測器。
第二部分為合成量子點鎘化碲(Quantum Dots,CdTe)，利用正負電作用力吸附方式固定量子點鎘化碲於高分子刷上，形成具有螢光圖案的高分子刷。由場發射穿透式電子顯微鏡(FE-TEM)、光激發螢光光譜儀(PL)、紫外光/可見光光譜儀(UV-Vis)、X光繞射分析儀(XRD)分析CdTe，再由雷射掃描式共軛焦顯微鏡(CLSM)進行觀察，可得到接上量子點的高分子刷之螢光圖案，利用AFM觀察不同pH值間含量子點之高分子刷的伸縮。

In this study, we divide into two parts, First, we grafted Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes from the initiator-modified surface of patterened silicon wafer by Atom Transfer Radical Polymerization (ATRP). After the reactions finish, we can use Fourier Transform Infrared Spectroscope (FTIR), X-ray photoelectron spectroscopy (XPS), Field Emission Scanning Electron Microscope (FE-SEM) and Contact Angle System (CA) to analyze the surface of polymer brushes.
One-dimensional grating of the polymer brushes on the silicon wafer with the different widths are 1, 1.5, 2, 3μm. Using Atomic Force Microscope (AFM) to investigate the relationship between polymerization time and thickness. The highest thickness is 457nm. Polymer brushes are stimuli-responsive, they will swell and collapse when environment changes. When pH value is 4, 7 and 10, the highest thickness is 1323nm, 831nm and 783 nm, because of the positive repulsive force. There are almost double or triple changes of thickness, so we can use the characteristics in grating sensor.
Furthermore, we immobilize quantum dots (CdTe) on the PDMAEMA brushes, and then use UV-vis light to make fluorescent pattern. After we finish the reaction, we use Field-emission transmission electron microscope (FE-TEM), Spectrofluorometer (PL), Ultraviolet-visible spectroscope (UV-Vis) and X-ray Diffractometer (XRD) to analyze quantum dots. Then using Confocal Laser Scanning Microscopy (CLSM) captures the different widths of fluorescent patterns, and find that CdTe was bound to the patterned PDMAEMA brushes.Observing switch of polymer brushes between different pH value by Atomic Force Microscope (AFM).

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審定書
摘要 I
Abstract III
致謝 V
目錄 VII
圖目錄 XII
表目錄 XVIII
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 11
2.5. 智能型高分子 13
2.6. 微影製程[26] 16
2.7. 晶圓蝕刻 23
2.8. 光柵效應 26
2.9. 量子點 28
3. 儀器簡介 32
3.1. 原子力顯微鏡 (AFM) 32
3.2. 掃描式電子顯微鏡 (SEM) 36
3.3. X射線光電能譜儀 (XPS) 38
3.4. 雷射掃描共軛焦顯微鏡(CLSM) 40
3.5. 傅立葉轉換紅外線光譜儀 (FT-IR) 42
3.6. 場發射穿透式電子顯微鏡 (FE-TEM) 46
3.7. 表面電位分析儀 (Zeta-potential) 49
3.8. 紫外光/可見光光譜儀 (UV-Vis) 50
3.9. 接觸角 (CA) 52
3.10. X光繞射分析儀 (XRD) 54
4. 實驗流程與方法 57
4.1. 實驗流程圖 57
4.2. 實驗藥品 58
4.3. 實驗儀器 60
4.4. 實驗步驟 62
4.4.1. 矽晶片表面起始聚合PDMAEMA高分子刷 62
4.4.2. 微影製程製備圖案化光阻層 64
4.4.3. 蝕刻製程製備圖案化矽晶圓 67
4.4.4. 圖案化矽晶片表面起始聚合高分子刷 67
4.4.5. 線型孔洞型矽晶圓表面起始聚合高分子刷 70
4.4.6. CdTe量子點之製備 73
5. 結果與討論 74
5.1. 矽晶圓表面高分子刷分析 74
5.1.1. FTIR光譜 74
5.1.2. ESCA化學能譜分析 76
5.1.3. 接觸角親疏水測定 83
5.2. 高分子刷表面形貌分析 84
5.3. 圖案化高分子刷表面分析 86
5.3.1. 微影製程光阻圖案 86
5.3.2. 圖案化APTES自組裝層 89
5.3.3. 圖案化ATRP起始劑層 89
5.3.4. 圖案化PDMAEMA高分子刷 90
5.3.5. 圖案化PDMAEMA高分子刷用於雷射分析 97
5.4. 高分子聚合於蝕刻表面分析 101
5.4.1. 矽晶圓表面分析 101
5.4.2. 高分子聚合於矽晶圓之形貌分析 104
5.5. 高分子酸鹼性測試分析 107
5.6. 奈米鎘化碲(CdTe)合成與分析 112
5.6.1. Zeta potential表面電位分析 112
5.6.2. SEM、TEM表面形態分析 114
5.6.3. XRD結晶分析 115
5.6.4. UV-Vis、PL光譜分析 116
5.7. 螢光圖案高分子刷檢測與分析 117
5.7.1. CLSM螢光圖案分析 117
5.7.2. SEM、AFM表面形態分析 120
6. 結論 122
參考文獻 123

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