臺灣博碩士論文加值系統

近年來，以奈米滴管探針(nanopipette)為基礎衍伸的掃描探針顯微技術(scanning probe technique)，於表面形貌量測、表面電性偵測及表面電化學活性分析等應用領域快速發展，但受限於其所檢測之表面性質與空間維度，較難以使用其他分析技術來輔佐驗證其實驗結果，於樣品或探針的物化性質的定量分析較難建立通用的標準。為解決缺乏對照數據的問題，在本文中使用COMSOL Multiphysics此模擬軟體，依照實際實驗所拍攝的電子顯微鏡影像建立幾何模型，並根據實驗條件建立對應模型後以模擬來預測實驗結果，或由實驗結果來近似得到對應樣品的物化性質。以此法建立的奈米滴管探針模型則能由近似法推測探針表面所具有的表面電荷，並從模擬結果得知幾何形狀與偵測所得電流的關聯性；而碳微電極模型能以近似法得到與利用熱裂解碳沉積法所製備之奈米碳電極相同的電化學性質，並由此預測不同電化學實驗條件下的結果。除了作為實驗的對比基準外，未來能用模擬模型模擬實驗條件，來事先預測實驗成果或從模擬得知樣品或探針所具備的物理、化學性質。

Nanopipette-based scanning probe techniques have been extensively applied in analysis of diverse surface properties with nanometer scale resolution, such as topology determination, surface charge detection and electro-chemical analysis at the interface. Limited by difficulties in batch fabrication of nanopipette-based probes with exactly the same geometry and surface charges, development in precise quantitative analysis of physiochemical properties at interface with pipette-based probes is significantly retarded. To solve this problem, we use a commercial software called “COMSOL Multiphysics” to simulate and predict numerical results obtained via laboratory experiments. The simulation model is built based on the designed experimental setup. The calculated results from simulation are applied to figure out interested properties of the experimental systems under study by fitting the calculated results to the experimental data. The model built in accordance with the nanopipette can figure out the surface charge density of the nanopipette by fitting with the experiment data, and consequently we can get the correlation between the ion current and the geometry of a nanopipette. On the other hand, the electrochemical properties of the carbon nanopipette electrode can be evaluated by the model which simulates the carbon nanoprobe system, and thus we can predict the influence of various parameters that affect electrochemical properties of carbon nanoprobe systems. With these models, quantitative analysis of interfacial physicochemical properties with nanopipette-based systems becomes more feasible.

中文摘要 I
Extended Abstracts II
致謝 XII
目錄 XIII
表目錄 XIV
圖目錄 XV
第1章 緒論與動機 1
1.1 掃描式探針顯微技術(Scanning probe microscopy technique，SPM technique)簡介 1
1.1.1 掃描離子電導顯微鏡 (Scanning ion conductance microscopy，SICM) 1
1.1.2 掃描電化學顯微鏡(Scanning electrochemical microscopy, SECM) 1
1.2 研究動機 2
第2章 文獻回顧 3
2.1奈米滴管探針(nanopipette)簡介 3
2.1.1 奈米滴管探針製備 3
2.1.2 應用離子電流的檢測技術 3
2.2 離子電流整流效應(Ion current rectification effect， ICR) 4
2.2.1 電雙層(Electric double layer，EDL) 4
2.2.2 流道尺寸與幾何形狀 7
2.2.3 表面誘導整流(surface induced rectification，SIR) 9
2.3 掃描離子電導顯微鏡(scanning ion conductance microscopy，SICM) 10
2.3.1 離子電流(ion current) 11
2.3.2 回饋控制模式(feedback mode) 12
2.4 掃描電化學顯微鏡(scanning electrochemical microscopy，SECM) 14
2.4.1 超微電極(ultramicroelectrode, UME) 15
2.4.2 正/負回饋模式(positive/negative feedback mode) 18
2.4.3 基材產生/尖端收集與尖端產生/基材收集模式(substrate generation/tip collection and tip generation/substrate collection mode) 19
2.4.4 微電極探針製備 21
2.5 掃描離子電導－掃描電化學顯微鏡( Scanning ion conductance－Scanning electrochemical microscopy，SICM-SECM) 23
2.6 模擬軟體 Comsol Multiphysics 介紹 24
2.6.1 有限元素分析法(finite element simulation, FEM) 25
2.6.2 COMSOL Multiphysics求解步驟 26
第3章 實驗方法與模擬 28
3.1 奈米滴管探針製備 28
3.1.1 奈米滴管拉製 28
3.1.2 掃描式電子顯微鏡(scanning electron microscope，SEM)影像鑑定 31
3.2 Nanopipette 系統模型建立 33
3.3 CNP (carbon nanoprobe)系統模型建立 36
3.4 奈米滴管－滴管碳電極複合系統模型建立 39
第4章 結果與討論 41
4.1 奈米滴管探針與碳微電極的孔徑與幾何形狀 41
4.2 奈米滴管的COMSOL模型驗證 46
4.2.1 離子整流效應和線性電位掃描伏安法(LSV) 47
4.2.2 Nanopipette作為SICM應用 52
4.3 奈米滴管碳電極的COMSOL模型驗證 57
4.3.1 穩態電流值 57
4.3.2 電化學動力學 62
4.3.3碳電極幾何形貌的影響 67
4.3.4 CNP作為SECM掃描探針的應用 75
4.4 奈米滴管－滴管碳電極複合系統 88
第5章 結論 91
第6章 參考資料 92
第7章 附錄 98

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