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研究生:鄭勝勻
論文名稱:金-石墨烯電組裝混成電極開發及其應用於低濃度多巴胺檢測
論文名稱(外文):Electrically-Assisted Assembly of Hybrid Gold-Graphene Electrodes and Their Application in Sensing of Dopamine at Low Concentrations
指導教授:洪健中
學位類別:碩士
校院名稱:國立清華大學
系所名稱:動力機械工程學系
學門:工程學門
學類:機械工程學類
論文種類:學術論文
論文出版年:2013
畢業學年度:101
語文別:中文
論文頁數:119
中文關鍵詞:電沉積三維結構混成電極
外文關鍵詞:electrodepositionthree-dimensional nanostructurehybrid electrode
相關次數:
  • 被引用被引用:0
  • 點閱點閱:135
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  • 下載下載:7
  • 收藏至我的研究室書目清單書目收藏:0
本論文研究利用電沉積的方式組裝奈米材料金粒子以及石墨烯於電極上,藉此方式開發出具三維結構之電極,三維結構的形成能增加電極的工作表面積,並佐以生醫微機電技術整合製作一微流道感測晶片,應用於多巴胺的感測上,期望藉由此高靈敏性的電極能夠在低濃度的環境下達到檢測的目的。
在電沉積組裝奈米材料的製程上,本研究對於金粒子及石墨烯兩種材料的沉積參數做了一系列的探討,對於金粒子的沉積其參數探討電壓、頻率以及時間,而石墨烯則探討其表面改質之活性劑以及沉積時間,在得到這兩種材料的最佳化沉積參數後,再混成沉積這兩種材料,由於金粒子能夠形成高深寬比的三維結構型態,石墨烯片狀的堆疊,結合這兩者的特點所得到的混成電極,將其與金粒子以及石墨烯電極作為對照比較,藉由表面型態、厚度、電性、阻抗以及附著性的探討得知電極的資訊,結果得知金-石墨烯混成電極有較好的特性。
將所開發三維結構之高靈敏感測器其應用於多巴胺的檢測上,由實驗的結果得知有金粒子沉積的電極因三維結構增加表面積大幅的關係,感測訊號電流與未修飾的裸金電極相比可增加約70倍;而濃度感測上則得知有石墨烯沉積在電極的最外層對於多巴胺有較好的感測結果,主要是因為石墨烯與多巴胺的苯環結構能夠產生π-π相互作用,藉此捕捉住多巴胺分子,且金-石墨烯混成電極因石墨烯沉積在金粒子所形成的高深寬比三維結構中,相比於沉積在平坦的裸金電極上能夠更大幅度地沉積,因此感測結果較石墨烯電極的要來的好,而感測的線性區間為2至20 ppb,偵測極限為2 ppb。
本研究所開發之金-石墨烯電組裝混成電極經由三維結構的形成而增加電極的工作表面積,除了對於生醫感測上能增加靈敏性外,對於電極的介面需要增加表面積來強化效能特性的燃料電池、超級電容器等也都具有應用的潛力。

In this research, a hybrid electrode with three-dimensional nanostructures has been developed, fabricated, and characterized. The nanogold and graphene were assembled on electrodes by electrodeposition to form three-dimensional nanostructures that increased surface area of working electrodes. Finally, microfluidic chips with the developed electrodes have been applied for sensing of dopamine at low concentrations.
In this research, the deposition parameters of nanogold and graphene, such as voltage, frequency, time, and surfactant, have been investigated and optimized systematically. The developed technology takes advantage of porous nanostructures, which are formed by gold nanoparticles. Then, graphene are deposited layer by layer on the gold nanoparticles to make the hybrid electrodes. By the measurements of surface morphology, thickness, electric property, resistance, and adherence, we can prove that the gold-graphene hybrid electrode has better characteristics than pure nanogold electrode and pure graphene electrode.
According to the experimental results, the sensing currents increase about 70 times, because the surface area of nanogold deposited electrode substantial increase by the fabricated three-dimensional nanostructures. In dopamine detection, due to π-π interaction between phenyl structure of dopamine and two-dimensional planar hexagonal carbon structure of graphene, dopamine can be captured on the electrode surface. In addition, the sensing results of gold-graphene hybrid electrode are better than the graphene electrode due to the increased surface area. The limit of detection is 2 ppb, and linear range is 2 to 20 ppb.
The gold-graphene hybrid electrode has larger working surface area by formation of three-dimensional nanostructures. In future, the developed technology could be applied to fuel cells and supercapacitors.

摘要 i
Abstract ii
誌謝 iv
目錄 v
圖目錄 vii
表目錄 x
第一章 緒論 1
1.1 微量生物樣本分析 1
1.2 生物感測器概述 2
1.3 高靈敏性生物感測器 5
1.3.1 預濃縮 6
1.3.2 指叉狀電極 6
1.3.3 分子拓印 7
1.3.4 三維結構電極 7
1.4 研究目的與方法 8
1.5 論文計劃書架構 9
第二章 金-石墨烯電組裝混成電極之電性分析 11
2.1 奈米材料 11
2.1.1 奈米金 12
2.1.2 石墨烯 13
2.2 金-石墨烯電組裝混成電極等效電路模型分析 15
2.2.1 表面積與電雙層電容之關係 15
2.2.2 電極等效電路數學模型 16
2.2.3 電化學阻抗頻譜分析原理 23
第三章 金-石墨烯電組裝混成電極開發 27
3.1 文獻回顧 27
3.1.1 奈米金沉積 27
3.1.2 奈米金沉積方法比較 28
3.1.3 石墨烯沉積 29
3.1.4 石墨烯電極沉積方法比較 33
3.2 電泳沉積現象與原理 34
3.3 金-石墨烯電組裝混成電極開發 37
3.3.1 金粒子沉積 37
3.3.2 石墨烯沉積 51
3.3.3 金-石墨烯混成電極 57
3.3.3.1 表面型態觀察 59
3.3.3.2 厚度量測 60
3.3.3.3 電性量測 61
3.3.3.4 阻抗量測 62
3.3.3.5 附著性探討 63
3.4 結論 66
第四章 金-石墨烯電組裝混成電極之電化學感測器應用於低濃度之多巴胺感測 70
4.1 電化學氧化還原反應感測概述 70
4.2 電化學之循環伏安法 73
4.3 電化學生醫感測平台 74
4.4 多巴胺感測 76
4.4.1 藥品準備與實驗步驟 77
4.4.2 電流放大訊號比較 77
4.4.3 多巴胺感測 79
4.4.3.1 π-π相互作用 79
4.4.3.2 多巴胺感測 81
4.5 結論 84
第五章 總結與未來研究建議 86
5.1 總結 86
5.2 論文學術貢獻 87
5.3 未來研究建議 89
附錄 93
A. 石墨烯(graphene)詳細規格 93
B. 量測儀器系統規格 94
C. 晶片微製程 96
D. 金-石墨烯電極旋轉角度及FIB處理後剖面SEM觀察圖 98
E. 阻抗掃頻原始數據 100
F. 甲殼素修飾之電極進行多巴胺感測 102
G. 選擇性測試 106
參考文獻 110
作者簡介 118
著作發表 119

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