臺灣博碩士論文加值系統

本研究以氮化鈦(TiN)作為葡萄糖感測之電極，並沉積Cu-Co雙金屬奈米粒子，利用雙官能的特性，提升非酵素型葡萄糖感測應用的靈敏度，此具新穎價值。利用非平衡直流磁控濺鍍法製備TiN薄膜，藉由調控鍍著參數影響薄膜的表面形貌與電阻率，探討電極性質對生成Cu-Co奈米粒子之影響，並比較Cu-Co奈米粒子形貌和大小對非酵素型葡萄糖感測的效果，進一步比較改變硫酸銅/硫酸鈷溶液比例對於Cu-Co奈米粒子及非酵素型葡萄糖感測的影響。
以不同形貌/不同電阻率之角錐狀高電阻率氮化鈦(PHR-TiN)及顆粒狀低電阻率氮化鈦(GLR-TiN)，與不同形貌/相近電阻率之角錐狀氮化鈦(P-TiN)及顆粒狀氮化鈦(G-TiN)進行比較，反應電壓為-1 V，沉積30秒，在改變硫酸銅/硫酸鈷溶液比例下，不論在不同形貌/不同電阻率或是不同形貌/相近電阻率氮化鈦結果中，都能生成Cu-Co奈米粒子，但電流密度結果中，顆粒狀氮化鈦皆高於角錐狀氮化鈦，而電流密度亦能表示為反應速率，因此，推測是因為顆粒狀表面較為平坦，有較多的成核位置，使反應速率較快，而角錐狀是先在角錐與角錐間成核，成核點較少，使Cu-Co奈米粒子反應較慢，氮化鈦表面形貌對於Cu-Co的生長較電阻率影響大。
探討改變硫酸銅/硫酸鈷溶液濃度比例對於沉積Cu-Co奈米粒子形貌、銅鈷含量比，以及應用於非酵素型葡萄糖感測之影響。在本實驗結果中，TiN形貌為影響Cu-Co形貌及對葡萄糖感測靈敏度的主要因素，在溶液濃度[Cu/(Cu+Co)]sol.=0.5時，葡萄糖感測最佳，以角錐狀氮化鈦為反應電極所沉積之Cu-Co奈米粒子尺寸為43±23 nm，其葡萄糖感測靈敏度為1473±23 μA/cm2․mM，而在顆粒狀氮化鈦為反應電極所沉積的Cu-Co奈米粒子尺寸為50±14 nm，其葡萄糖感測靈敏度為1646±64 μA/cm2․mM；研究中，Cu奈米粒子尺寸為97±30 nm，葡萄糖感測靈敏度為767±39 μA/cm2․mM，Cu-Co奈米粒子的葡萄糖感測靈敏度優於Cu奈米粒子，雙金屬奈米粒子確實能提升葡萄糖感測靈敏度。

This study focuses on the non-enzymatic glucose sensing and the deposition of Cu-Co bimetallic nanoparticles on titanium nitride (TiN) electrodes. The sensitivity of non-enzymatic glucose sensing was promoted by Cu-Co nanoparticles with bifunctional properties. The TiN thin films were deposited by DC unbalanced magnetron reactive sputtering. We discuss effect of the films with different surface morphologies and resistivity by varying the deposition parameters. Then, the Cu-Co nanoparticles were influenced by electrode properties, and compared to their different shapes and sizes for the non-enzymatic glucose sensing. To compare the ratio of CuSO4/CoSO4 solution on Cu-Co nanoparticles and the non-enzymatic glucose sensing, we changed the concentration of CuSO4/CoSO4 solution into different ratio.
The comparison between the different morphologies/different resistivity TiN and the different morphologies/similar resistivity TiN, including high resistivity pyramidal (PHR-TiN), low resistivity granular (GLR-TiN), and pyramidal (P-TiN), granular (G-TiN) structures, respectively. No matter what the solution concentration ratio of CuSO4/CoSO4 is, the Cu-Co nanoparticles were deposited not only on the different morphologies/different resistivity TiN but also the different morphologies/similar resistivity TiN under a potentiostatic mode with -1 V and an applied time with 30 s. The current density of the granular TiN was higher than the pyramidal one, and the current density can be expressed as the reaction rate. It might be the granular TiN with more flat surface so that would have more nucleation sites. The nanoparticles on pyramidal TiN are between the two pyramids with less nucleation sites. The result indicates that the growth of Cu-Co nanoparticles with more influence on the surface morphology of TiN than resistivity.
We investigated the effect of non-enzymatic glucose sensing with different Cu-Co nanoparticles and the content ratio of Cu and Co by changing the concentration of CuSO4/CoSO4 solution. According to the experiment results, the morphologies of TiN are the main factor to cause the different type of morphologies of Cu-Co nanoparticles and the sensitivity of glucose sensing. When the solution concentration [Cu/(Cu+Co)]sol. was 0.5, the sensitivity of glucose sensing was the best. The Cu-Co nanoparticle sizes and the sensitivities of glucose sensing were 43±23 nm/1473±23 μA/cm2․mM for pyramidal TiN (P-TiN) and 50±14 nm/1646±64 μA/cm2․mM for granular TiN (G-TiN). In this study, Cu nanoparticle sizes were 97±30 nm and sensitivities of glucose sensing were 767±39 μA/cm2․mM. As the results, the Cu-Co nanoparticles sensitivities of glucose sensing were better than the Cu nanoparticles, and the bimetallic nanoparticles can promote the sensitivities of glucose sensing.

誌謝 i
摘要 ii
Abstract iii
目次 v
表目次 vii
圖目次 viii
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
1.3 研究目的 3
第二章 理論背景與文獻回顧 4
2.1 電化學原理 4
2.1.1 伏安法 5
2.1.2 安培法 7
2.2 葡萄糖感測原理及現況發展 8
2.3 奈米金屬應用於非酵素型葡萄糖感測之文獻回顧 10
2.3.1 Co及含Co之雙金屬奈米粒子應用於葡萄糖感測 10
2.3.2 Cu及含Cu之雙金屬奈米粒子應用於葡萄糖感測 12
2.4 以TiN為電極控制金屬奈米粒子應用於葡萄糖感測之文獻回顧 18
第三章 實驗方法 20
3.1 實驗流程 20
3.2 TiN/Si電極製備 21
3.3 電化學法沉積Cu-Co奈米粒子於TiN電極 22
3.4 Cu-Co奈米粒子應用於葡萄糖感測 23
3.5 分析儀器 23
3.5.1 電化學分析儀 23
3.5.2 X光繞射分析儀 23
3.5.3 場發射掃描式電子顯微鏡 / X光能量散射光譜儀 24
3.5.4 四點探針 24
3.5.5 場發射穿透式電子顯微鏡 25
第四章 結果 26
4.1 TiN/Si基材分析 26
4.2 以電化學法於TiN/Si沉積Cu-Co奈米粒子 30
4.2.1 不同形貌/不同電阻率之TiN/Si電極 30
4.2.2 不同形貌/相近電阻率之TiN/Si電極 42
4.3 葡萄糖感測 52
4.3.1 以不同形貌/不同電阻率TiN沉積之Cu-Co奈米粒子 52
4.3.2 以不同形貌/相近電阻率TiN沉積之Cu-Co奈米粒子 58
第五章 討論 65
5.1 以不同形貌/電阻率TiN沉積之Cu-Co微結構與成分分析 65
5.2 葡萄糖感測影響因子 72
5.2.1 TiN之形貌與電阻率 72
5.2.2 電解液中硫酸銅/硫酸鈷溶液比例 77
第六章 結論 82
參考文獻 83

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