臺灣博碩士論文加值系統

本次研究主要分為兩個階段，第一階段使用了低溫且低成本之水熱法製作氧化鋅奈米柱作為基準。第二階段，使用直流濺鍍系統將金奈米粒子濺鍍於氧化鋅奈米柱表面上，並將其研製為非酶葡萄糖感測器。其結果再與第一階段相比，作為催化劑的金奈米粒子將感測器之性能有效的提升。
使用物性分析(場發射掃描電子顯微鏡、X-射線繞射分析、穿透式電子顯微鏡)，觀察其表面型貌、材料結構、元素含量都有良好結果，也更確切了解了影響感測器之因素。利用電性分析(循環伏安法)觀察有無吸附金奈米粒子的氧化鋅奈米柱，測量各種濃度下葡萄糖溶液(0~8mM)之循環伏安圖，其靈敏度分別為63.4μA/cm2-mM及182.96μA/cm2-mM，由此可觀察到吸附金奈米粒子可以有效提升反應靈敏度與大幅增加其對葡萄糖分子的感測催化能力。

The research was divided into two phases. The first stage is ZnO nanorods were synthesized by hydrothermal growth technique. The second stage, ZnO nanorods decorated with Au nanoparticles and development of non-enzyme glucose sensor. The Au nanoparticles, acting as a catalyst, effectively enhanced the non-enzyme glucose sensor performance in comparison with the initial ZnO nanorods.
The surface morphology and physical properties were characterized by SEM, X-ray and TEM. Sensing response to compared in a 0~8mM glucose solution pure ZnO nanorods and ZnO nanorods decorated with Au nanoparticles by using cyclic voltammetry method. The sensitivities of the glucose sensors were 63.4μA/cm2-m and 182.96μA/cm2-mM, respectively. It was observed that ZnO nanorods decorated with Au nanoparticles can effectively improve the sensitivity and enhance its catalytic properties for glucose molecules.

摘要......................................i
Abstract.................................ii
誌謝....................................iii
目錄.....................................iv
表目錄...................................vi
圖目錄..................................vii
第一章 緒論..............................1
1.1前言..................................1
1.2研究動機..............................2
第二章 文獻回顧...........................4
2.1何謂生物感測器.........................4
2.2葡萄糖感測器歷史.......................5
2.2.1第一代葡萄糖感測器....................5
2.2.2第二代葡萄糖感測器....................6
2.2.3第三代葡萄糖感測器....................6
2.3第四代非酶葡萄糖感測器...................7
2.3.1奈米材料被應用於非酶葡萄糖感測器....7
2.3.2氧化鋅奈米結構修飾電極.............7
2.3.3 IHOAM模型.......................7
2.4電化學原理..............................8
2.4.1三極式電化學量測系統...............9
2.4.2循環伏安法.......................10
2.5氧化鋅奈米材料簡介......................12
2.6薄膜製成方法...........................14
2.7氧化鋅奈米結構之合成方式................15
2.7.1化學氣相沉積法(CVD)..................15
2.7.2水溶液法 (Aqueous solution method)..16
2.7.3水熱法 (Hydrothermal method)........17
第三章 實驗步驟與量測設備分析..............19
3.1實驗室藥品............................19
3.2儀器介紹..............................20
3.2.1射頻磁控濺鍍系統 (RF magnetic sputtering system)....20
3.2.2場發射掃描式電子顯微鏡 (Field Emission Scanning Electron Microscopy, FE-SEM)....................................22
3.2.3 X射線繞射儀(X-ray diffraction, XRD)...23
3.2.5能量散佈分析儀(Energy Dispersive Spectrometer，EDS)........25
3.2.6穿透式電子顯微鏡(Transmission Electron Microscopy，TEM)....25
3.2.7電化學分析儀器(Electrochemistry Workstation)...............27
3.3氧化鋅奈米柱實驗步驟.........................................28
3.3.1基板清洗............................29
3.3.2氧化鋅晶種層製程.....................30
3.3.3氧化鋅奈米柱生長.....................31
3.3.4氧化鋅奈米奈米結構製作葡萄糖感測器.....33
3.3.5氧化鋅奈米柱及吸附金奈米粒子氧化鋅奈米柱材料特徵分析...........34
3.3.6葡萄糖電解質溶液的調配...............34
3.3.7電化學量測系統......................34
3.3.8系統葡萄糖濃度控制..................35
3.3.9循環伏安法(Cyclic Voltammetry)......36
第四章 結果與討論........................37
4.1氧化鋅奈米柱材料特徵分析...............37
4.1.1氧化鋅奈米柱場發射電子顯微鏡分析......37
4.1.2金屬觸媒吸附氧化鋅奈米柱場發射電子顯微鏡分析.....39
4.1.3 金屬觸媒吸附於氧化鋅奈米柱之穿透式掃描式電子顯微鏡.....40
4.1.4 X-ray繞射儀之氧化鋅奈米柱分析.......43
4.1.5光致發光之氧化鋅奈米柱分析...........44
4.2氧化鋅奈米柱葡萄糖感測器之電化學分析....45
4.2.1氧化鋅奈米柱CV掃描-濃度對電流值之量測..45
4.2.2氧化鋅奈米柱之電流-時間圖(I-t curve)量測.....47
4.2.3氧化鋅奈米柱之不同掃描速率量測.......48
4.2.4氧化鋅奈米柱之穩定性量測.............49
4.2.5氧化鋅奈米柱之干擾物質和選擇性測試....50
4.3氧化鋅奈米柱吸附金奈米粒子之葡萄糖感測器電化學分析.....51
4.3.1氧化鋅奈米柱CV掃描-濃度對電流值之量測..............51
4.3.2氧化鋅奈米柱吸附金奈米粒子之電流-時間圖(I-t curve)量測....53
4.3.3氧化鋅奈米柱吸附金奈米粒子之不同掃描速率量測........54
4.3.4氧化鋅奈米柱吸附金奈米粒子之穩定性量測.............55
4.3.5氧化鋅奈米柱吸附金奈米粒子之干擾物質和選擇性測試....56
第五章 結論..........................................57
5.1結論.............................................57
5.2未來展望..........................................57
參考文獻.............................................58

[1]M. Ahmad, C.F. Pan, and J. Zhu, "Electrochemical determination of l-Cysteine by an elbow shaped, Sb-doped ZnO nanowire-modified electrode," Journal of Materials Chemistry, vol. 20, no. 34, pp. 7169-7174, Sep. 2010.
[2]M. Ahmad, C.F. Pan, J. Iqbal, L. Gan, and J. Zhu, "Bulk synthesis route of the oriented arrays of tip-shape ZnO nanowires and an investigation of their sensing capabilities," Chemical Physics Letters, vol. 480, no.1-3, pp. 105-109, Sep. 2009.
[3]G. Gao, Q. Xi, H. Zhou, Y. Zhao, C. Wu, L. Wang, et al., "Selectivity of quantum dot sensitized ZnO nanotube arrays for improved photocatalytic activity," Phys Chem Chem Phys, vol. 19, no. 18, pp. 11366-11372, May. 2017.
[4]K. Thirunavukkarasu and R. Jothiramalingam, "Synthesis and structural characterization of Ga-ZnO nanodisk/nanorods formation by polymer assisted hydrothermal process," Powder Technology, vol. 239, pp. 308-313, May. 2013.
[5]S.J. Young and Y.H. Liu, "High Response of Ultraviolet Photodetector Based on Al-Doped ZnO Nanosheet Structures," IEEE Journal of Selected Topics in Quantum Electronics, vol. 23, no.5, Sep. 2017.
[6]F. Huang, J. Hou, Q. Zhang, Y. Wang, R. C. Masse, S. Peng, et al., "Doubling the power conversion efficiency in CdS/CdSe quantum dot sensitized solar cells with a ZnSe passivation layer," Nano Energy, vol. 26, pp. 114-122, Aug. 2016.
[7]Y. Feng, L. Liu, S. Hu, Y. Ren, Y. Liu, J. Xiu, et al., "Four-photon-excited fluorescence resonance energy transfer in an aqueous system from ZnSe:Mn/ZnS quantum dots to hypocrellin A," Optics Express, vol. 24, no. 17, pp. 19627-19637, Aug 2016.
[8]Y. Zhang, Z. Cui, Y. Ding, and T. Liu, "Density functional theories study on optoelectronic properties of arsenic-doped GaN nanowires," Optical and Quantum Electronics, vol. 48, no. 12, Dec. 2016.
[9]經濟日報“國際糖尿病聯盟：最新數據顯示全球目前有4.63億人患有糖尿病”2019年11月15日.
[10]王少均“血糖感測器”科學發展，2007年12月，420期.
[11]H. Tian, M. Jia, M. Zhang, and J. Hu, "Nonenzymatic glucose sensor based on nickel ion implanted-modified indium tin oxide electrode," Electrochimica Acta, vol. 96, pp. 285-290, 2013.
[12]P. Lu, Q. Liu, Y.Xiong, Q. Wang, Y. Lei, S. Lu, L. Lu, Li Yao, "Nanosheets-assembled hierarchical microstructured Ni(OH)2 hollow spheres for highly sensitive enzyme-free glucose sensors," Electrochimica Acta, vol. 168, pp. 148-156, 2015.
[13]B. Zhang, Y. He, B. Liu, and D. Tang, "Nickel-functionalized reduced graphene oxide with polyaniline for non-enzymatic glucose sensing," Microchimica Acta, vol. 182, no. 3-4, pp. 625-631, 2014.
[14]R. Wilson and A. P. F. Turner, "Review article Glucose oxidase: an ideal enzyme, "Biosens. Bioelectron., 7, pp. 165-185, 1922.
[15]F. Cao, S. Guo, H. Ma, G. Yang, S. Yang, and J. Gong, "Highly sensitive nonenzymatic glucose sensor based on electrospun copper oxide-doped nickel oxide composite microfibers," Talanta, vol. 86, pp. 214-20, Oct 30 2011.
[16]A. E. Kitabchi, G. E. Umpierrez, J. M. Miles, and J. N. Fisher, "Hyperglycemic crises in adult patients with diabetes," Diabetes Care, vol. 32, no. 7, pp. 1335-43, Jul 2009.
[17]https://www.diabetesatlas.org/upload/resources/material/20200302_133351_IDFATLAS9e-final-web.pdf
[18]蘇宏基"化學生物感測器講義"東華大學化學系.
[19]S. Park, H. Boo, and T. D. Chung, "Electrochemical non-enzymatic glucose sensors," Anal Chim Acta, vol. 556, no. 1, pp. 46-57, Jan 18 2006.
[20]K. E. Toghill and R. G. Compton, "Electrochemical Non-enzymatic Glucose Sensors: A Perspective and an Evaluation," (in English), International Journal of Electrochemical Science, vol. 5, no. 9, pp. 1246-1301, Sep 2010.
[21]Z. Zhu, L. Garcia-Gancedo, A. J. Flewitt, H. Xie, F. Moussy, and W. I. Milne, "A critical review of glucose biosensors based on carbon nanomaterials: carbon nanotubes and graphene," Sensors (Basel), vol. 12, no. 5, pp. 5996-6022, 2012.
[22]P. D. Hale, T. Inagaki, H. I. Karan, Y. Okamoto, and T. A. Skotheim, "A new class of amperometric biosensor incorporating a polymeric electron-transfer mediator," Journal of the American Chemical Society, vol. 111, no. 9, pp. 3482-3484, 1989.
[23]K. E. Toghill and R. G. Compton, Int. J. Electrochem. Sci.,2010, 5, 1246–1301.
[24]S. Park, H. Boo, and T. D. Chung, "Electrochemical non-enzymatic glucose sensors," Anal Chim Acta, vol. 556, no. 1, pp. 46-57, Jan 18 2006.
[25]M. M. Rahman, A. J. Ahammad, J. H. Jin, S. J. Ahn, and J. J. Lee, "A comprehensive review of glucose biosensors based on nanostructured metal-oxides," Sensors (Basel), vol. 10, no. 5, pp. 4855-86, 2010.
[26]L. D. Burke, "Premonolayer Oxidation and Its Role in Electrocatalysis," Electrochimica Acta, vol. 39, no. 11-12, pp. 1841-1848, Aug 1994.
[27]H. Zhu, L. Li, W. Zhou, Z. Shao, and X. Chen, "Advances in non-enzymatic glucose sensors based on metal oxides," Journal of Materials Chemistry B, vol. 4, no. 46, pp. 7333-7349, 2016.
[28]Steckhan E., "Organic synthese with with electrochemically regenerable redox systems, " Topic in Current Chemistry, Vol.142, Steckhan E. eds, Springer-Verlag,Berlin Heidelberg, 1987.
[29]M. E. Tess and J. A. Cox, "Chemical and biochemical sensors based on advances in materials chemistry," Journal of Pharmaceutical and Biomedical Analysis, vol. 19, no. 1-2, pp. 55-68, 1999.
[30]P. T. K. W. R. Heineman, "Cyclic Voltammetry".
[31]Wang, Analytical Electrochemistry, 2nd Edition. John Wiley & Sons, Inc.,New York.
[32]F. Zhou, Weixuan Jing, Qiong Wu, Weizhuo Gao, Zhuangde Jiang, Jiafan Shi, Qibing Cui, "Effects of the surface morphologies of ZnO nanotube arrays on the performance of amperometric glucose sensors," Materials Science in Semiconductor Processing, vol. 56, pp. 137-144, 2016.
[33]R. Wen, L. Wang, X. Wang, G.H. Yue, Y. Chen, and D.L. Peng, "Influence of substrate temperature on mechanical, optical and electrical properties of ZnO:Al films," Journal of Alloys and Compounds, vol. 508, no. 2, pp. 370-374, Oct. 2010.
[34]M. Chen, Z. L. Pei, X. Wang, C. Sun, and L. S. Wen, "Structural, electrical, and optical properties of transparent conductive oxide ZnO:Al films prepared by dc magnetron reactive sputtering," Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol. 19, no. 3, pp. 963-970, May. 2001.
[35]V. Assuncao, E. Fortunato, A. Marques, H. Aguas, I. Ferreira, M. E. V. Costa, et al., "Influence of the deposition pressure on the properties of transparent and conductive ZnO:Ga thin-film produced by r.f. sputtering at room temperature," Thin Solid Films, vol. 427, no. 1-2, pp. 401-405, Mar. 2003.
[36]K. C. Park, D. Y. Ma, and K. H. Kim, "The physical properties of Al-doped zinc oxide films prepared by RF magnetron sputtering," Thin Solid Films, vol. 305, no. 1-2, pp. 210-219, Aug. 1997.
[37]P.C. Chang, Z. Fan, D. Wang, W.Y. Tseng, W.A. Chiou, J. Hong, et al., "ZnO Nanowires Synthesized by Vapor Trapping CVD Method," Chemistry of Materials, vol. 16, no. 24, pp. 5133-5137, Nov. 2004.
[38]Y. Tak and K. Yong, "Controlled Growth of Well-Aligned ZnO Nanorod Array Using a Novel Solution Method," Journal of Physical Chemistry B, vol. 109, no. 41, pp. 19263-19269, Oct. 2005.
[39]S. Baruah and J. Dutta, "Hydrothermal growth of ZnO nanostructures," Science and Technology of Advanced Materials, vol. 10, no. 1, Mar. 2009.
[40]B. Liu and H. C. Zeng, "Hydrothermal Synthesis of ZnO Nanorods in the Diameter Regime of 50 nm," Journal of The American Chemical Society, vol. 125, no. 15, pp. 4430-4431, Apr. 2003.
[41]H. Zhang, D. Yang, Y. Ji, X. Ma, J. Xu, and D. Que, "Low Temperature Synthesis of Flowerlike ZnO Nanostructures by Cetyltrimethylammonium Bromide-Assisted Hydrothermal Process," Journal of Physical Chemistry B, vol. 108, no. 13,pp. 3955-3958, Apr. 2004.
[42]P.F. Carcia, R.S. McLean, M.H. Reilly, and G. Nunes,"Transparent ZnO thin-film transistor fabricated by rf magnetron sputtering," Applied Physics Letters, vol. 82, no. 7, pp. 1117-1119, Feb. 2003.
[43]S.-H. Jeong, B.-S. Kim, and B.-T. Lee, "Photoluminescence dependence of ZnO films grown on Si(100) by radio-frequency magnetron sputtering on the growth ambient," Applied Physics Letters, vol. 82, pp. 2625-2627, 2003.
[44]K. Hassan and G.S. Chung, "Catalytically activated quantum-size Pt/Pd bimetallic core–shell nanoparticles decorated on ZnO nanorod clusters for accelerated hydrogen gas detection," Sensors and Actuators B: Chemical, vol. 239, pp. 824-833, Feb. 2017.
[45]F. Fan, J. Zhang, J. Li, N. Zhang, R. Hong, X. Deng, et al., "Hydrogen sensing properties of Pt-Au bimetallic nanoparticles loaded on ZnO nanorods," Sensors and Actuators B: Chemical, vol. 241, pp. 895-903, Mar. 2017.
[46]Y.H. Liu, S.J. Young, L.W. Ji, and S.J. Chang, "Ga-Doped ZnO Nanosheet Structure-Based Ultraviolet Photodetector by Low-Temperature Aqueous Solution Method," IEEE Transactions on Electron Devices, vol. 62, no. 9, pp. 2924-2927, Sep. 2015.
[47]S. Akin, E. Erol, and S. Sonmezoglu, "Enhancing the electron transfer and band potential tuning with long-term stability of ZnO based dye-sensitized solar cells by gallium and tellurium as dual-doping," Electrochimica Acta, vol. 225, pp. 243-254, Jan. 2017.
[48]B. Khalfallah, F. Chaabouni, G. Schmerber, A. Dinia, and M. Abaab, "Investigation of physico-chemical properties of conductive Ga-doped ZnO thin films deposited on glass and silicon wafers by RF magnetron sputtering," Journal of Materials Science: Materials in Electronics, vol. 28, no. 1, pp. 75-85, Jan. 2017.
[49]R. H. FOWLER, F.R.S, and L. NORDHEIM, "Electron Emission in Intense Electric Fields," Series A, vol. 119, pp. 173-181, 1928.
[50]http://web.nuu.edu.tw/~carlu/html/eBook/ZigBee/CH1.pdf
[51]M. Ahmad, L. Gan, C. Pan, and J. Zhu, "Controlled synthesis and methanol sensing capabilities of Pt-incorporated ZnO nanospheres," Electrochimica Acta, vol. 55, pp. 6885-6891, 2010.
[52]Keshuang Zheng, Zhipeng Zhang, Ximiao Wang, Runze Zhan, Huanjun Chen, Shaozhi Deng, Ningsheng Xu, and Jun Chen, " Mechanism of photoluminescence quenching in visible and ultraviolet emissions of ZnO nanowires decorated with gold nanoparticles." To cite this article: Keshuang Zheng et al 2019 Jpn. J. Appl. Phys. 58 051005
[53]Siou-Yi Lin,Shoou-Jinn Chang, and Ting-Jen Hsueh "ZnO nanowires modified with Au nanoparticles for non-enzymatic amperometric sensing of glucose,"APPLIED PHYSICS LETTERS 104,193704,2014.