本研究使用靜電場輔助電鍍法(electrostatic field-assisted electrodeposition)，於銦錫氧化物(indium tin oxide, ITO)導電玻璃表面電鍍生成具微米構形之白金薄膜(micropatterned platinum thin film, mPt)。以具有微米構形之靜電膜貼附於ITO表面，移除後進行循環伏安電鍍可得mPt。以光學顯微鏡與掃描式電子顯微鏡觀察表面形貌，可知mPt由密度不同之Pt叢集所組成，且其構形尺寸與靜電膜大致相同。使用掃描式電化學顯微鏡(scanning electrochemical microscope, SECM)對其電催化性質進行分析，mPt表面Pt叢集密度較大處，具有較高催化氧氣還原反應(oxygen reduction reaction)與I-/I2氧化還原反應之能力。
為了解微米構形的電鍍機制，本研究使用SECM對經由靜電膜接觸起電程序(contact electrification)於ITO表面所造成的靜電場進行量測。於含有ferrocene methanol/ferrocenium methanol (FcM/FcM+)氧化還原對的水溶液中，分析表面靜電場對探針逼近曲線(probe approaching curve)所造成之影響，並取得表面靜電場之SECM影像。探針於ITO表面經接觸起電位置處所測得的FcM氧化電流，較於原始ITO表面所得值小，顯示表面靜電場之作用為降低ITO還原FcM+的能力。當ITO電位控制於0.1 V~ 0.2 V (vs. Ag/AgCl)時進行SECM掃描，可得清晰的微米構形靜電場影像。

In this study, micropatterned platinum thin films (mPt) are successfully fabricated on the surface of indium tin oxide (ITO) conducting glass by electrostatic field-assisted cyclic voltammetric deposition. A micropatternd electrostatic film is firstly attached onto the ITO surface through contact electrification for at least 7 days, then is removed before cyclic voltammetric deposition of Pt and a mPt can thus being obtained. The surface morphology of the resulting mPt is observed using optical microscope and scanning electron microscope. It is found that its pattern dimensions are almost the same as that of the micropatternd electrostatic film, and the mPt is composed of Pt clusters with different areal densities. The electrocatalytic properties of the mPt are investigated using scanning electrochemical microscopy (SECM). The areas of mPt with high Pt cluster density have superior catalytic ability toward oxygen reduction reaction and I-/I2 redox reaction.
In order to understand the micropatterning mechanism, SECM is used to investigate the electrostatic field on the ITO surface induced by the contact electrification process. The influence of the surface electrostatic field on the probe approaching curve is analyzed in an aqueous solution containing ferrocene methanol/ ferrocenium methanol (FcM/FcM+) redox couple, and the SECM images of the surface electrostatic field under different substrate applying potentials are obtained. The probe FcM oxidation currents measured above the ITO surface which has been attached with the electrostatic film is smaller than that obtained on the original ITO surface, suggesting that the effect of the surface electrostatic field is to diminish the FcM+ reduction ability of the ITO surface. Distinct SECM images of the micropatternd electrostatic field can be acquired while the ITO substrate applying potential is controlled between 0.1 V to 0.2 V (vs. Ag/AgCl).

中文摘要 I
英文摘要 II
目錄	IV
圖目錄	VI
表目錄	X
第一章	緒論	1
1.1	前言	1
1.2	靜電發現與成因	3
1.3	研究目的與動機	7
第二章	文獻回顧	8
2.1	靜電場輔助電鍍製備微米構形薄膜	8
2.2	摩擦帶電序列與量測方法	12
2.3	接觸起電機制	16
2.4	掃描式電化學顯微鏡（SECM）	19
第三章	實驗	27
3.1	研究架構	27
3.2	實驗藥品與儀器	27
3.3	靜電膜介紹	30
3.4	基材之製備	32
3.4.1.	接觸起電程序	32
3.4.2.	白金微米構形之電鍍	34
3.5	表面電場分析	35
3.5.1.	白金微米構形薄膜(mPt-ITO)之SECM實驗	38
3.5.2.	Glass	40
3.5.3.	導體(ITO)	41
第四章	結果與討論	43
4.1	超微電極RG	43
4.2	白金微米構形薄膜(mPt-ITO)	45
4.2.1.	mPt-ITO催化氧氣還原反應之能力	48
4.2.2.	mPt-ITO催化I-/I2氧化還原反應之能力	52
4.3	接觸起電對表面電場之影響	56
4.3.1.	Glass	56
4.3.2.	導體ITO(PA)與ITO之表面電場分析	58
4.3.3.	導體ITO(mPA)之表面電場分析	68
4.3.4.	導體ITO(mPA)之SECM影像分析	75
第五章	結論	79
第六章	附錄	80
6.1	電解液2.0 mM K3[Fe(CN)6] /0.1 M KCl (aq)	80
6.2	電解液2.0 mM Fc /0.01 M TBABF4 (DMSO)	82
第七章	參考文獻	84

圖1.1.1、微米構形普魯士藍薄膜之製作流程圖。	2
圖1.2.1、絲絹與波棒之摩擦起電示意圖。	5
圖1.2.2、導體之感應起電示意圖。	5
圖1.2.3、絕緣體之分極狀態示意圖。	6
圖2.1.1、於 0.5 V定電位電鍍10 SEC之微米構形普魯士藍薄膜SEM圖。	8
圖2.1.2、不同電荷極性之帶電體與接觸起電工作電極之交互作用。	9
圖2.1.3、靜電膜與基材接觸時間，對普魯士藍電鍍電量的影響。	10
圖2.1.4、基材移除靜電膜後於空氣中放置天數對電鍍電量的影響。	11
圖2.2.1、摩擦帶電序列。	13
圖2.2.2、循環摩擦帶電序列。	13
圖2.2.3、金屬球與聚合物之接觸帶電裝置與靜電計紀錄之感應電荷圖。	14
圖2.2.4、以非導電微米球測量接觸帶電裝置與靜電計紀錄之電荷應答。	15
圖2.3.1、電子轉移與離子轉移式意圖。	16
圖2.3.2、絕緣材料表面的三種起電機制示意圖。	17
圖2.3.3、絕緣材料之接觸起電氫氧根離子吸附模型。	18
圖2.4.1、SECM示意圖。	19
圖2.4.2、CHI 920C SECM三軸控制器、探針與電解槽載台示意圖。	20
圖2.4.3、UME示意圖。	21
圖2.4.4、UME典型CV圖，電解液為2.0 MM FCM /0.1 M KCL (AQ)。	22
圖2.4.5、SECM電流回饋模式示意圖。	24
圖2.4.6、標準化後UME電流對應距離之逼近曲線。	25
圖2.4.7、SECM之生成/收集模式示意圖。	26
圖3.2.1、實驗流程圖。	29
圖3.3.1、靜電膜之結構示意圖。	30
圖3.3.2、微米構形靜電膜之OM圖。	30
圖3.3.3、靜電膜之收納方式與帶電示意圖。	31
圖3.4.1、基材之種類與表示法。	32
圖3.4.2、基材之清洗與接觸起電程序流程圖。	33
圖3.4.3、白金微米構形之電鍍流程圖。	34
圖3.5.1、表面電場分析之SECM實驗裝置圖。	36
圖4.1.1、以玻璃作為基材之UME逼近曲線。	44
圖4.1.2、UME玻璃絕緣鞘RG與電極半徑A之比例示意圖。	44
圖4.2.1、MPT-ITO不同電鍍圈數之OM圖。	45
圖4.2.2、MPT-ITO不同電鍍圈數之SEM圖。	46
圖4.2.3、MPT-ITO於0.5 M H2SO4水溶液之CV圖。	47
圖4.2.4、靜電場輔助電鍍法製備MPT-ITO之機制與程序。	47
圖4.2.5、AU UME於0.5 M H2SO4水溶液之CV圖。	49
圖4.2.6、MPT-ITO之大面積與小面積示意圖。	49
圖4.2.7、小面積MPT-ITO於0.5 M H2SO4水溶液之CV圖。	50
圖4.2.8、MPT-ITO以TG/SC模式進行氧氣還原反應之示意圖。	50
圖4.2.9、MPT-ITO催化氧氣還原反應之SECM圖。	51
圖4.2.10、MPT-ITO於5.0 MM LII /0.1 M KCL水溶液中之CV圖。	53
圖4.2.11、MPT-ITO與ITO於5.0 MM LII /0.1 M KCL水溶液之CV圖。	53
圖4.2.12、PT UME於5.0 MM LII /0.1 M KCL水溶液中之CV圖。	54
圖4.2.13、MPT-ITO以TG/SC模式進行I-/I2氧化還原反應之示意圖。	54
圖4.2.14、MPT-20C催化I2還原反應之SECM圖。	55
圖4.3.1、GLASS之接觸起電機制。	56
圖4.3.2、以PT UME對GLASS與GLASS(PA)進行PSC-Z之I_T應答曲線。	57
圖4.3.3、ITO(PA)之接觸起電機制。	58
圖4.3.4、PT UME與ITO於2.0 MM FCM /0.1 M KCL (AQ)之循環伏安圖。	59
圖4.3.5、UME對ITO(PA)進行PSC-Z，改變基材電位之I_T應答曲線。	60
圖4.3.6、UME對ITO進行PSC-Z，改變基材電位之I_T應答曲線。	60
圖4.3.7、ITO與ITO(PA)於-0.2 V~ 0.1 V之UME標準化電流應答比較圖。	61
圖4.3.8、ITO與ITO(PA)於0.15 V~ 0.35 V之UME標準化電流應答比較圖。	62
圖4.3.9、UME與ITO於 2.0 MM FCM /0.1 M KCL (AQ)之TG/SC與競爭模式示意圖。	63
圖4.3.10、UME距離ITO(PA)不同水平高度下之標準化電流。	65
圖4.3.11、UME距離ITO不同水平高度下之標準化電流。	65
圖4.3.12、不同水平高度ITO與ITO(PA)之UME標準化電流比較圖。	66
圖4.3.13、ITO(MPA)之微米構形接觸起電機制。	68
圖4.3.14、UME於ITO(MPA)表面進行PSC- Z的位置示意圖。	69
圖4.3.15、UME在ITO(MPA)表面進行PSC-Z之實際位置。	69
圖4.3.16、UME對ITO(MPA)之ITO位置進行PSC-Z之I_T應答曲線。	70
圖4.3.17、UME對ITO(MPA)之MPA位置進行PSC-Z，之I_T應答曲線。	70
圖4.3.18、不同基材電位ITO與MPA位置之UME標準化電流應答比較圖。	71
圖4.3.19、UME距離MPA位置不同水平高度下之標準化電流。	72
圖4.3.20、UME距離ITO位置不同水平高度下之標準化電流。	72
圖4.3.21、不同水平高度ITO與MPA位置之UME標準化電流比較圖。	73
圖4.3.22、UME於ITO(MPA)表面進行XY方向SECM掃描之示意圖。	75
圖4.3.23、ITO(MPA) 於2.0 MM FCM /0.1 M KCL (AQ)施加不同電位之SECM影像掃描。	76
圖4.3.24、ITO(MPA)與ITO於2.0 MM FCM /0.1 M KCL (AQ)中之開路電位。	77
圖4.3.25、UME與基材於2.0 MM FC /0.1 M TBAPF6之TG/SC模式示意圖。	78
圖4.3.26、ITO(MPA)於2.0 MM FC /0.1 M TBAPF6之SECM影像掃描。	78
圖6.1.1、UME與ITO於2.0 MM K3[FE(CN)6] /0.1 M KCL (AQ)之循環伏安圖。	80
圖6.1.2、ITO(MPA)於2.0 MM K3[FE(CN)6] /0.1 M KCL (AQ)施加不同電位之SECM影像掃描。	81
圖 6.2.1、UME與ITO於2.0 MM FC/0.01 M TBABF4 (DMSO)之循環伏安圖。	82
圖6.2.2、UME施加0.6 V，ITO(MPA)施加-0.2 V於2.0 MM FC /0.01 M TBABF4 (DMSO)之SECM影像掃描。	83
圖6.2.3、UME施加-0.4 V，ITO(MPA)施加0.4 V於2.0 MM FC /0.01 M TBABF4 (DMSO)之SECM影像掃描。	83

表3.5.1、表面電場分析之實驗條件列表。	37
表4.1.1、負回饋逼近曲線理論公式在不同RG情況下所對應的參數值。	43
表4.3.1、ITO(PA)與ITO之UME標準化電流差異百分比。	67
表4.3.2、ITO(mPA)表面mPA與ITO位置之UME標準化電流差異百分比。	74

1. Thalladi, V. R., & Whitesides, G. M. (2002). Crystals of crystals: fabrication of encapsulated and ordered two-dimensional arrays of microcrystals. Journal of the American Chemical Society, 124(14), 3520-3521.
 2. Buse, K., Adibi, A., & Psaltis, D. (1998). Non-volatile holographic storage in doubly doped lithium niobate crystals. Nature, 393(6686), 665-668.
 3. Odom, T. W., Huang, J. L., Kim, P., & Lieber, C. M. (1998). Atomic structure and electronic properties of single-walled carbon nanotubes. Nature, 391(6662), 62-64.
 4. Malsch, N. H. (Ed.). (2005). Biomedical Nanotechnology. Crc Press.
 5. Zhao, D., Yang, P., Melosh, N., Feng, J., Chmelka, B. F., & Stucky, G. D. (1998). Continuous mesoporous silica films with highly ordered large pore structures. Advanced Materials, 10(16), 1380-1385.
 6. Arpin, K. A., Mihi, A., Johnson, H. T., Baca, A. J., Rogers, J. A., Lewis, J. A., & Braun, P. V. (2010). Multidimensional architectures for functional optical devices. Advanced Materials, 22(10), 1084-1101.
 7. Narazaki, A., Kawaguchi, Y., Niino, H., Shojiya, M., Koyo, H., & Tsunetomo, K. (2005). Formation of a TiO2 micronetwork on a UV-absorbing SiO2-based glass surface by excimer laser irradiation. Chemistry of materials, 17(26), 6651-6655.
 8. Djurišić, A. B., & Leung, Y. H. (2006). Optical properties of ZnO nanostructures. small, 2(8‐9), 944-961.
 9. Shipway, A. N., Katz, E., & Willner, I. (2000). Nanoparticle arrays on surfaces for electronic, optical, and sensor applications. ChemPhysChem, 1(1), 18-52.
 10. Yan, H., Zhao, Y., Qiu, C., & Wu, H. (2008). Micropatterning of inorganic precipitations in hydrogels with soft lithography. Sensors and Actuators B: Chemical, 132(1), 20-25.
 11. Campbell, C. J., Smoukov, S. K., Bishop, K. J., & Grzybowski, B. A. (2005). Reactive surface micropatterning by wet stamping. Langmuir, 21(7), 2637-2640.
 12. Asoh, H., Sakamoto, S., & Ono, S. (2007). Metal patterning on silicon surface by site-selective electroless deposition through colloidal crystal templating. Journal of colloid and interface science, 316(2), 547-552.
 13. Yang, P., Zou, S., & Yang, W. (2008). Positive and negative ZnO micropatterning on functionalized polymer surfaces. Small, 4(9), 1527-1536.
 14.廖禮君. (2014). 以靜電力場輔助電鍍法製備具微米構形電致色變薄膜及其性質之研究. 淡江大學化學工程與材料工程學系碩士班學位論文, 1-124.
 15.丁坤億. (2013). 以靜電場輔助電鍍具微米構形普魯士藍薄膜之研究. 淡江大學化學工程與材料工程學系碩士班學位論文, 1-108.
 16. Bard, A. J., Fan, F. R. F., Kwak, J., & Lev, O. (1989). Scanning electrochemical microscopy. Introduction and principles. Analytical Chemistry, 61(2), 132-138.
 17. Engstrom, R. C., & Pharr, C. M. (1989). Scanning electrochemical microscopy. Analytical Chemistry, 61(19), 1099A-1104A.
 18. Schafer, D., Puschhof, A., & Schuhmann, W. (2013). Scanning electrochemical microscopy at variable temperatures. Physical Chemistry Chemical Physics, 15(14), 5215-5223.
 19. Takahashi, Y., Shevchuk, A. I., Novak, P., Murakami, Y., Shiku, H., Korchev, Y. E., & Matsue, T. (2010). Simultaneous noncontact topography and electrochemical imaging by SECM/SICM featuring ion current feedback regulation. Journal of the American Chemical Society, 132(29), 10118-10126.
 20. Nogala, W., Szot, K., Burchardt, M., Roelfs, F., Rogalski, J., Opallo, M., & Wittstock, G. (2010). Feedback mode SECM study of laccase and bilirubin oxidase immobilised in a sol–gel processed silicate film. Analyst, 135(8), 2051-2058.
 21. Lee, C., Kwak, J., & Bard, A. J. (1990). Application of scanning electrochemical microscopy to biological samples. Proceedings of the National Academy of Sciences, 87(5), 1740-1743.
 22. Song, W., Yan, Z., & Hu, K. (2012). Electrochemical immunoassay for CD10 antigen using scanning electrochemical microscopy. Biosensors and Bioelectronics, 38(1), 425-429.
 23. Sanchez-Sanchez, C. M., Solla-Gullon, J., Vidal-Iglesias, F. J., Aldaz, A., Montiel, V., & Herrero, E. (2010). Imaging structure sensitive catalysis on different shape-controlled platinum nanoparticles. Journal of the American Chemical Society, 132(16), 5622-5624.
 24. Castle, G. S. P. (2001). Industrial applications of electrostatics:: the past, present and future. Journal of Electrostatics, 51, 1-7.
 25. Schein, L. B. (1999). Recent advances in our understanding of toner charging. Journal of electrostatics, 46(1), 29-36.
 26. Clark, H. E., & Dessauer, J. H. (Eds.). (1965). Xerography and Related Processes. Focal Press.
 27. Schein, L. B. (2013). Electrophotography and development physics (Vol. 14). Springer Science & Business Media.
 28. Taylor, D. M., & Secker, P. E. (1994). Industrial electrostatics: Fundamentals and measurements (Vol. 13). Research Studies Pre.
 29. Frenot, A., & Chronakis, I. S. (2003). Polymer nanofibers assembled by electrospinning. Current opinion in colloid & interface science, 8(1), 64-75.
 30. Sessler, G. M. (2001). Electrets: recent developments. Journal of Electrostatics, 51, 137-145.
 31. Kawamoto, H., & Umezu, S. (2007). Development of electrostatic paper separation and feed mechanism. Journal of electrostatics, 65(7), 438-444.
 32. Moshkin, A. A., & Moshkina, S. A. (1997). Electrical filters made of polymer materials. Journal of electrostatics, 40, 681-685.
 33. Perrin, L., Laurent, A., Falk, V., Dufaud, O., & Traore, M. (2007). Dust and electrostatic hazards, could we improve the current standards?. Journal of loss prevention in the process industries, 20(3), 207-217.
 34. Iversen, P., & Lacks, D. J. (2012). A life of its own: The tenuous connection between Thales of Miletus and the study of electrostatic charging. Journal of Electrostatics, 70(3), 309-311.
 35. 林清涼& 戴念祖. (2001). 啟發性物理學電磁學-宏觀電磁學，光學和狹義相對論. 五南圖書.
 36. Olenick, R. P., Apostol, T. M., & Goodstein, D. L. (1986). Beyond the mechanical universe: from electricity to modern physics. Cambridge University Press.
 37. 二澤正行. (2005). 圖解靜電管理入門. 全華圖書出版社.
 38. Wu, J. J., Hsieh, M. D., Liao, W. P., Wu, W. T., & Chen, J. S. (2009). Fast-switching photovoltachromic cells with tunable transmittance. ACS nano, 3(8), 2297-2303.
 39. Diaz, A. F., & Felix-Navarro, R. M. (2004). A semi-quantitative tribo-electric series for polymeric materials: the influence of chemical structure and properties. Journal of Electrostatics, 62(4), 277-290.
 40. Harper, W. R. (1967). Contact and frictional electrification. Clarendon Press.
 41. Moore, A. D. (1997). Electrostatics: Exploring, Controlling, and Using Static Electricity: Including the Dirod Manual. Electrostatic Applications.
 42. Sessler, G. M. (2001). Electrets: recent developments. Journal of Electrostatics, 51, 137-145.
 43. Heilbron, J. L. (1979). Electricity in the 17th and 18th centuries: A study of early modern physics. Univ of California Press.
 44. Shaw, P. E. (1917). Experiments on tribo-electricity. I. The tribo-electric series. Proceedings of the Royal Society of London. Series A, Containing Papers of a Mathematical and Physical Character, 94(656), 16-33.
 45. McCarty, L. S., & Whitesides, G. M. (2008). Electrostatic charging due to separation of ions at interfaces: contact electrification of ionic electrets. Angewandte Chemie International Edition, 47(12), 2188-2207.
 46. Wiles, J. A., Grzybowski, B. A., Winkleman, A., & Whitesides, G. M. (2003). A tool for studying contact electrification in systems comprising metals and insulating polymers. Analytical chemistry, 75(18), 4859-4867.
 47. McCarty, L. S., Winkleman, A., & Whitesides, G. M. (2007). Ionic electrets: electrostatic charging of surfaces by transferring mobile ions upon contact. Journal of the American Chemical Society, 129(13), 4075-4088.
 48. Lowell, J., & Rose-Innes, A. C. (1980). Contact electrification. Advances in Physics, 29(6), 947-1023.
 49. Grzybowski, B. A., Fialkowski, M., & Wiles, J. A. (2005). Kinetics of contact electrification between metals and polymers. The Journal of Physical Chemistry B, 109(43), 20511-20515.
 50. Diaz, A. F., & Guay, J. (1993). Contact charging of organic materials: Ion vs. electron transfer. IBM Journal of Research and Development, 37(2), 249-260.
 51. Meunier, M., & Quirke, N. (2000). Molecular modeling of electron trapping in polymer insulators. The Journal of Chemical Physics, 113(1), 369-376.
 52. Galembeck, F., Burgo, T. A., Balestrin, L. B., Gouveia, R. F., Silva, C. A., & Galembeck, A. (2014). Friction, tribochemistry and triboelectricity: recent progress and perspectives. RSC Advances, 4(109), 64280-64298.
 53. Liu, C., & Bard, A. J. (2008). Electrostatic electrochemistry at insulators. Nature materials, 7(6), 505-509.
 54. Salaneck, W. R., Paton, A., & Clark, D. T. (1976). Double mass transfer during polymer‐polymer contacts. Journal of Applied Physics, 47(1), 144-147.
 55. Bard, A. J., & Mirkin, M. V. (Eds.). (2012). Scanning electrochemical microscopy. CRC Press.
 56. Fang, Y., & Leddy, J. (1995). Cyclic voltammetric responses for inlaid microdisks with shields of thickness comparable to the electrode radius: a simulation of reversible electrode kinetics. Analytical Chemistry, 67(7), 1259-1270.
 57. Mirkin, M. V., Fan, F. R. F., & Bard, A. J. (1992). Scanning electrochemical microscopy part 13. Evaluation of the tip shapes of nanometer size microelectrodes. Journal of Electroanalytical Chemistry, 328(1-2), 47-62. 
 58. Tabet-Aoul, A., & Mohamedi, M. (2012). Interrelated functionalities of hierarchically CNT/CeO2/Pt nanostructured layers: synthesis, characterization, and electroactivity. Physical Chemistry Chemical Physics, 14(13), 4463-4474.
 59. Demaille, C., Brust, M., Tsionsky, M., & Bard, A. J. (1997). Fabrication and characterization of self-assembled spherical gold ultramicroelectrodes. Analytical chemistry, 69(13), 2323-2328.