臺灣博碩士論文加值系統

摘要
本論文分為兩個部分，第一部分為主要探討以微波電漿化學氣相沉積法
(MPCVD)成長不同時間成長超奈米結晶鑽石的品質以及不同時間成長之還原氧
化石墨烯，並以泡沫鎳來當作工作電極，分別在泡沫鎳基板上沉積超奈米鑽石以
及結合還原氧化石墨烯，將其分別製作成電容電極元件來做分析；第二部分為成
長超奈米鑽石後經過氧電漿表面後處理，並加入還原氧化石墨烯溶液後，進一步
探討對於其擬電容性質分析，並分別進行物性及電性之分析。
經本研究發現，不同成長時間之超奈米鑽石經場發射掃描式電子顯微鏡分析
擁有不同晶粒尺寸與成膜性質，使用1M NaOH 水溶液做為電解質，可以得知成
長六分鐘超奈米鑽石比起成膜後的結構有較大的比表面積，有利於增加反應面積，
經過電性測量過後可以得出其電容值為163.3F/g。而經過不同時間成長之還原氧
化石墨烯溶液經拉曼光譜儀分析擁有不同缺陷程度，得知成長7.5 小時之還原氧
化石墨烯擁有較好的品質同時擁有較好的電性，其擬電容性質分析後得出其電容
值為408 F/g。
最後綜合將成長7.5 小時的還原氧化石墨烯與成長六分鐘的超奈米鑽石做複
合結構，因其有最佳披覆效果增加對於電解質的接觸面積，經測量後其電容值可
達875 F/g，而經由充放電測試後，其整體圖形接近對稱等腰三角形，說明其具
有良好的電化學可逆性；經過1000 圈循環伏安測試後，其電容還維持在88%，
也可說明此結構具有良好的循環穩定性。

Abstract
In this study, we used microwave systems to deposit ultra-nano diamonds on
nickel foam substrates. In addition, we use reduced graphene oxide to increase the
characteristics of pseudo-capacitors. This study is divided into two parts. The first part
is mainly to discuss the quality of ultra-nanocrystalline diamond, which was grown by
microwave plasma enhanced chemical vapor deposition (MPECVD) at different time
durations. And also focused on the preparation of glucose derived reduced graphene
oxide grown for different time durations at 200 ºC. We focus on the fabrication of
pseudo-capacitor using nanosized diamond material with glucose derived reduced
graphene oxide. The second part illustrates the oxygen plasma treatment on the
surface ultra-nanocrystalline diamond, and in addition with the reduced graphene
oxide solution. We explored the analysis of its pseudo-capacitance properties and
analyzed the physical and electrical properties separately.
According to the results, the nano-diamonds with different growth time have
different grain size and film-forming properties by field emission scanning electron
microscopy (FESEM). We used 1M NaOH aqueous solution as electrolyte, and it was
observed that the 6-minute growth of the ultra-nanocrystalline diamond has a larger
specific surface area than the structure after the film formation (i.e a film grown for
10 to 12 min). It possessed a highest specific capacitance of 163.3 F/g at a scan rate of
10 mV/s. Finally, we fabricate the materials using rGO-7.5hr/N-UNCD-6min for high
performance pseudo-capacitors. It has a capacitance value 875 F/g at a scan rate of 10
mV/s, and also has good cycle stability with capacitance retention of 88% after 1000
cycles. It also exhibited an outstanding electrochemical stability, and can be one of the
promising active materials in pseudo-capacitor applications.

目錄
中文摘要......................................................................................................................Ⅰ
英文摘要......................................................................................................................Ⅱ
致謝..............................................................................................................................Ⅲ
目錄..............................................................................................................................Ⅵ
圖目錄........................................................................................................................ XI
表目錄...................................................................................................................... XII
第一章緒論..............................................................................................................1
1.1 前言.................................................................................................................1
1.2 研究動機.........................................................................................................2
第二章文獻探討.....................................................................................................3
2.1 鑽石薄膜之特性簡介......................................................................................3
2.1.1 鑽石薄膜基本結構及性質...................................................................3
2.1.2 結晶鑽石成長機制..............................................................................4
2.1.3 鑽石成長結晶尺寸...............................................................................5
2.2 還原氧化石墨烯的特性簡介.........................................................................7
2.2.1 還原氧化石墨烯的結構與性質...........................................................7
2.2.2 還原氧化石墨烯製備方法...................................................................9
2.2.3還原氧化石墨稀的特性........................................................................9
2.3 超級電容器機制與種類............................................................................... 11
2.4 電化學分析法................................................................................................15
2.5 葡萄糖感測器................................................................................................16
2.5.1 葡萄糖感測發展世代.........................................................................16
V
2.5.2 葡萄糖感測器之檢測方式.................................................................18
第三章實驗方法..................................................................................................19
3.1 實驗設計與流程...........................................................................................19
3.2 製備之材料介紹...........................................................................................22
3.3 基板清洗.......................................................................................................23
3.4 微波電漿化學氣相沉積法成長奈米結晶鑽石...........................................24
3.5 水熱法(Hydrothermal method)成長還原氧化石墨烯.................................26
3.6 儀器設備與材料分析方法...........................................................................27
3.6.1 場發射掃描式電子顯微鏡(FE-SEM) .............................................27
3.6.2 拉曼光譜儀(Raman spectrum) ........................................................28
3.6.3 X 射線繞射儀(X-ray diffraction，XRD) ........................................29
3.6.4 電化學分析儀(Electrochemical Workstation) ..................................31
3.8 葡萄糖感測器試片封裝及循環伏安法表面改質........................................34
3.8.1 葡萄糖試片封裝................................................................................34
3.8.2 葡萄糖感測器表面改質....................................................................35
第四章還原氧化石墨烯/超奈米鑽石與泡沫鎳複合結構之擬電容特性
......................................................................................................................................36
4.1 超奈米鑽石之特性分析..................................................................................36
4.1.1 表面型態分析....................................................................................36
4.1.2 拉曼光譜儀分析................................................................................38
4.1.3 X-ray 繞射儀分析..............................................................................39
4.1.4 循環伏安法分析................................................................................41
4.1.5 電化學阻抗測試................................................................................47
4.2 還原氧化石墨烯/超奈米鑽石與泡沫鎳複合結構之特性分析....................48
4.2.1 表面型態分析....................................................................................48
4.2.2 拉曼光譜儀分析................................................................................51
VI
4.2.3 X-ray 繞射儀分析..............................................................................55
4.2.4 循環伏安法分析................................................................................58
4.2.5 電化學阻抗測試................................................................................68
4.2.6 恆電流充放電分析............................................................................69
第五章超奈米鑽石與泡沫鎳結構之葡萄糖量測電化學分析..............74
5.1 超奈米鑽石與泡沫鎳結構之特性分析.......................................................74
5.1.1 表面型態分析....................................................................................74
5.1.2 超奈米鑽石與泡沫鎳之葡萄糖量測電化學分析............................76
5.1.2 表面改質............................................................................................76
5.1.3 循環伏安法分析................................................................................76
5.1.4 定電位沉積分析法..........................................................................77
5.2 超奈米鑽石與泡沫鎳結構之氧電漿後處理葡萄糖量測電化學分析.......80
5.2.1 表面型態分析....................................................................................80
5.2.2 超奈米鑽石與泡沫鎳結構之氧電漿後處理葡萄糖量測分析........84
5.2.1 表面改質............................................................................................84
5.2.2 循環伏安法分析................................................................................84
5.2.3 定電位沉積分析法..........................................................................85
5.3 超奈米鑽石與泡沫鎳結構之氧電漿後處理擬電容感測分析...................94
5.4 還原氧化石墨烯(7.5hr)/超奈米鑽石與泡沫鎳之氧電漿後處理擬電容感
測分析........................................................................................................100
第六章結論與未來展望..............................................................................107
6.1 結論.............................................................................................................107
6.2 未來展望..................................................................................................... 111
參考文獻................................................................................................................. 112

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