臺灣博碩士論文加值系統

本論文分為兩個部分，利用固體碳源生長石墨烯碳膜於銅箔，以及運用此一石墨烯碳膜構裝掃描穿隧顯微鏡(Scanning Tunneling Microscopy, STM)用之探針。

第一部分是使用化學氣相沉積法(Chemical Vapor Deposition, CVD)於高溫單區管狀爐管中生長類石墨烯碳膜。樟腦(Camphor)，因其便宜、易揮發、無害因此將其選為本實驗所使用之固體碳源。將管內反應區之溫度升高至1050℃並通過氬氫混合氣(95:5 sccm)將樟腦揮發之氣體推至反應區並借由其高溫裂解為碳原子並沉積到基板上形成類石墨烯薄膜。
為製備出較高品質的石墨烯，實驗中將調變各種實驗參數如壓力、生長時間、溫度以期優化生長出石墨烯之薄膜，並利用拉曼光譜儀、穿透式電子顯微鏡觀測生長石墨烯之品質。

第二部分將通過化學氣相沉積法生長類石墨烯薄膜於銅線上並將其構裝成掃描穿隧顯微鏡(Scanning Tunneling Microscopy, STM)用之探針。探針通過拉曼光譜的量測確認其針尖具有石墨烯的訊號。同時探針也將用於量測高熱向定解石墨(Highly Ordered Pyrolytic Graphite, HOPG)以及花生酸自組裝分子之結構以及其穿隧掃描能譜(Scanning Tunneling Spectroscopy, STS)，並與市售之Pt/Ir針比較。我們發現使用石墨烯碳針量測含碳材質時，其能隙值大於一般金屬碳針量測之結果，我們推論此一現象的可能是π電子穿隧禁制所致。

關鍵詞: 掃描穿隧式顯微鏡、石墨烯、化學氣相沉積法、自組裝分子、掃描穿隧能譜

This study is contain two sections. First we use solid carbon source to synthesize graphene on copper foils. Then we apply our graphene as a thin film edge probes for scanning tunneling microscopy.

We report synthesis of grapheme thin film on copper foil using solid camphor as a carbon source in a chemical vapor deposition. Owing its non-hazardous, less expensive and easily sublimable properties at a low temperature, camphor was used as the solid carbon source in this experiment. When the temperature in the reaction zone was increased to 1050 ℃, camphor was slowly evaporated and pushed to the growth zone by the Ar and H2 (95:5 sccm) gas mixture and carbon atoms obtained by the thermal cleaved will be deposited on the substrate. The optimal fabrication condition was determined through a series of experiments performed under various ambient conditions such as pressure, growth time, temperature. Synthesized graphene on the copper foil was characterized by Raman spectroscopy and transmission electron microscope.

In the second part we report the growth of the graphene thin film on copper wire to act as the scanning tunneling microscopy tip. We use Raman spectroscopy to confirm the presence of graphene. The tip then was used in scanning tunneling microscopy to measure the surface of highly oriented pyrolytic graphite and self assembling molecules: arachidic acid. Scanning tunneling spectroscopy measurements were also made on these two samples: highly oriented pyrolytic graphite and arachidic acid, the results were compared with that obtained by using the Pt/Ir tip. We found the band gap was measured when graphene probe was used. This may be due to the tunneling forbidden from π-electron(from tip) to π-state(to sample).

Keywords: scanning tunneling microscope, graphene, chemical vapor deposition, self-assembling molecules, scanning tunneling spectroscopy

目錄
摘要 I
Abstract II
目錄 III
圖目錄 VI
表目錄 IX
第一章、 緒論 1
1.1 研究動機 1
1.2 簡介 3
1.2.1 石墨烯由來 3
1.2.2 石墨烯結構 4
1.3.1膠帶剝離法 6
1.3.2以氧化石墨（graphite oxide）製備石墨烯 7
1.3.3 單（多）壁奈米碳管製備石墨烯 7
1.3.4 化學氣相沈積法製備石墨烯 8
第二章、 儀器工作原理以及應用 10
2.1利用拉曼光譜判別石墨烯 10
2.1.1拉曼光譜簡介 10
2.1.2石墨烯層數判別 11
2.2掃描探針顯微術(Scanning Probe Microscopy ,SPM) 13
2.2.1簡介 13
2.2.2原子力顯微術 14
2.2.3掃描穿隧式顯微術 15
2.3STM應用 17
2.3.1原子移動 17
2.3.2微影技術 18
第三章、 石墨烯製備以及材料分析 19
3.1 石墨烯製備方式 19
3.1.1化學氣相沉積法 19
3.1.2化學氣相沉積法原理 20
3.1.3薄膜成形之原理[31] 21
3.2 石墨烯生長 22
3.2.1實驗裝置 23
3.2.2實驗步驟 24
3.3拉曼分析 25
3.3.1 Origin數據整理 27
3.4製程優化 29
3.5掃描式電子顯微鏡分析 31
3.6穿透式電子顯微鏡分析 33
3.7石墨烯結構改善 35
3.7.1 製程時間與薄膜成形 35
第四章、 類石墨烯探針製備以及量測 39
4.1STM系統 39
4.1.1探針 39
4.1.2掃描器 40
4.1.3步進器 40
4.1.4防震裝置 40
4.1.5控制系統[40] 41
4.2STM取像方式 42
4.2.1定電流取像法 42
4.2.2定高度取像法 42
4.2.3電流密度取像法 43
4.3石墨烯探針製作 44
4.3.1前言 44
4.3.2石墨烯碳針製作 45
4.3.3拉拔法 46
4.3.4探針拉曼分析 47
4.3.5探針SEM觀察 48
4.4 STM量測 49
4.4.1鉑銥合金針量測 49
4.4.2純銅針量測 50
4.4.3純銅針回火後量測 51
4.4.3類石墨烯探針量測 52
4.5自組裝分子量測 53
4.5.1鉑铱合金針量測 54
4.5.2類石墨烯探針量測 55
第五章、 穿隧掃描能譜觀察 57
5.1前言 57
5.2掃描穿隧能譜 57
5.2.1能帶關係說明 58
5.3實驗步驟 59
5.4 HOPG STS量測 60
5.4.1鉑銥合金針量測 60
5.4.2類石墨烯探針量測 61
5.5 花生酸STS量測 62
5.5.1鉑銥合金針量測 62
5.5.2類石墨烯探針量測 63
第六章、 結論與未來展望 64
參考文獻 65
附錄A: Preparing and installing the STM tip[38] 68
附錄B: Graphite (HOPG) on sample support[38] 69

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