臺灣博碩士論文加值系統

本研究以交流濺鍍法鍍碳層薄膜於矽晶圓及二氧化矽基板上，將試片浸至隔水加熱至100℃的氨水、磷酸中，透過已經加熱的氨水、磷酸，使少量氮原子以及磷原子擴散進入試片內，再以交流濺鍍法覆蓋上銅薄膜，銅元素扮演控制使少量碳析出於銅膜與基材之間，銅膜可降低碳膜熱裂解所需之溫度，同時銅膜亦可扮演保護氮原子以及磷原子隨著加熱而逸出試片，最後將樣品加熱至於600℃、700℃、800℃、900℃，並持溫一分鐘再以氯酸鐵蝕刻。
而後以光學顯微鏡和場發式電子鏡觀察到其中幾組參數下之試片可以觀察到石墨薄膜以及可能多層石墨烯之生成，多層石墨烯為石墨層與層之間的凡得瓦爾力弱化使石墨薄膜具有石墨烯特性，同時由拉曼光譜儀測量樣品薄膜中的G band往高波數偏移以及G band 半高寬窄化之現象，間接證明所製作的碳層薄膜產生石墨化以及D band往高波數偏移可說明摻入氮原子以及磷原子使的石墨晶格產生曲應變之現象。由X-ray繞射光譜儀說明在直接以矽晶圓為基材的碳薄膜中，氨水沒有雜相隨著摻雜過程產生；磷酸則是有五氧化二磷相產生；最後以四點探針和霍爾量測，量測到摻雜之後有面電阻下降和載子濃度上升趨勢，皆已得證明此方法為以簡易的化學溶液法製備摻雜氮以及磷之石墨薄膜或多層石墨烯。
相對其他摻雜方式皆需要超過1000℃以上方能使氣體與石墨烯產生熱裂解進而摻雜，本研究透過簡易的製備方式製備摻雜氮以及磷原子於具有石墨烯特性石墨烯薄膜。

In the present study, we demonstrate the facile and green synthesis of nitrogen and phosphorus doped graphite films by using simple chemical solution method. We successfully doped nitrogen and phosphorus onto the graphite film by doping with ammonium hydroxide and phosphoric acid respectively. For a typical synthesis of composite, we used the silicon wafer as a substrate then it was oxidized to form silicon dioxide layer, and carbon thin film was deposited onto sample. Then it was immersed into the ammonium hydroxide and phosphoric acid solution followed by heated at 100℃ for various dwelling time. After the immersion the copper was deposited onto the obtained sample by using sputtering method; here copper is acting as a cap layer between the carbon layers for inhibiting the loss of doped material during the heat treatment process. Finally the product was annealed at 600℃, 700℃, 800℃ respectively, which leads to the formation of graphitic film. It should be noted that here we used copper as a control for the formation of graphite. The surface morphology of the composite was characterized by using optical microscope, which revealing that graphitic layers are formed as the combination of multiple graphene layers via Van der Waals interactions between individual graphite layers.
Raman spectroscopy has been used to determine the properties of graphitic layers and the disorder of graphitic structure after graphitization. The synthesized composite films have been confirmed XRD. Further, the nitrogen and phosphorus doped graphite films have shown to improved sheet resistance and carrier concentration, implying the nitrogen and phosphorus leads to the enhanced and synergetic activity onto the graphitic film rather than intrinsic graphite. Finally, the versatile route of composite preparation could be a promising route for other composite materials preparation in near future.

摘要 ii
Abstract iv
Acknowledge vi
Contents vii
Figure Caption ix
Table Caption xiii
Chapter 1 Introduction 1
1.1 Introduction 1
1.2 Motivation 3
Chapter 2 Literature Review 4
2.1 Introduction of carbon material 4
2.1.1 Graphite 4
2.1.2 Graphene 5
2.2 Raman spectroscopy 6
2.2.1 The fundamental of Raman spectroscopy 6
2.3 Various methods for preparation of Graphene 9
2.3.1 Mechanical Exfoliation 9
2.3.2 Epitaxial graphene growth on silicon carbide 10
2.3.3 Chemical vapor deposition (CVD) 11
2.3.4 Chemical reduction of graphene oxide 17
2.3.5 Solid carbon source 19
2.4 Doping of nitrogen on graphite films 23
Chapter 3 Experiment and Method 25
3.1 Materials 25
3.2 Fabrication process 25
3.2.1 Schematic of synthesis flow 25
3.2.2 The process of synthesis of nitrogen and phosphorous doped graphite 26
3.3 Analysis apparatus 27
3.3.1 XRD 27
3.3.2 Raman spectrum 27
3.3.3 OM 28
3.3.4 FESEM 29
3.3.5 Four Point Probe 30
3.3.6 Hall effect 30
Chapter 4 Result and Discussion 31
4.1 Design of the experiment 31
4.1.1 Optimization of the concentrations 31
4.1.2 Optimization of the parameters 34
4.1.2.1 Sheet Resistance 36
4.1.2.2 XRD 37
4.2 Analysis of graphite films characteristics 39
4.2.1 Raman spectroscopy 39
4.2.2 The morphology of graphite films 44
4.3 Investigation of the electric properties 49
4.3.1 Sheet resistance 49
4.3.2 Hall measurement 52
Charter 5 Conclusion 60
Reference 62

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