臺灣博碩士論文加值系統

近年來，石墨烯材料被大量地研究以及產品化，因為石墨烯本身具有優越的性質，如質量很輕、耐酸鹼、良好的導電與導熱的特性，可被用來發展在複合材料、生醫工程、電子元件、太陽能電池及感測器上等等，但石墨烯因為有零價帶的特性，讓材料的應用受到了限制，那根據最近的實驗研究表明，利用摻雜原子的方式形成具有異原子的摻雜石墨烯，而摻雜石墨烯除了有獨特的電子特性之外，上述所說的應用領域也被發展得更廣更遠，那本文所應用在的石墨烯增強拉曼散射(GERS)是近年來被廣為討論及研究的領域。利用摻雜石墨烯獨特的sp2結構以及摻雜結構，使待測物分子吸附在摻雜石墨烯後，因為化學機制導致可以得到增強的拉曼信號，再來，因為摻雜異原子的關係，使摻雜石墨烯不具有零價帶的特性而且還調整了費米能階的位置，在藉由適當的拉曼雷射光，也可以得到增強的拉曼信號。所以說，摻雜石墨烯非常適合應用在石墨烯增強拉曼散射上面。然而，目前異原子摻雜石墨烯片的合成方法通常很繁雜也很耗時，難以實現工業規模生產。因此，如何開發簡單且可控的方式合成異原子摻雜石墨烯片將會導致科學領域以及應用層面上會有很重要的突破。在這裡，我們透過球磨法以機械化學的方式剝離石墨，它的原理是提供足夠的能量來削弱石墨層與層之間的凡德瓦力並促進異原子能嵌入石墨烯中。本文將會合成具有不同摻雜類型且可控制摻雜濃度的數層摻雜石墨烯，並進行詳細的材料鑑定並在最後提出我們所製備的異原子摻雜石墨烯確實可以提供拉曼訊號增強的結果。

Recent theoretical and experimental studies have suggested that heteroatom-doped graphene nanosheets as emerging materials with exceptional optoelectronic properties for applications including nanoelectronics, energy storage, fuel cells, and electrochemical sensing. Besides those applications, graphene-enhanced Raman scattering (GERS) is a new phenomenon and has attracted intense interest recently. Because of the unique 2D heteroatom-doped sp2 carbon structure, graphene provides particularly enhanced Raman signals for molecules adsorbed on its surface. However, current synthesis methods of heteroatom-doped graphene nanosheets usually involve complicated vacuum systems and time-consuming process, making it difficult to enable industrial-scale production. Consequently, the development of a facile and controllable synthesis of heteroatom-doped graphene nanosheets will lead to important advances on both scientific studies and innovation applications.

Here we report the production of few-layered heteroatom-doped graphene nanosheets with varying dopant types and controlled concentration by an efficient solid phase mechanochemical exfoliation of graphite using ball milling. Ball milling has many advantages, such as time-saving, easy to operate, safe, non-polluting. The physical principle of the ball mill which is provided sufficient energy to weaken the van der Waals interactions and promoted the intercalation of solvent molecules into the graphene sheets within bulk graphites. At this moment, the foreign atom we added will change the graphene original structure and it will improve the electrical properties and enhance the Raman signals. Detailed materials characterizations including transmission electron microscopy, UV-Vis spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and Atomic force microscopy suggest that boron-, nitrogen-, sulfur-, and phosphorus-doped few-layer graphene nanosheets with varying dopant concentrations were successfully prepared. In our work, we successfully confirm that the as-prepared heteroatom-doped graphene nanosheets process the GERS properties.

Abstract i
摘要 ii
致謝 iii
Acknowledge iv
Content v
Table of content vii
List of figure vii
List of table xvi
1. Introduction 1
1.1 Introduction of graphene nanosheets 1
1.2 Introduction of doped graphene nanosheets 5
1.3 Synthesis of doped graphene nanosheets 8
1.3.1 Chemical vapor deposition (CVD) 10
1.3.2 Ball milling 13
1.3.3 Plasma and other methods 17
1.4 Advanced application of heteroatom-doped graphene nanosheets 18
1.5 Surface-enhanced Raman scattering (SERS) 19
1.6 Graphene-enhanced Raman scattering (GERS) 27
2. Characterization 34
2.1 Raman spectroscopy (Raman) 34
2.2 X-ray photoelectron spectroscopy (XPS) 34
2.3 Scanning electron microscope (SEM) 34
2.4 Transmission electron microscope (TEM) 35
2.5 Model MCP-T610 35
2.6 Ultraviolet-visible spectroscopy (UV-Vis) 35
2.7 Atomic force microscopy (AFM) 35
2.8 Ultraviolet Photoelectron Spectroscopy (UPS) 36
2.9 Four point probe resistivity measurement 36
3. Experiment Section 37
3.1 Experiment chemical 37
3.2 Experiment progress 37
3.2.1 Synthesis of blank graphene nanosheets 37
3.2.2 Synthesis of doped graphene nanosheets 38
3.3 GERS-based substrate preparation 39
3.4 The band gap of doped graphene (Tauc plot) 40
3.5 Adsorption ability of various material toward R6G 40
4. Result and discussion 42
Property of Blank-Graphene / Doped-Graphene 42
4.1 Blank Graphene 43
4.2 Nitrogen doped-graphene 47
4.3 Boron doped-graphene 57
4.4 Sulfur doped-graphene 67
4.5 Phosphorus doped-graphene 77
5. Doped graphene nanosheets as GERS substrate 89
5.1 GERS performance 89
5.2 Adsorption ability effect on GERS 95
5.3 Band structure effect on GERS (Tauc plot、UPS) 103
5.4 Limit of detection of Rhodamine 6G 109
5.5 GERS-based Folic Acid Detection 111
6. Conclusion & Future work 112
7. Reference 113

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