臺灣博碩士論文加值系統

本研究是以微波電漿化學氣相沉積系統去合成奈米碳管，觀察以硼、氮元素參雜碳管後，其顯微結構之改變及電子場發射性質受到化學鍵結之影響的關係。經由紅外線光譜分析，氮原子參雜進入碳管石墨層的所形成的主要鍵結為碳-氮單鍵。藉由微波電漿化學氣相系統和電子迴旋共振系統對碳管參雜，氮原子會使的碳管內的sp2 鍵增加，而使的sp3鍵減少，並且使的碳管的電子場發射性質提高。起始電壓由3 V/μm 降到2.5 V/μm, 電場加強因子則可以提高到40~120%。以微波電漿化學氣相沉積系統所生成的氮電漿具有較高的能量，可以穿透到碳管內層的石墨層並與碳原子置換，改變其原來直立結構的石墨壁成為螺旋狀。而使用電子迴旋共振化學氣相沉積系統所激發出的氮電漿只有對碳管的表面局部改質，形成容易發射出電子的斷鍵。若對碳管參雜硼原子則會使的碳管內的sp3鍵結增加並使的電子場發射性質降低，起始電壓會提高到3.5V/μm而電場加強因子會降低35%。這是因為三族的硼元素相較於碳原子少一個電子，在場發射中電洞捕捉電子效應造成電子場發射性質較差。

In this study, we using the microwave plasma enhanced chemical vapor deposition (MPE-CVD) system to synthesize the carbon nanotubes, and observing the structures, chemical bonding and the field emission properties of carbon nanotubes doped by the nitrogen and boron elements. From the results of FTIR, the primary chemical bonds of C/N are single bonds. It is found that N doped carbon nanotubes using ECR-CVD and MPE-CVD can increase the sp2 bonding and decrease the sp3 bonding, which can enhance the properties of field emission. The onset voltages are decreasing from 3 V/μm to 2 V/μm, and the enhancement factor is increasing to 40 ~ 120 %. The nitrogen plasma excited by MPE-CVD has higher energy to substitute the carbon and penetrate the graphite walls. However, the nitrogen plasma excited by ECR-CVD only can treat the surface of carbon nanotubes and form dangling bond that are well to emit electrons. If the carbon nanotubes are doped by boron atoms, the sp3 bonding will increase and the onset voltages will also increase to 3 V/μm. The enhancement factor will decrease in the percentage of 35, it is because of the boron has less electrons, and electron holes will trap the electrons when emitting.

Content
摘要 ……………………………………………………………………...I
Abstract .....................................................................................................II
誌謝 ……………………………………………………………………III
1.Overview of Carbon Nanotubes .......................................................1-1
1.1 Inotroduction ................................................................................1-2
1.2 Structures of carbon nanotubes.................................................... 1-2
1.3 Electronic properties of carbon nanotubes................................... 1-3
1.4 Production of carbon nanotubes ...................................................1-4
1.4.1 Arc discharge method ............................................................1-4
1.4.2 Laser vaporization ………………………………………….1-6
1.4.3 Chemical vapor deposition …………………………………1-7
1.5 The growth mechanism………………………………………….1-9
1.5.1Carbon nanotubes growth without catalyst …………………1-9
1.5.2 Carbon nanotubes growth in the presence of catalyst …….1-10
1.6 The application of carbon nanotubes ..........................................1-11
1.6.1 Field emission display …………………………………….1-11
1.6.2 AFM tips ………………………………………………….1-13
1.6.3 Energy storage …………………………………………….1-13
1.6.4 Interconnect ……………………………………………….1-14
References ……………………………………………………………1-25
2. Carbon Related Materials ………………………………………...2-1
2.1 Bonding of Carbon ……………………………………………...2-1
2.2 Forms of Carbon ………………………………………………..2-3
2.2.1 Ideal Graphite ………………………………………………2-3
2.2.2 Graphite Whiskers ………………………………………….2-3
2.2.3 Carbon Fiber ………………………………………………..2-4
2.2.4 Carbon Blacks and Carbon Onions ………………………...2-5
2.2.5 Amorphous Carbon ………………………………………...2-6
2.2.6 Diamond ……………………………………………………2-7
Reference ……………………………………………………………..2-14
3.Experimental and Characterization ………………………………3-1
3.1 Thin Film of Catalyst ………………………………………...3-1
3.2 Growth of Carbon Nanotubes ………………………………..3-2
3.3 Doping Carbon nanotubes ……………………………………3-2
3.4 CVD system ………………………………………………….3-3
3.4.1.Microwave Plasma Enhanced Chemical Vapor Deposition ..3-3
3.4.2 Electron Cyclotron Resonance CVD ……………………….3-5
3.5 Characterization .………………………………………………..3-7
3.5.1. Scanning Electron Microscope (SEM) …………………….3-8
3.5.2. Transmission Electron Microscopy (TEM) ………………..3-8
3.5.3. Raman Spectroscopy ………………………………………3-8
3.5.4. Fourier Transform Infrared Spectroscopy (FTIR) …………3-9
3.5.5. Electron Field Emission ………………………………….3-10
3.5.6. X-ray Photoelectron spectroscopy (XPS) …………...…...3-10
3.5.7. Flowchart …...…………………………………………….3-12
Reference..…………………………………………………………….3-13
4. Characterization of doped carbon nanotubes …………………...4-1
4.1. Introduction …………………………………………………….4-1
4.2. Results and discussion of doped carbon nanotubes ……………4-2
4.2.1. SEM images ……………………………………………….4-2
4.2.2. TEM images ……………………………………………….4-6
4.2.3. Selected area diffraction (SAD) ………………………….4-13
4.2.4. Raman spectrums ………………………………………...4-21
4.2.5. FTIR ……………………………………………………...4-25
4.2.6 XPS ……………………………………………………….4-27
4.2.7. EELS ……………………………………………………..4-39
4.2.8. Field emission ……………………………………………4-50
4.3. Conclusions …………………………………………………..4-60
Reference……………………………………………………………..4-61
5. Characterization of Carbon Nanotubes Treated by Oxygen Plasma and the Forming of Pd nanowire ……………………………………5-1
5.1 Introduction ……………………………………………………..5-2
5.2 Results and discussion …………………………………………..5-3
5-3 Conclusions ……………………………………………………5-11
Reference ……………………………………………………………..5-12
6. Future Work ……………………………………………………….6-1

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