場發射是近期應用於科學或是工業領域中相當常見電子供給方法之一，其應用如電子顯微鏡、微波放大器、螢幕顯示器、陰極射線管、電漿生成器以及X光發射器電子源。其發射電子之機制在於，當對材料施加電場時，其對表面電子產生肖特基效應，使部分電子憑藉低於突破能障所需之能量，透過穿隧效應脫離材料表面，並進入真空環境中之機率大幅提升。由於場發射效應與電場具有直接的關聯性，因此適當的分布場發射材料之發射尖端，將有助於製造更均勻的分布、提升場發射效率、並且降低場遮蔽效應。有鑑於此，目前仍有許多的研究致力於開發相關製程技術，以通過調整發射端的密度及分布方式，或是改用較低功函數材料等方式，改善場發射的特性。
本研究所使用之材料為一種三維結構之碳系複合材料：奈米碳片球。奈米碳片球為 2018年時由實驗室成員蔡秉桓所開發之碳系複合材料。該複合材料係由多個方向之碳系複合材料薄片所組成之球狀結構，而每個薄片皆由一個鑽石核心及多層石墨稀之覆蓋層所組成。該結構使奈米碳片球在場發射過程中，由鑽石核心提供堅固結構及良好導熱性質，與由墨稀層透過較低的電阻值進行電子的傳送，達到出色的場發射性質。而奈米碳片球另一個特色在於其合成機制，若使用微波電漿化學氣相沉積法進行合成時，奈米碳片球之成核點有高機率會沉積於基板表面具有缺陷之區域。本研究即利用這個特性，提出了兩種利用雷射在矽表面創建缺陷圖案之方法來研究使奈米碳片球在指定區域內生長，並討論了雷射與奈米碳片球成核之關係。而為了進一步提高納米碳片球的場發射特性，在具有圖樣之奈米碳片球上沉積了一層碳納米管。而場發射的結果顯示，起始電場由原先的28.4 降至 4.2 V/μm，降幅達到85.9 %，而在壽命的表現上奈米碳片球以及奈米碳管之複合材料，在高密度沉積之條件下，擁有超過十天以上的穩定表現。

Field emission is one of the electron-emitting methods recently applied to scientific or industrial fields, such as the electron microscope, microwave amplifier, display, cathode ray tube, plasma generator, and x-ray source. When an electrical field is applied to the material, it creates the tunneling effect or Schottky effect on the electrons at the surface, increasing the possibility of these electrons conquering the energy barrier with energy lower than required and emitting to the environment. Since the field emission effect is highly related to the electrical field, proper emitter distribution guarantees better emission efficiency and reduces the screening effect. As a result, many previous studies are dedicated to improving the field emission properties by adjusting the density and distribution of the emitters or changing the material with lower work functions.
This study uses the carbon nanoflake ball (CNFB) as the emitter’s material. CNFB is a novel carbon-based composite material discovered by Ping-Huan Tsai, 2018. It is a sphere-like material constructed with multi-direction carbon composite flakes. Each flake has a diamond core covered by a few graphite layers. During the field emission process, the diamond core provides a robust construction with good heat conduction, while the graphene layer transports the electrons with lower resistance. Another unique characteristic of the CNFB is the synthesis mechanism. When synthesizing CNFB with microwave plasma chemical vapor deposition (MPCVD), the nucleation sites of the CNFB are highly possible to be generated at the surface's defect.
With the properties of the CNFB, this study proposed a method of using the laser to create designed defect patterns on the silicon surface to study the selective growth of CNFB and the relationship between the laser and the deposition of CNFB is discussed. To further improve the field emission characteristics of the CNFB, A layer of carbon nanotubes (CNT) is deposited on the patterned CNFB. The result of the field emission shows a promising improvement in the turn-on field voltage and the threshold voltage with the designed pattern. The turn-on field decreased from 28.4 to 4.2 V/μm, while the CNFB-CNT composite material revealed long-term and stable stability.

摘要 III
Abstract IV
致謝 VI
Index X
Figures Caption XV
Tables Caption XX
Chapter 1 Introduction 1
Chapter 2 Literature Review 3
2.1 Carbon-based material 3
2.1.1 Carbon nanotube 4
2.1.2 Graphene 10
2.1.3 Diamond 11
2.1.4 Carbon nanoflake ball 16
2.2 Electron field emission 17
2.2.1 Electron field emission theory 17
2.2.2 Thermionic emission 18
2.2.3 Cold field emission 20
2.2.4 Theory of cold emission 20
2.2.5 Electron field emission with non-planar emitters 21
2.2.6 Screening effect 22
2.3 Laser manufacturing 25
2.3.1 Laser heat affected zone 25
2.3.2 Nd:YAG Laser manufacturing 25
2.4 Image processing 26
2.4.1 Image de-noising 26
2.4.2 Image segmentation 27
2.4.3 Image morphology 28
Chapter 3 Methods and Equipment 30
3.1 Equipment 30
3.1.1 Microwave plasma chemical vapor deposition 30
3.1.2 Scanning electron microscopy 32
3.1.3 Field emission 33
3.1.4 Laser 35
3.1.5 Ultrasonic cleaner 36
3.1.6 Optical Emission Spectroscopy (OES) 37
3.2 Method 38
3.2.1 Laser-induced CNFB (LI-CNFB) 38
3.2.2 Laser selective growth of CNFB (LSG-CNFB) 44
3.2.3 Deposition of CNFB-CNT 47
3.2.4 Field emission 48
3.3 Data recording program 49
3.3.1 Temperature data 50
3.3.2 OES data 50
3.3.3 Pressure data 50
3.3.4 Timer update 50
3.3.5 Non-real timer 51
Chapter 4 Results 52
4.1 Laser-induced CNFB 52
4.1.1 Laser Engraving Process 52
4.1.2 Ultrasonic treatment 54
4.1.3 MPCVD deposition process 54
4.1.4 SEM image processing 56
4.1.5 Laser-induced pattern designed CNFB 60
4.2 Laser selective growth of CNFB 62
4.2.1 Ultrasonic treatment 63
4.2.2 Laser Engraving process 64
4.2.3 MPCVD deposition 66
4.2.4 The average power of LSG-CNFB 67
4.2.5 Pattern-designed LSG-CNFB 68
4.2.6 Image process of the LSG-CNFB 74
4.3 CNFB-CNT 79
4.3.1 Laser-induced CNFB-CNT 81
4.3.2 Laser selective growth of CNFB-CNT 84
4.4 Field emission properties 86
4.4.1 Field emission of laser-induced CNFB 86
4.4.2 Field emission of LSG-Carbon-based material 88
4.4.3 Field emission properties 96
4.5 Field emission stability 98
4.5.1 Stability of Nan_W0L0 98
4.5.2 Stability of Hex_W50L80 100
4.5.3 Long-term stability 102
4.6 Data recording program 106
4.7 Mechanisms 110
4.7.1 Nucleation layer 110
4.7.2 Deactivated Nucleation layer 114
4.7.3 CNFB deposition on the activated nucleation layer 116
4.7.4 Deposition on the Deactivated nucleation layer 118
Chapter 5 Uncertainty 121
5.1 Ultrasonic treatment 121
5.1.1 Solution of the Ultrasonic treatment 121
5.1.2 Power of the ultrasonic treatment 121
5.2 Laser engraving process 122
5.3 Deposition of CNFB 122
5.3.1 Temperature during the deposition process 122
5.3.2 Duration of the deposition process 123
5.4 Deposition of CNFB-CNT 123
Chapter 6 Conclusion and future work 124
6.1 Conclusions 124
6.2 Future work 125
Reference 127

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