由於鑽石具有許多優異的物理及化學特性，因此有極高的應用潛力。其中又以作為電子場發射源材料，吸引各地研究團隊進行相關研究，但是微米晶鑽石其導電性差、粗糙的刻面(facet)表面不利於微型化的元件和電子場發射應用。為了克服上述問題，近幾年來合成超奈米晶鑽石，成為相當熱門的研究主題，這是因為奈米晶鑽石晶界中含有sp2鍵結材料，使其導電性明顯增加，且大輻降低表面粗糙度。故在真空電子場發射元件中的應用上具有很大的潛力。

因此本論文中利用「IPLAS系統」，微波電漿輔助化學氣相沉積法(MPCVD，microwave plasma chemical vapor deposited)，沉積超奈米晶鑽石薄膜於矽基板上。接著使用「IPLAS系統」對超奈米晶鑽石薄膜進行電漿後處理，使其能得到較佳導電性，讓超奈米晶鑽石薄膜的電子場發射表現改善。

實驗共分成三大部分：
第一部分為製備超奈米晶鑽石薄膜時，在基板載台施加不同偏壓(0 V、-200 V)，作為不同特性之電漿後處理薄膜。接著再對不同特性之超奈米晶鑽石薄膜，利用甲烷氮氣混合電漿進行電漿後處理。電漿後處理同時基板載台施加不同偏壓(0 V、-200 V)作為比較。製程結束後利用掃描式電子顯微鏡（SEM）、拉曼光譜（Raman）、電子場發射、穿透式電子顯微鏡，評估超奈米晶鑽石薄膜在不同的製程條件下，對於電子場發射表現最佳之製程條件。
發現利用原始UNCD薄膜(未添加偏壓)作為第一層材料，經過電漿後處理製程之薄膜，擁有最佳場發射特性表現。

接著利用第一部分得到，最佳的超奈米晶鑽石薄膜基底，再使用甲烷氮氣混合電漿進行電漿後處理，製程時對基板載台施加偏壓(0 V、-100 V、-200 V)，觀察電漿後處理製程時，施加偏壓大小對於電子場發射的影響。可發現隨著偏壓增加，超奈米晶鑽石薄膜的電子場發射表現也隨之優化。
第二部分利用超奈米晶鑽石薄膜基底，使用甲烷氮氣混合電漿，添加微量氫氣(0%、0.1%、1%)，並改變電漿後處理時間(10、30、60分鐘)。藉此評估不同電漿後處理氣氛，以及電漿後處理時間，對於超奈米晶鑽石薄膜之電子場發射影響。
發現利用未添加氫氣之電漿後處理，製程超奈米晶鑽石薄膜電子場發射有較佳表現，且較長時間的電漿後處理，對於超奈米晶鑽石薄膜電子場發射有較佳改善。

第三部分為單晶鑽石製程實驗:內容大致分為，鉬載台設計對於單晶鑽石製程的影響，以及單晶鑽石製程參數部分(對於鉬載台的尺寸、製程時間、氣體摻雜、單晶鑽石拼接大面積化有初步的討論)。

Growth, microstructure and electron field emission (EFE) characteristics of ultrananocrystalline diamond (UNCD) films were investigated in this research work, where the UNCD films have been grown by using the microwave plasma enhanced chemical vapor deposition (MPECVD) process. A simple and robust method has been developed to enhance the EFE properties of UNCD films. To achieve such enhanced EFE properties of UNCD films, firstly the granular structure of UNCD films is being modified by post-treatment of the films by subjecting the CH4(6%)/N2(94%) plasma at low substrate temperature to acquire a unique granular structure. The ppt-processed UNCD films exhibited a high conductivity of σ=518 S/cm, as well as excellent EFE properties with a turn-on field of E0=5.84 V/μm (Je=0.72 mA/cm2 at 11.8 V/μm). TEM investigation revealed that the prime factor which enhanced the conductivity/EFE properties of the UCND films via ppt-process is the anisotropic growth of diamond grains in UNCD films, forming flakiness-like granular structure. However, for achieving such phenomena, the granular structure of the primary UNCD layer has to be relatively open. That is, the size of grains should be sufficiently small, whereas the grain boundaries should be of considerable thickness, containing abundant hydrocarbon species.

To understand the mechanism of ppt process, during the ppt process, we have added a small amount of hydrogen gas as working gas, and the ppt process has been performed at different process time. The constituents in the post-treatment plasma have imposed a significant effect on the granular structure modified UNCD films through ppt-process, which results in altered conductivity/EFE properties. TEM investigations revealed that the presence of CH and H specie in the plasma inhibit the effect of C2 and CN species on the induction of the anisotropic growth of the ultra-small diamond grains or the formation of dendrite-like diamond grains. In other words, the formation of flakiness-like grains is restricted.

Moreover, the surface microstructure has not been changed by ppt-process, even employed for a long time. Instead, the evolution in granular structure has been occurred for entire UNCD films and converted into a new granular structure by the ppt-process. While the longtime ppt-process causes a deeper interaction of the plasma with the UNCD materials, which roots in a significant change in the conductivity and EFE properties of the ppt processed UNCD films.

Finally, we have investigated the growth irregularity of single crystalline diamond (SCD) in the MPECVD growth process. To avoid the formation of polycrystalline diamond (PCD) at the edge of SCD substrates during SCD growth process, we have designed a movable Mo substrate holder with a recess to maintain the same distance between plasma and surface of SCD substrate in the growth process. Therefore, the surface temperature of SCD could be uniform and hinder the PCD growth at the edge of SCD substrates.

中文摘要 .................................................i
Abstract .........................................iii
致謝 .................................................v
目錄 .................................................vi
表目錄 .................................................xi
圖目錄 .................................................xii

第一章 序論 .........................................1
1.1 介紹 .........................................1
1.2 實驗動機 .........................................3

第二章 文獻回顧 .........................................8
2.1 鑽石介紹 .........................................8
2.1.1 鑽石分類 .........................................13
2.1.2 鑽石外觀呈色 .................................15
2.1.3 鑽石製程 .........................................15
2.1.4 鑽石孕核 .........................................16
2.1.5 超奈米晶鑽石薄膜成長 .........................17
2.1.6 電子場發射理論 .................................18
2.1.7 鑽石薄膜電子場發射 .........................20
2.1.8 實驗目標 .........................................21

第三章 研究方法與實驗步驟 .........................22
3.1 化學氣相沉積法鑽石薄膜製程 .................22
3.1.1 IPLAS CVD系統 .................................22
3.1.2 超奈米晶鑽石製備 .................................23
3.1.3 超奈米晶鑽石電漿後處理製程 .................25
3.2 鑽石薄膜檢測 .................................26
3.2.1 掃描式電子顯微鏡(Scanning electron microscope - LEO(ZEISS), LEO 1530VP) .........................................26
3.2.2 拉曼光譜(Raman spectrum - Horiba Jobin Yvon, LABRAM HR 800 UV)….. .................................................28
3.2.3 光發射光譜 (Optical Emission Spectra, OES – Ocean, USB4000) .........................................................29
3.2.4 電子場發射 (自製系統) .........................31
3.2.5 霍爾效應 (Hall Effect) .........................33
3.2.6 穿透式電子顯微鏡 (Transmission Electron Microscope - JEOL, JEM-2100F-HR) .........................................36
3.3 穿透式電子顯微鏡樣品製備 .........................39
3.3.1 樣品手動研磨步驟 .................................39
3.3.2 離子蝕薄機(Precision ion polishing system)步驟 .40

第四章 高導電性鑽石薄膜製備之不同性質「前置層」超奈米晶鑽石薄膜的影響 .........................................................41
4.1 實驗背景 .........................................41
4.2 結果討論 .........................................42
4.2.1 不同性質超奈米晶鑽石薄膜之影響 - 鑽石薄膜特性分析 .42
4.2.2 不同性質超奈米晶鑽石薄膜之影響 - 材料微結構觀察 .55
4.3 小結 .........................................67

第五章 不同「後處理電漿」條件對高導電性鑽石薄膜之電性影響 .68
5.1 實驗背景 .........................................68
5.2 結果討論 .........................................68
5.2.1 電漿後處理製程中，使用不同摻氫濃度、電漿後處理時間之影響 .........................................................68
5.2.2 電漿後處理製程施加不同偏壓之影響 .................89
5.2.3 利用單晶鑽石基板進行兩步驟MPCVD製程製備高導電性鑽石薄膜 .........................................................96
5.4 小結 .........................................103

第六章 單晶鑽石製程優化 – 多晶鑽石生成抑制 .................106
6.1 介紹 .........................................106
6.1.1 實驗動機 .........................................107
6.2 單晶鑽石文獻回顧 .................................108
6.2.1 微波電漿化學氣相沉積法製備單晶鑽石 .........108
6.2.2 微波電漿化學氣相沉積法鑽石成長機制 .........109
6.2.3 美國卡內基實驗室 .................................117
6.2.4 日本國家先進工業科學技術研究所 (AIST，National Institute of Advanced Industrial Science and Technology) .........121
6.3 研究方法與實驗步驟 .........................138
6.3.1 IPLAS CVD系統 .................................138
6.3.2 工作氣體 .........................................139
6.3.3 單晶鑽石基板 .................................140
6.3.4 鉬基板載台設計 .................................142
6.3.5 單晶鑽石前處理 .................................144
6.3.6 單晶鑽石成長製程 .................................145
6.3.7 單晶鑽石表面溫度監測與控制 .................146
6.3.8 系統與鉬載台清潔 .................................147
6.3.9 CVD單晶鑽石與基板分離以及研磨拋光 .................147
6.4 單晶鑽石製程實驗 .................................148
6.4.1 單晶鑽石鉬基板載台設計 .........................148
6.4.2 多晶鑽石生成 .................................153
6.5 小結 .........................................158

第七章 總結 .........................................159
7.1 總結 .........................................159
7.2 未來展望 .........................................160

第八章 附錄 .........................................162
8.1 高導電性鑽石微結構 – 針狀鑽石或是片狀鑽石? .........162
8.2 電漿後處理或是二次成長 .........................165
8.3 鑽石成長機制 .................................168
8.4 偏壓影響 .........................................171
8.5 鑽石薄膜場發射機制 .........................174

參考文獻 .................................................177

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