鑽石擁有許多優異的物理與機械性質，因此已成為機械、通訊與光電產業上的重要工程材料之ㄧ。在本研究中，熱重熔（thermal reflow）技術被運用在化學氣相沉積（CVD）鑽石膜上製作金屬微遮罩，並使用反應離子蝕刻（RIE）系統蝕刻鑽石膜，藉以製作出不同的鑽石微結構。實驗中反應離子蝕刻的參數條件如下：射頻功率為180W，混合氣體CF4/O2的比例範圍為0~20%，蝕刻時間為5分鐘至20分鐘，根據不同的金屬遮罩、形狀與尺寸，以及蝕刻時反應氣體的壓力與比例，可在鑽石膜上製作出直徑約為20nm~5μm、高度為100nm到數微米的錐狀/柱狀鑽石微結構。並使用微拉曼頻譜儀分析蝕刻後的鑽石微結構；結果顯示，蝕刻後的鑽石微結構仍保持良好的鑽石結構，並且其表面存在有一層非常薄的石墨和無晶形碳。

Diamond, having many advanced physical and mechanical properties,is one of the most important materials used in the mechanical,telecommunication and optoelectronic industry. In the present study,thermal reflow technique was employed to generate metal micro-masks over the CVD diamond film. The reactive ion etching (RIE) systems were subsequently used to etch the diamond film and to produce various micro-structures. RIE was performed under conditions that RF power at 180 W, and the CF4/O2 ratio  ranged from 0~20%. The etching time ranged from 5min to around 20min. Depending on the size,shape and material of the metal mask, gas pressure and reactant gases ratio used in etching, micro-structures of 20nm~5μm in diameter, 100nm to several micrometers in height and cone/pillar in shape were generated on the diamond film. Micro-Raman spectra were used to analyze the etched specimens and the results showed that the obtained micro-structures retained the perfect diamond structure with a very thin layer of graphite and amorphous carbon on the surface of etched diamond film.

目錄
誌謝............................................................................................................. I
中文摘要....................................................................................................II
英文摘要...................................................................................................III
目錄............................................................................................................V
圖目錄....................................................................................................VIII
表目錄..................................................................................................... XII
第一章 緒論..............................................................................................1
1-1 前言..............................................................................................1
1-2 研究背景......................................................................................6
1-3 研究動機與目的..........................................................................9
第二章 文獻回顧...................................................................................................10
2-1 鑽石膜合成法............................................................................10
2-2 鑽石材料移除............................................................................12
2-2-1 微裂（Micro-chipping）..................................................12
2-2-2 石墨化（Graphitization）................................................12
2-2-3 氣化（Evaporation） .......................................................13
2-2-4 濺射（Sputtering） ..........................................................13
2-2-5 化學反應（Chemical reaction）......................................13
2-3 CVD 鑽石膜拋光........................................................................14
2-3-1 機械拋光(Mechanical polishing).....................................14
2-3-2 化學輔助機械拋光與平坦化(CAMPP)..........................14
2-3-3 雷射拋光(Laser polishing) ...............................................15
2-3-4 離子束拋光(Ion beam polishing) ....................................16
2-3-5 複合拋光(Compound Polishing) .....................................16
2-4 電漿原理....................................................................................17
2-5 鍍膜機制....................................................................................18
2-6 蝕刻原理與反應離子蝕刻系統................................................19
2-7 鑽石微結構................................................................................21
第三章 實驗方法...................................................................................................28
3-1 實驗規劃.....................................................................................28
3-2 實驗流程圖.................................................................................29
3-3 實驗步驟.....................................................................................30
3-4 實驗設備.....................................................................................34
3-4-1 鍍金機...............................................................................34
3-4-2 反應離子蝕刻系統...........................................................35
3-4-3 高溫爐管...........................................................................35
3-4-4 分析檢測儀器...................................................................36
第四章 結果與討論..............................................................................................39
4-1 金遮罩的形成機制....................................................................39
4-1-1 金屬遮罩之選擇...............................................................39
4-1-2 鍍金厚度與蝕刻影響.......................................................39
4-1-3 以熱重融法製作金屬遮罩...............................................41
4-2 通氧弱化鑽石膜結構................................................................46
4-2-1 氧弱化鑽石初成膜...........................................................46
4-2-2 氧弱化拋平鑽石膜...........................................................50
4-3 氧弱化鑽石膜對反應離子蝕刻影響........................................55
4-3-1 以反應離子蝕刻加工經氧弱化鑽石初成膜...................55
4-3-2 以不同反應氣體加工經氧弱化鑽石初成膜...................63
4-3-3 以反應離子蝕刻加工經氧弱化鑽石拋平膜...................69
4-3-4 以不同氣體加工經氧弱化拋平鑽石膜...........................75
第五章 結論............................................................................................................81
參考文獻...................................................................................................................83
圖目錄
圖1-1、陣列式雷射用鑽石散熱片...................................................................5
圖1-2、高頻率表面聲波元件.............................................................................5
圖1-3、X 光微影之鑽石罩幕.............................................................................5
圖1-4、合成鑽石的區間......................................................................................7
圖2-1、鑽石膜沉積法示意圖(a)熱燈絲法(b)NIRIM 微波法(c)ASTEX
微波法(d)直流電弧法...........................................................................................11
圖2-2、CAMPP 示意圖..........................................................................................15
圖2-3、雷射拋光示意圖....................................................................................15
圖2-4、鑽石膜理想的蝕刻深度......................................................................16
圖2-5、(A)電漿的電中性(B)電漿放電簡圖................................................17
圖2-6、退火製程金奈米粒子(A)退火前(B)退火後金奈米粒子...........19
圖2-7、蝕刻原理示意圖(A)化學性蝕刻 (B)物理性蝕刻......................20
圖2-8、反應離子刻蝕反應腔剖面示意圖...................................................21
圖2-9、(A)隨機方向微米晶鑽石膜(B)在鑽石膜上形成金遮罩(C)蝕刻
後形成微米鑽石奈米柱狀物陣列....................................................................24
圖2-10、使用反應離子蝕刻化學氣相沉積鑽石製作壓阻式壓力感測器
.....................................................................................................................................25
圖2-11、經遮罩保護加工後之垂直側壁鑽石微結構...............................26
圖3-1、實驗規劃流程圖.........................................................29
圖3-2、本研究所使用鑽石膜(A)鑽石初成膜(B)拋平鑽石膜...............30
圖3-3、金屬鍍層熱重融後蝕刻示意圖........................................................33
圖3-4、鍍金機.......................................................................................................34
圖3-5、(a)RIE 反應主機(b)供氣系統(c) RF generator.........................35
圖3-6、高溫爐管..................................................................................................35
圖3-7、光學顯微鏡.............................................................................................36
圖3-8、表面形貌儀.............................................................................................36
圖3-9、場發射電子顯微鏡...............................................................................37
圖3-10、拉曼光譜儀...........................................................................................38
圖3-11、拉曼光譜檢測圖(A)鑽石初成膜(B)鑽石拋平膜.......................38
圖4-1、鑽石初成膜與拋平鑽石膜鍍金前後SEM 圖(A)(B)鑽石初成膜
與拋平鑽石膜無鍍金之原始表面，(C)(D)鑽石初成膜與拋平鑽石膜鍍
金2.7nm 之表面，(E)(F)鑽石初成膜與拋平鑽石膜鍍金5.5nm 之表面
.....................................................................................................................................40
圖4-2、拋平鑽石膜鍍金2.7nm 經熱重融後之表面(A)650 度(B)700 度
(C)750 度(D)800 度，拋平鑽石膜鍍金5.5nm 經熱重融後之表面結果
(E)650 度(F)700 度(G)750 度(H)800 度.............................43
圖4-3、鑽石初成膜鍍金2.7nm 經熱重融後之表面(A)650 度(B)700 度
(C)750 度(D)800 度，鑽石初成膜鍍金5.5nm 經熱重融後之表面結果
(E)650 度(F)700 度(G)750 度(H)800 度.............................44
圖4-4、鑽石初成膜鍍金2.7nm 經熱重融後利用氧氣弱化後之表面
(A)650 度(B)700 度(C)750 度(D)800 度，對照組無氧氣弱化後之表面
(E)650 度(F)700 度(G)750 度(H)800 度.............................48
圖4-5、鑽石初成膜鍍金5.5nm 經熱重融後利用氧氣弱化後之表面
(A)650 度(B)700 度(C)750 度(D)800 度，對照組無氧氣弱化後之表面
(E)650 度(F)700 度(G)750 度(H)800 度.............................49
圖4-6、鑽石初成膜鍍金經850 溫度熱融後表面(A)通氧 (B)未通氧之
表面結果...................................................................................................................50
圖4-7、拋平鑽石膜鍍金2.7nm 經熱重融後利用氧氣弱化後之表面
(A)650 度(B)700 度(C)750 度(D)800 度，對照組無氧氣弱化後之表面
(E)650 度(F)700 度(G)750 度(H)800 度.............................52
圖4-8、拋平鑽石膜鍍金5.5nm 經熱重融後利用氧氣弱化後之表面
(A)650 度(B)700 度(C)750 度(D)800 度，對照組無氧氣弱化後之表面
(E)650 度(F)700 度(G)750 度(H)800 度.............................53
圖4-9、拋平鑽石膜鍍金經850 溫度熱重融後表面(A)通氧 (B)未通氧
之表面結果..............................................................................................................54
圖4-10、氧弱化與RIE 製作鑽石微結構示意圖.......................................57
圖4-11、鑽石初成膜鍍上2.7nm 厚之金薄膜經熱重融氧弱化後以反應
離子蝕刻加工結果(A)650 度(B)700 度(C)750 度(D)800 度。無氧弱化
對照結果(E)650 度(F)700 度(G)750 度(H)800 度...................58
圖4-12、鑽石初成膜鍍上5.5nm 厚之金薄膜經熱重融氧弱化後以反應
離子蝕刻加工結果(A)650 度(B)700 度(C)750 度(D)800 度。無氧弱化
對照結果(E)650 度(F)700 度(G)750 度(H)800 度...................61
圖4-13、鑽石初成膜經熱氧化以反應離子蝕刻加工後以拉曼光譜檢測
之結果(A)650(B)700(C)750(D)800 度。無經氧弱化加工後之結果
(E)650(F)700(G)750(H)800 度.....................................62
圖4-14、鑽石初成膜鍍上2.7nm 厚金薄膜經熱重融氧弱化後以反應離
子蝕刻加工結果(A)650 度(B)700 度(C)750 度(D)800 度。無氧弱化對
照結果(E)650 度(F)700 度(G)750 度(H)800 度......................65
圖4-15、鑽石初成膜鍍上5.5nm 厚金薄膜經熱重融氧弱化後以反應離
子蝕刻加工結果(A)650 度(B)700 度(C)750 度(D)800 度。無氧弱化對
照結果(E)650 度(F)700 度(G)750 度(H)800 度......................67
圖4-16、鑽石初成膜經熱氧化以反應離子蝕刻加工後以拉曼光譜檢測
之結果(A)650(B)700(C)750(D)800 度。無經氧弱化加工後之結果
(E)650(F)700(G)750(H)800 度.....................................68
圖4-17、拋平鑽石膜鍍上2.7nm 厚之金薄膜經熱重融氧弱化後以反應離子蝕刻加工結果(A)650 度(B)700 度(C)750 度(D)800 度。無氧弱化
對照結果(E)650 度(F)700 度(G)750 度(H)800 度...................71
圖4-18、拋平鑽石膜鍍上5.5nm 厚之金薄膜經熱重融氧弱化後以反應
離子蝕刻加工結果(A)650 度(B)700 度(C)750 度(D)800 度。無氧弱化
對照結果(E)650 度(F)700 度(G)750 度(H)800 度...................73
圖4-19、拋平鑽石膜經熱氧化以反應離子蝕刻加工後以拉曼光譜檢測
之結果(A)650(B)700(C)750(D)800 度。無經氧弱化加工後之結果
(E)650(F)700(G)750(H)800 度.....................................74
圖4-20、拋平鑽石膜鍍上2.7nm 厚金薄膜經熱重融氧弱化後以反應離
子蝕刻加工結果(A)650 度(B)700 度(C)750 度(D)800 度。無氧弱化對
照結果(E)650 度(F)700 度(G)750 度(H)800 度......................76
圖4-21、拋平鑽石膜鍍上5.5nm 厚金薄膜經熱重融氧弱化後以反應離
子蝕刻加工結果(A)650 度(B)700 度(C)750 度(D)800 度。無氧弱化對
照結果(E)650 度(F)700 度(G)750 度(H)800 度......................79
圖4-22、拋平鑽石膜經熱氧化以反應離子蝕刻加工後以拉曼光譜檢測
之結果(A)650(B)700(C)750(D)800 度。無經氧弱化加工後之結果
(E)650(F)700(G)750(H)800 度.....................................80
表目錄
表1-1 鑽石與其他材料特性比較表........................... 3
表1-2 奈米鑽石的主要應用................................. 4
表1-3 各種CVD 法製作鑽石膜之比較........................ 8
表2-1 物理性蝕刻與化學性蝕刻比較表...................... 20
表2-2 反應離子蝕刻參數與蝕刻結果比較表.................. 27
表3-1 鑽石膜鍍膜實驗參數................................ 30
表3-2 鑽石膜氧弱化實驗參數.............................. 31
表3-3 以氧氣反應離子蝕刻鑽石膜之實驗參數................ 32
表3-4 以CF4 混合氣體RIE 蝕刻鑽石膜之實驗參數............ 32
表3-5 鍍金機之鍍率表.................................... 34
表4-1 拋平鑽石膜鍍金經不同溫度熱重融之金球遮罩直徑分佈圖45
表4-2 鑽石初成膜鍍金經不同溫度熱重融之金球遮罩直徑分佈圖45

【1】	宋健民，"鑽石合成"全華科技圖書股份有限公司，台北市，第7-2-5-53頁，2000。
【2】	http://www.cvd-diamond.com/tfdipo/frames_e.htm
【3】	http://www.bccresearch.com/images_trend/AVM008B.gif Andrew McWilliams, Report ID: AVM008B, 2003.
【4】	宋健民，"鑽石底半導體及鑽石的半導體"，機械工業 Septembert，No.282，p102-113，2006
【5】	宋健民，"奈米鑽石的大千世界" ,工業材料雜誌,217期,p158-170 ,2005.
【6】	H. O. Pierson, Handbook of Carbon, Graphite, Diamond and Fullerenes, Noyes Publications, Park Ridge, New Jersey, U.S.A., 1993
【7】	P. W. May, "Diamond thin films: A 21st-century material", Volume 358, pp.473-495, Number 1766/January 15, 2000
【8】	A. Feldman, E. N. Farabaugh, L. H. Robins, Ceramic Film and Coatings, Chap12 Chemical Vapor Deposited Diamond, Noyes Publications, Park Ridge, New Jersey, U.S.A., 1993
【9】	A. P. Malshe, "A review of techniques for polishing and planarizing chemical vapor-deposited diamond and substrates", Diamond and Related Materials 8, pp.1198, 1999
【10】	C. J. Tang, A. J. Neves, A. J. S. Fernandes, J. Grácio, N. Ali, "A new elegant technique for polishing CVD diamond films", Diamond and Related Materials 12, pp.1411, 2003
【11】	F.M. van Bouwelen, " Diamond polishing from different angles ", Diamond Relat. Mater. Vol. 9, p.925, 2000
【12】	J. E. Field, S.E. Grillo, " Investigation of the possibility of electrical wear by sparking in diamond polishing ", Appl. Phys. Vol. 33, pp.985-990, 2000
【13】	張克從，張樂潓主編，"晶體生長科學與技術"，科學出版社，北京市，Chapter 14，1997
【14】	A.P. Semenov, V.V. Pozdnjakov, L.B. Kraposhina, " Friction and Contact Interaction of Graphite with Metals and Alloys ", Nauka, Moscow, p.108, 1974
【15】	F. K. Theije, "Oxidative etching of diamond ", Diamond and Related Materials 9, pp.929, 2000
【16】	W.N.G. Hitchon, " Plasma processes for semiconductor fabrication ", SPIE Vol. 4227, pp.118-130, 2000
【17】	J.Kuhnle, O.Weis, "Mechanochemical superpolishing of diamond using NaNO3 or KNO3 as oxidizing agents", Surface Science 340,pp16-22, 1995
【18】	N. Toyoda, N. Hagiwara, "Surface treatment of diamond films with Ar and O2 cluster ion beams", Nuclear Instruments and Methods in Phys. Research B 148, pp.639, 1999
【19】	C. L. Chao, W. H. Fan, W. C. Chou, C. Y. Chien, H. Y. Lin, J. G. Duduch, Research on Quick Polishing of CVD Diamond Film, Key Materials Vols. 364, pp.668-673, 2008
【20】	王世敏，奈米材料原理與製備，五南圖書出版公司，2004。
【21】	Y. J. Chen, D. J. Yao, F. G. Tseng, "Construction of Two dimensional Au Sphere Array using Nanosphere Lithography", ISBE, 2008
【22】	丁志明、許家維，碳、鎳、白金之薄膜及奈米級薄膜之特性研究，國立成功大學材料科學與工程學系碩士論文，2006。
【23】	Y. J. Chen, D. J. Yao, F. G. Tseng, "Construction of Two dimensional Au Sphere Array using Nanosphere Lithography", ISBE, 2008
【24】	莊尚餘、陳學禮、鄭旭君、王鉦元、朱鐵吉、林俊宏，金奈米粒子之特殊光學特性與應用之研究，國家奈米元件實驗室，奈米通訊，第十二券，第三期，pp.8-15，2005
【25】	S. J. Pearton, " Dry etching processes for fabrication of QWIPs and other detector structures ", SPIE Vol. 2999, pp.1108-1117, 1997
【26】	G. M. R. Sirineni, H. A. Naseem, A. P. Malshe, W. D. Brown, "Reactive ion etching of diamond as a means of enhancing chemically-assisted mechanical polishing efficiency", Diamond and Related Materials 6, pp.952-958, 1997
【27】	E. S. Baik, Y. J. Baik, D. Jeon, "Diamond tip fabrication by air-plasma etching of diamond with an oxide mask", Diamond and Related Materials 8, pp.2169–2171, 1999
【28】	Y. Ando, Y. Nishibayashi, K. Kobashi, T. Hirao, K. Oura, "Smooth and high-rate reactive ion etching of diamond", Diamond and Related Materials 11, pp.824–827, 2002
【29】	C. Y. Li, A. Hatta, "Effect of metal coating on the formation of diamond whiskers in O2 RF plasma", Diamond & Related Materials 15, pp.357 – 360, 2006
【30】	D. S. Hwang, T. Saito, N. Fujimori, "New etching process for device fabrication using diamond", Diamond & Related Materials 13, pp.2207–2210, 2004
【31】	J. Enlund, J. Isberg, M. Karlsson, F. Nikolajeff, J. Olsson, D. J. Twitchen, "Anisotropic dry etching of boron doped single crystal CVD diamond", Carbon 43, pp.1839–1842, 2005
【32】	G. M. R. Sirineni, H. A. Naseem, A. P. Malshe, W. D. Brown, "Reactive ion etching of diamond as a means of enhancing chemically-assisted mechanical polishing efficiency", Diamond and Related Materials 6, pp.952-958, 1997
【33】	H. Uetsuka, T. Yamada, S. Shikata, "ICP etching of polycrystalline diamonds: Fabrication of diamond nano-tips for AFM cantilevers", Diamond & Related Materials 17, pp.728–731, 2008
【34】	C. L. Chao, W. C. Chou, H. C. Lin, R. C. Liao, "Microstructures Research of Plasma Etching CVD Diamond Films", MRS-T, pp.292, 2007
【35】	Y. S. Zou, Y. Yang, W. J. Zhang, Y. M. Chong, B. He, I. Bello, and S. T. Lee, "Fabrication of diamond nanopillars and their arrays", Applied Physics Letters 92, 053105, 2008
【36】	V. Ovchinnikov *, A. Malinin, S. Novikov, C. Tuovinen, "Materials Science and Engineering" B69–70 459–463, 2000
【37】	R. Otterbach*, U.Hilleringmann, "Diamond and Related Materials" 841–844,2002
【38】	C. L. Lee, H. W. Choi, E. Gu, M. D. Dawson, H. Murphy, "Fabrication and characterization of diamond micro-optics", Diamond & Related Materials 15, pp.725 – 728, 2006
【39】	G.F. Ding, H.P. Mao, Y.L. Cai *, Y.H. Zhang, X. Yao, X.L. Zhao, "Micromachining of CVD diamond by RIE for MEMS applications", Diamond & Related Materials 14 pp.1543 – 1548,2005
【40】	X. D. Wang, G. D. Hong, J. Zhang, B. L. Lin, H. Q. Gong, W. Y. Wang, "Precise patterning of diamond films for MEMS application", Journal of Materials Processing Technology 127, pp.230–233, 2002
【41】	周文成，CVD鑽石膜複合拋光及微加工之加工機制與加工表面性狀研究，淡江大學機械與機電工程研究所博士論文，2007
【42】	林夏蓁，以常壓空氣電漿及反應離子蝕刻製作鑽石微結構之研究，淡江大學機械與機電工程研究所碩士學位論文，2007
【43】	廖仁誠，以反應離子蝕刻製作鑽石微結構之研究，淡江大學機械與機電工程研究所碩士學位論文，2008
【44】	何琨，苟立，冉均国，"鑽石薄膜的表面成分和形貌對表面能的影響"，矽酸鹽學報，第38卷，第2期，2010
【45】	S. P. McGeoch, F. Placido, Z. Gou, C. J. H. Wort, and J.A. Savage, "Coatings for the protection of diamond in high-temperature enironments", Diamond & Related Materials 8 p16 – p919,1999
【46】	J. Filik, "Raman spectroscopy: a simple, non-destructive way to characterize diamond and diamond-like materials", Spectroscopy Europe, vol.17, no.5, 2005