本論文是以一電容式的電漿輔助化學氣相沉積系統(PECVD)，進行類鑽石薄膜(Diamond-like carbon)覆膜實驗。反應氣體為乙炔(C2H2)、甲烷(CH4)、O2、氬氣(Ar)95﹪＋氫氣(H2)的混合氣體、以Si(100)及鈮酸鋰(LiNbO3)為基板成長類鑽石(DLC)薄膜，研究在不同基板、不同氣體成份比例的條件下對類鑽石薄膜(DLC)品質的影響。並在不同條件DLC薄膜的雙層結構(DLC/LiNbO3)上製作指叉換能器,以探討薄膜在不同條件下對雙層SAW元件的影響。
所成長的類鑽石薄膜，在其特性分析的研究上,分別做原子力顯微鏡(AFM)、掃描式電子顯微鏡(SEM)以及拉曼光譜分析儀(Raman spectrometer)的量測，觀察類鑽石薄膜的性質及特性。
由拉曼光譜分析結果顯示，DLC薄膜的G-band 的波長大多數位於1585~1600cm-1，同時，D-band在1390cm-1處呈現一寬且平坦的曲線，這顯示這些DLC薄膜含有相當量的石墨sp2鍵結以及少量非晶質類鑽石sp3鍵結。由實驗得知在反應氣體為C2H2＋Ar的條件下所成長的DLC薄膜，其製成的SAW元件的插入損失相對效果比較好。由AFM及SEM分析知，DLC覆膜十分緻密且薄膜表面粗糙度均小於10nm，可知薄膜表面平坦，可供元件之製作。

In the present thesis, diamond-like carbon thin films were deposited on Si(100) and LiNbO3 substrates by a planar capacitor plasma-enhence-chemical-vapor-deposition system. The reaction gases were C2H2,CH4,O2 and mixed with Ar (95﹪) and H2(5﹪).The influence of the growth of the thin film from different substrates and three different source gases flow ratios have been studied. The bi-layers structure of SAW(Surface Acoustic Wave) device was then fabricated.
The interdigital transducers (IDTs) were fabricated on the bi-layers structure. The conditions of the DLC thin film of the bi-layers structure was varied in order to discuss its effects on SAW devices.
In addition to Raman analyses, SEM and AFM have been employed to characterize the DLC thin film quality.
From the experimental results of Raman spectrum analysis reveals that the DLC film has wide and flat spectrum region at wavelength of 1585~1600cm-1 of G-band and 1390cm-1 of D-band .It indicates that the DLC film contains much graphite sp2 bonds and a small part of amorphous DLC sp3 bonds.
The optimal deposition conditions of the DLC film have been found for the reaction gas of C2H2 and Ar, from which the insertion loss of the SAW filter shows the quality better than from the others. SEM and AFM analyses shows that the roughness of the DLC film is below 10 nm and the faces of the DLC films are flat to be made into devices.

目錄---------------------------------------------------------------------------I附圖目錄---------------------------------------------------------------------III
中文摘要---------------------------------------------------------------------VII
Abstract--------------------------------------------------------------------VIII
第一章 緒論
1-1 文獻回顧----------------------------------------------------------------1
1-2 碳類薄膜----------------------------------------------------------------4
1-3 鈮酸鋰(LiNbO3)結構與特性------------------------------------------------6
第二章 理論基礎
2-1 RF電漿基礎原理----------------------------------------------------------8
2-2 電容耦合電漿-----------------------------------------------------------10
2-3 電漿輔助化學氣相沈積系統---------------- ------------------------------11
2-4 類鑽碳膜成長機制-------------------------------------------------------12
2-5 SAW 元件的理論與特性---------------------------------------------------15
第三章 實驗方法與步驟
3-1 實驗設備與材料---------------------------------------------------------17
3-2 樣品的準備與鍍膜製程---------------------------------------------------17
3-3 SAW元件的製作----------------------------------------------------------19
3-4 薄膜性質之分析鑑定與SAW元件的參數性質----------------------------------21
第四章 結果與討論
4-1 Raman 光譜分析---------------------------------------------------------25
4-2 SEM分析----------------------------------------------------------------28
4-3 AFM分析----------------------------------------------------------------28
4-4 Interdigital Transducers (IDTs)製作及元件分析--------------------------29
第五章 結論------------------------------------------------------------------31
參考文獻---------------------------------------------------------------------33
附圖-------------------------------------------------------------------------37

附圖目錄
圖1-2-1 鑽石及石墨的結晶形態結構--------------------------------------------37
圖1-2-2 Raman a-C：H film 圖------------------------------------------------38
圖1-3-1 (a)當溫度低於居里溫度時，LiNbO3晶體呈現鐵電性
(b)當溫度低於居里溫度時，LiNbO3晶體呈現順電性-----------------------39
圖2-2-1 電容耦合式電漿源示意圖----------------------------------------------40
圖2-2-2 直流偏壓與射頻功率關係----------------------------------------------41
圖2-3-1 化學氣相沉積法的五個主要機制(a)導入反應物主氣流 (b)反應物內擴散
(c)原子吸附(d)表面化學反應(e)生成物外擴散及移除---------------------42
圖2-3-2 電漿輔助化學氣相沈積系統的結構示意圖--------------------------------43
圖2-4-1 碳離子進入非晶質類鑽碳膜的表面穿透機制示意圖
(a) 直接穿透(b)knock-on 穿透----------------------------------------44
圖2-4-2 非晶質類鑽碳膜的成長機制示意圖(a)表面擴散與聚集(b)高能量離子轟擊基板
(c)交鏈鍵結---------------------------------------------------------45
圖2-5-1 由縱波與剪波組合而成的SAW：(a)縱波傳播模式(c) 剪波傳播模式(c)SAW傳播
模式----------------------------------------------------------------46
圖2-5-2 DLC/LiNbO3雙層結構之SAW元件-----------------------------------------47
圖3-1-1 PECVD系統示意圖-----------------------------------------------------48
圖3-3-1 IDTs電極製作之流程圖------------------------------------------------49
圖3-3-2 舉離法製程之示意圖--------------------------------------------------50
圖4-1-1 不同沉積時間與C2H2：O2：Ar＝8：8：8 條件下的拉曼光譜圖(樣品A)-------51
圖4-1-2 不同沉積時間與C2H2：Ar＝3：9 條件下的拉曼光譜圖(樣品B)--------------52
圖4-1-3 不同沉積時間與CH4：Ar＝4：8 條件下的拉曼光譜圖(樣品C)---------------53
圖4-2-1 沉積條件C2H2：O2：Ar＝8：8：8，60min. 於Si基板上之DLC薄膜SEM橫截面結
構------------------------------------------------------------------54
圖4-2-2 沉積條件C2H2：O2：Ar＝8：8：8，80min. 於Si基板上之DLC薄膜SEM橫截面結
構------------------------------------------------------------------55
圖4-2-3 沉積條件C2H2：O2：Ar＝8：8：8，100min. 於Si基板上之DLC薄膜SEM橫截面結
構------------------------------------------------------------------56
圖4-2-4 沉積條件C2H2：O2：Ar＝8：8：8，120min. 於Si基板上之DLC薄膜SEM橫截面結
構------------------------------------------------------------------57
圖4-2-5 沉積條件CH4：Ar＝4：8 ， 100min. 於Si基板上之DLC薄膜SEM橫截面結構--58
圖4-2-6 沉積條件CH4：Ar＝4：8 ， 80min. 於Si基板上之DLC薄膜SEM橫截面結構---59
圖4-2-7 沉積條件CH4：Ar＝4：8 ， 60min. 於Si基板上之DLC薄膜SEM橫截面結構---60
圖4-2-8 沉積條件CH4：Ar＝4：8 ， 40min. 於Si基板上之DLC薄膜SEM橫截面結構---61
圖4-2-9 沉積條件C2H2：Ar＝3：9，120min. 於Si基板上之DLC薄膜SEM橫截面結構---62
圖4-2-10 沉積條件C2H2：Ar＝3：9，100min. 於Si基板上之DLC薄膜SEM橫截面結構---63
圖4-2-11 沉積條件C2H2：Ar＝3：9，80min. 於Si基板上之DLC薄膜SEM橫截面結構----64
圖4-2-12 沉積條件C2H2：Ar＝3：9，60min. 於Si基板上之DLC薄膜SEM橫截面結構----65
圖4-2-13 沉積條件為C2H2：O2：Ar＝8：8：8時薄膜厚度與沉積時間的關係-----------66
圖4-2-14 沉積條件為C2H2：Ar＝3：9時薄膜厚度與沉積時間的關係------------------67
圖4-2-15 沉積條件為CH4：Ar＝4：8時薄膜厚度與沉積時間的關係-------------------68
圖4-3-1 在C2H2：O2：Ar＝8：8：8，80min 條件下的AFM表面形態-------------------69
圖4-3-2 在C2H2：O2：Ar＝8：8：8，100min 條件下的AFM表面形態------------------70
圖4-3-2 在C2H2：O2：Ar＝8：8：8，120min 條件下的AFM表面形態------------------71
圖4-4-1 C2H2 : O2 : Ar = 8 : 8 : 8，120min 條件下DLC/LiNbO3雙層結構之
頻率響應-------------------------------------------------------------72
圖4-4-2 C2H2 : Ar =3：9 ，100min 條件下DLC/LiNbO3雙層結構之頻率響應---------73
圖4-4-3 CH4 : Ar =4：8 ，80min條件下DLC/LiNbO3雙層結構頻率響應---- --------74
圖4-4-4 條件為C2H2：O2：Ar＝8：8：8的DLC/LiNbO3 SAW元件薄膜剝離情形-------75

[1] Z. Ring and T.D.Mantei, ”Low-temperature diamond growth in a pulsed microwave plasma”, J. Vac. Sci.Technol.,A13(1995)1617
[2] Z. Ring and T.D. Mantei,”Plasma synthesis of diamond at low temperature with a pulse modulated magnetoactive discharge”, Appl. Phys. Lett., 66(1995)3380
[3]T. Yara, .M. Yuasa, M. Shimizu and H. Makita,”Fabrication of diamond films at low pressure and low-temperature by magneto-active microwave plasma chemical vapor deposition”, Jpn. J.Appl.Phys.,33(1994)4404
[4]S. H.Kim, Y.S. Park and S.K. Jung, “Effect of the substrate state on the formation of diamond film in a low temperature microwave-plasma-enhanced chemical vapor deposition system”, J.Vac. Sci.Technol.,A13(1995)1619
[5]I. Watanabe, T. Matsushita and K. Sasahara,”Low-temperature synthesis of diamond films in thermoassisted RF plasma chemical vapor deposition”,
Jpn.J.Appl.,Phys.31(1992)1428
[6]Steve J.Bull and Paul .Chalker,”High-Performance Diamond and
Diamond-like Coatings”,JOM.Aprill,1995,pp.16-19.
[7]張瑞發,「類鑽薄膜技術」,化工資訊,民國八十二年四月,68-77頁。
[8] 宋健民 著,「超硬材料」、「鑽石合成」,全華出版社,2000,1
[9]J.Seth,M.I.Chaudhry and S.V. Babu,”Electrical characteristics of plasma-deposited diamondlike carbon/silicon metal-insulator-
semiconductor structures”, J.Vac.Sci.Technol.,10(1992)3125
[10]G.F. Zhang and X. Zheng,”Optical transmittance of antireflective diamond-like coatings on ZnS substrates”,Sur. Coat. Technol.,82(1996)110
[11]J. Robertson,”Properites of diamond-like carbon”, Surf.Coat.Technol.,
50(1992)185
[12]A.Grill,”Plasma-deposited diamondlike carbon and related materials”,IBM journal,168(1993)143
[13]C.Y.Hsu,L.Y. Chen and F.C.N.Hong, “The effect of substrate temperature on the growth CNx films with β-C3N4-like microcrystallites by an inductively coupled plasma(ICP) sputtering method”,Diamond Relat.Mater.,8(1999)1315
[14]J.J.Cuomo,D.L. Pappas,J.Bruley,J.P. Doyle and K.L. Saenger, ”Vapor deposition processes for amorphous carbon film with sp3 fractions approaching diamond”,J.Appl.Phys.,70(1991)1706
[15]S.S.Camargo,Jr. A.L.BaiaNeto,R.A.Santos,F.L. Freire,Jr,R Carius,
F.Finger, “Improved high-temperature stability of Si incorporated a-C:H films”,Diamond Relat. Mater.,7(1998)1155
[16]Weng-Jin Wu, Min-Hsiung Hon,”Thermal stability of diamond-like carbon films with added silicon”,Surface and Coating Technology, 111(1999)134
[17]H.L.Bai, E.Y. Jiang,”Improvement of the thermal stability of diamond-like carbon films by incorporation of nitrogen”, Thin Solid Films,353(1999)157
[18]D.R.Tallant, J.E. Parmeter,M.P. Siegal,R.L.Sompson,”The thermal stability of diamond-like carbon”, Diamond Relat.Mater.4(1995)191
[19]C.M. Chan,t.m.Ko and H. Hiraoka,”Polymer surface modification by plasma and photons”,Surf.Sci. Rep.,24(1996)241
[20]N. Mustukuza, S.Tomita and Y. Mizum,”The mechanical properties of hydrogenated hard carbon films”,Thin Solid Films,214(1992)58
[21] R.W.G. Wyckoff,”Crystal Structure,Interscience”,New York(1964)
[22] J.C.Angus,F. Aa Buck,M. Sunkara,T. F. Gorth,C. C. Hayman,and R. Gat, MRS Bull, 10(1989)14
[23] B.T. Kelly,”Physics of Graphite”, Applied Science, London(1981)
[24] 陳培麗,科儀新知,13(2) (1991) 82.
[25] 邱建超,「氫原子對類鑽石薄膜材料反應之光譜研究」,中國材料科學學會研討會,民國八十七年,第107-110頁。
[26] D.Drescher, J.Koskinen, H.J. Scheibe, A.Mensch,”A model for particle growth in arc deposited armophous carbon films”, Diamond and Related Material 7(1998)1375-1380.
[27] R.S Weis and T.K.Gaylord, “Lithium Niobat: Summary of Physics Properties and Crystal Structure”,Appl. Phys. A. 37(1985) 191-203
[28] Boris D. Zaitsev and Iren E. Kuznetsova,”Behavior of Acoustic Axes and Internal Conical Refraction in LiNbO3 an SrTiO3 Crystals Placed in an External Electric Field”,IEEE Trans.Ultra.Ferro. and Freq.,Vol 45, No 2,march(1998)361-336.
[29] Hong Xiao 著,羅正忠、張鼎張 譯,”半導體製程技術導論”,歐亞書局.2002.1
[30]莊達人,VLSI製造技術,pp.183-198
[31]J.C. Angus and C.C. Hayman,”Low-pressure,metastable growth of diamond and diamondlike phases”, Science,241(1999)13
[32]I. Garnev and V. Orlinov, “Evaluation and parametric modelling of abrasive wear resistance of ion-plated thin DLC films”,Diamond Relate.Mater., 4(1995)1041
[33]B.A. Pailthorpe ,”Molecular-dynamics simulations of atomic processes at the low-temperature diamond(111) surface”,J. Appl. Phys.,70(1991)543
[34]H.P. Kaukonen and R.M. Nieminen,”Molecular-dynamics simulation of the growth of diamondlike films by energetic carbon-atom beams”,Phys.Rev.Lett.,68(1992)620
[35] J. Robertson,”Deposition mechanism of cubic boron nitride”, Diamond Relat. Mater.,5(1996)519
[36] J. Robertson,”Diamond-like amorphous carbon”, Mater.Sci.&
Enginering R 37(2002)129
[37]彭宣揚,”以微波電子迴旋共振化學氣相沉積法成長類鑽碳膜之研究”,國立成功大學材料科學及工程研究所碩士論文,(2000)
[38]高國陞,”鈮酸鋰基板上沉積氮化鋁薄膜及其表面聲波元件之應用”,國立中山大學電機工程研究所碩士論文(1996)
[39]張振褔,「應用鑽石膜至表面聲波濾波器」,工業材料,民國九十年五月,171-174頁
[40]廖學良,「原子力顯微鏡的原理與應用」, 化工資訊,民國八十三年十月,38-51頁
[41]S.J.Yu,Z.F.Ding,J.Xu,J.L.Zhang,T.C.Ma,”CVD of hard DLC films in a radio frequency inductively coupled plasma source”,Thin Solid Films 390(2001)98~103