臺灣博碩士論文加值系統

本實驗以射頻電漿輔助化學氣相沈積法沈積類鑽碳膜，藉由改變反應氣體、氣體流量、電漿功率、工作壓力與沈積時間等製程條件，利用拉曼測量碳膜的微結構，邁克森干涉儀與奈米壓痕量測碳膜的機械性質，更進一步在相同基板上沈積不同厚度的非晶質矽中間層與在不同基板上沈積相同厚度的非晶質矽中間層，研究中間層與基材對類鑽碳膜結構與性質之影響。
由實驗結果顯示，利用射頻甲烷與乙炔電漿在工作壓力0.3 torr、功率60 W條件下，碳膜的sp3鍵結含量、硬度與楊氏模數皆隨著氣體流量的增加而下降。以乙炔為反應氣體所沈積碳膜的硬度與楊氏模數均大於以甲烷為反應氣體所沈積的碳膜。殘留應力則隨著乙炔流量的增加而下降，但隨著甲烷流量的改變並沒有明顯的變化。碳膜中sp3鍵結含量隨著工作壓力的增加，鍍膜離子能量下降而下降，導致碳膜的硬度、楊氏模數與殘留應力下降。在乙炔工作壓力0.3 torr、氣體流量10 sccm條件下，功率20 W(-270 V)的離子能量不足，碳膜為微晶石墨結構，硬度、楊氏模數與殘留應力低。隨著功率增加，碳膜內sp2鍵結含量下降，在功率60 W(-780 V)有最大硬度、楊氏模數與殘留應力。至功率80 W(-950 V)時，過高的離子能量使得碳膜產生熱震(thermal spike)之現象，導致sp2鍵結含量增加，硬度楊氏模數與殘留應力下降的趨勢。碳膜中sp3鍵結含量、硬度、楊氏模數隨著膜厚的增加而增加，但其殘留應力卻隨著沈積時間增加導致極板溫度上升而下降。另一方面，非晶質矽中間層可有效善類鑽碳膜於SK6工具鋼以及氧化鋁剛玉(Al2O3 sapphire)上之附著狀況。對於矽基材而言，沈積在中間層上的類鑽碳膜，其sp2鍵結含量相對於無中間層之類鑽碳膜高，硬度與楊氏模數也有些微下降的趨勢；而中間層膜厚在20 nm到100 nm之間的變化，對類鑽碳膜的結構與性質影響小。

Diamond-like carbon (DLC) films were deposited by RF plasma enhanced chemical vapor deposition. The influence of deposition parameters, i.e. reactive gas, gas flow rate, working pressure, r.f. power, deposition time and amorphous silicon intermediate layer on microstructure as well as the mechanical properties were addressed. The microstructure and mechanical properties of the DLC film were successively measured by Raman spectroscopy, nanoindentation and phase-shifting Michelson interferometer. Further, the DLC films deposited on four different substrates (silicon wafer, glass, SK6 tool steel, Al2O3 sapphire) and amorphous silicon intermediate layer were investigated.
The results showed that all of the film sp3 content, hardness and Young’s modulus decrease with increasing gas flow rate while the supplied power and working pressure are fixed. On the other hand, the hardness and modulus of DLC films deposited by acetylene plasma are greater than those deposited by methane plasma. The residual stress decreases with increasing acetylene flow rate but no obvious changes were found with increasing methane flow rate. The sp3 content, hardness, Young’s modulus and residual stress decrease with increasing working pressure. The results of Raman spectrum indicate that carbon films deposited under 20 W have a microcrystalline graphite-like structure. The film sp3 content increases with increasing power under fixed flow rate and working pressure. The maximum values of hardness, modulus and residual stress of carbon films occur when the supplied is set to be 60 W. The higher ion energy under 80 W causes the thermal spike effect, which lead to the drop of sp3 content, hardness, modulus and residual stress. In addition, the adherence of DLC films on SK6 tool steel and Al2O3 sapphire was improved by amorphous silicon intermediate layer. For the Si substrate, we observed that the sp3 content, hardness and Young’s modulus of DLC films deposited with amorphous silicon intermediate layer are less than those of DLC films deposited without intermediate layer. However, the changes of intermediate layer thickness from 20 nm to 100 nm have no significant effect on microstructure and mechanical properties of DLC films.

中文摘要………………………………………………………………….…………….....I
英文摘要…………………………………………………………………….……………II
總目錄…………………………………………………….……………….……………..IV
圖目錄……………………………………………………..…………....……………...VIII
表目錄…………………………………………………...……………….……………..XII
第一章 緒論
1.1 前言……………………………………………………………….…………….1
1.2 研究目地………………………………………...…….……………….……….2
第二章 理論基礎與前人研究
2.1類鑽碳
2.1.1類鑽碳的原子結構與鍵結型態…………………………………….3
2.1.2類鑽碳的成膜機制…………………………………….....................5
2.2射頻電漿輔助化學氣相沈積碳膜的基本理論……………………….............10
2.3分析原理
2.3.1拉曼光譜………………………………..………………………….12
2.3.2奈米壓痕試驗原理
2.3.2.1負載對位移關係圖……………………..……………17
2.3.2.2連續剛性量測……………………...………………...18
2.3.3殘留應力
2.3.3.1類鑽碳膜的殘留應力……………..…………………21
2.3.3.2光學干涉技術量測類鑽碳膜曲率的基本理論……..22
2.4中間層、基材與膜厚效應………………………..…………………………….26
第三章 實驗流程與分析儀器
3.1實驗流程……………….……………………………………………....………28
3.2射頻電漿輔助化學氣相沈積系統…………………………...………………..29
3.3碳膜沈積條件及沈積步驟
3.3.1基材前處理…………………….…………………………………..30
3.3.2中間層沈積條件…………………………………………………...31
3.3.3類鑽碳膜沈積條件………………………………………………...31
3.4薄膜分析與儀器介紹
3.4.1表面粗糙度測定儀……………………………...............................32
3.4.2拉曼光譜分析儀…………………………………………………...32
3.4.3奈米壓痕量測系統………………………………………………...32
3.4.4薄膜殘留應力量測………………………………………………...33
第四章 結果與討論
4.1起始氣體與氣體流量的影響
4.1.1不同氣體流量下的自偏壓………………………………………...34
4.1.2不同氣體流量下的碳膜厚度……………………………………...34
4.1.3不同氣體流量下的鍵結型態……………………………………...35
4.1.4不同氣體流量下的表面硬度與楊氏模數………………………...35
4.1.5不同氣體流量下的殘留應力…………….………………………..36
4.2工作壓力的影響
4.2.1不同工作壓力下的自偏壓值……………………………………...44
4.2.2不同工作壓力下的碳膜厚度……………………………………...44
4.2.3不同工作壓力下的鍵結型態……………………………………...45
4.2.4不同工作壓力下的表面硬度與楊氏模數………………………...45
4.2.5不同工作壓力下的殘留應力…………………………….………..45
4.3電漿功率的影響
4.3.1不同電漿功率下的自偏壓………………………………………...53
4.3.2不同電漿功率下的碳膜厚度………………………………...……53
4.3.3不同電漿功率下的鍵結型態……………………………………...53
4.3.4不同電漿功率下的表面硬度與楊氏模數………………………...54
4.3.5不同電漿功率下的殘留應力……………………………………...54
4.4碳膜厚度的影響
4.4.1不同碳膜厚度下的鍵結型態……………………………………...63
4.4.2不同碳膜厚度下的表面硬度與楊氏模數………………………...63
4.4.3不同碳膜厚度下的殘留應力……………………………………...64
4.5非晶質矽中間層的影響
4.5.1不同厚度中間層的碳膜鍵結型態………………………………...71
4.5.2不同厚度中間層的碳膜表面硬度與楊氏模數…………………...71
4.6不同基材與非晶質矽中間層對類鑽碳膜的影響
4.6.1表面型貌觀察……………………………………………………...75
4.6.2類鑽碳膜的鍵結型態……………………………………………...75
4.6.3類鑽碳膜的表面硬度與楊氏模數…………………………….......75
第五章 結論……………………………………………………………………………..83
參考文獻………………………………………..………………………………………..85
Chinese abstract……….......………………………………….…………….....I
English abstract………………………………………...…………………….……………II
Tables of contents…...…………………………………….……………….……………..IV
List of figures…….……………………………….…………....……………...VIII
List of tables…………………………....……………………...…………..XIII
Cheaper 1 Introduction
1.1 Foreword………………………………………………………….…………….1
1.2 Motivations…….………………………………...…….……………….……….2
Chapter 2 Literature review
2.1 Diamond-like carbon
2.1.1 Atomic structure and bonding……..…………………………..…….3
2.1.2 Growth mode…………………………………….……......................5
2.2 The principle of radio frequency plasma enhanced
chemical vapor deposition..................................................................11
2.3 Characterization techniques
2.3.1 Raman spectroscopy………...…………..………………………….13
2.3.2 Nanoindentation
2.3.2.1 Loading-displacement curves…………...……………18
2.3.2.2 Continuous stiffness measurement…………………...19
2.3.3 Residual stress
2.3.3.1 The residual stress of DLC films..……………………22
2.3.3.2 The interference technique of
curvature measurement for DLC films…………….....23

2.4 Effects of intermediate layer, substrates and
film thickness……………………………………………………….………….27
Chapter 3 Experimental procedures and apparatus
3.1 Experimental procedures…………………………………….………....………29
3.2 The Radio frequency plasma enhanced chemical vapor deposition…………....30
3.3 Experimental procedures and deposition parameters
3.3.1 Pretreatment of substrates…………………………………...……..31
3.3.2 Deposition parameters of intermediate layer……………..………...32
3.3.3 Deposition parameters of DLC films……………………….……...32
3.4 Apparatus and measurement
3.4.1 Surface Profiler………………..........................................................33
3.4.2 Raman spectrum………………………………………….………...33
3.4.3 Nanoinsentation………………………..…………………………...33
3.4.4 Residual stress………………………....…………………………...34
Chapter 4 Results and discussion
4.1 Effect of reactive gas and gas flow rate
4.1.1 The self-bias under different gas flow rate………………………....35
4.1.2 The films thickness under different gas flow rate……………….....35
4.1.3 The structure under different gas flow rate………………………...36
4.1.4 The hardness and Young’s modulus
under different gas flow rate……………………………………......36
4.1.5 The residual stress under different gas flow rate……………….…..37
4.2 Effect of working pressure
4.2.1 The self-bias under different working pressure………………….....45
4.2.2 The films thickness under different working pressure………...…...45
4.2.3 The structure under different working pressure…………………....46
4.2.4 The hardness and Young’s modulus
under different working pressure…………………………………...46
4.2.5 The residual stress under different working pressure….…….……..46
4.3 Effect of power
4.3.1 The self-bias under different power……………………...………...54
4.3.2 The films thickness under different power……...……………….…54
4.3.3 The structure under different power………………………………..54
4.3.4 The hardness and Young’s modulus
under different power………………………………………….…...55
4.3.5 The residual stress under different power……………………..…...55
4.4 Effect of DLC films thickness
4.4.1 The structure under different DLC films thickness………………...64
4.4.2 The hardness and Young’s modulus
under different DLC films thickness…………………………….....64
4.4.3 The residual stress under different DLC films thickness………......64
4.5 Effect of amorphous silicon intermediate layer
4.5.1 The structure under different intermediate layer thickness………...72
4.5.2 The hardness and Young’s modulus
under different intermediate layer thickness………………….........72
4.6 Effect of different substrate
4.6.1 Surface morphology…………………………………………...…...76
4.6.2 Structure of DLC films……………………………………………..76
4.6.3 Mechanical properties of DLC films…….................................77
Chapter 5 Conclusions……………………………………..……………………………..84
References…………..…………………………..………………………………………..86

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