大氣電漿束之電漿特性與應用之研究｜國立清華大學博碩士論文庫

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研究生：	簡士傑 Jian, Shih-Jie
論文名稱：	大氣電漿束之電漿特性與應用之研究 Study of the Characteristics and Applications of Atmospheric Pressure Plasma Jets
指導教授：	寇崇善 Kuo, Chwung-Shan
口試委員:	李政道柳克強周賢鎧黃振昌
學位類別：	博士 Doctor
系所名稱：	理學院 - 物理學系 Department of Physics
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	263
中文關鍵詞：	大氣電漿、預傾角、操作頻率、氣流
外文關鍵詞：	atmospheric pressure plasma, driving frequency, preitlt angle, gas flow
相關次數：	點閱：1 下載：0
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本研究利用大氣電漿系統研究操作頻率對電漿特性的影響、氣流對薄膜沉積和電漿分佈的影響、沉積有機矽薄膜以及藉由調整薄膜特性達到控制液晶分子預傾角的目的。
　　本研究在增加操作頻率下，觀察到以下幾種電漿特性變化：(1)電漿的崩潰電壓從256 V降低至204 V、(2)維持α模式放電的最高電漿密度從0.798×〖10〗^12 〖cm〗^(-3)上升至2.218×〖10〗^12 〖cm〗^(-3)以及電流從0.125 A提高至0.224 A、(3)放電模式轉換前的鞘層厚度從0.348 mm減少為0.257 mm、(4)電漿功率為25 W時電子激發溫度從0.535 ev降為0.316 ev。
　　本實驗在研究過程中，發現當進氣量為5 slm時，氣流分佈不均勻，進而導致薄膜厚度的不均勻分佈。藉由改變風刀結構來改善氣流分佈的均勻性，可使薄膜厚度均勻分佈在基材上，由於薄膜沉積的均勻性和電漿密度分佈有關，因此可判斷氣流分佈對電漿密度分佈有重大的影響。
　　本實驗使用大氣電漿源與有機矽化合物HMDSO沉積有機矽膜，藉由控制製程參數可調整薄膜結構與物理特性，實驗中發現HMDSO薄膜的主要結構為Si–CH3和Si–O–Si，提高分子平均能量可使薄膜結構偏向Si–O–Si；反之則偏向Si–CH3。Si–CH3為非極性分子，其結構較脆弱且較容易被破壞；Si–O–Si為極性分子，其結構較為堅固不易被破壞。當Si–O–Si的含量比例較高時，薄膜具有較高的表面能，可達68 mJ/m2，親水性質較明顯，表面硬度比較高，可達到5H；若是Si–CH3的含量比例較高，薄膜具有較低的表面能，可低至25 mJ/m2，疏水性質較明顯。
　　本實驗藉由控制薄膜的表面能，達到控制液晶分子預傾角的目的。實驗結果顯示預傾角角度會隨著薄膜的表面能改變，當表面能低於34 mJ/m2時，預傾角角度趨近於90o，當表面能高於60 mJ/m2時，預傾角角度趨近於0o，由此可知，欲控制預傾角，表面能的範圍必須控制在34~60 mJ/m2。

In study, we used atmospheric pressure plasma source (APPS) to study the effect of driving frequency on the characteristic of plasma, the effect of gas flow on the deposition process and plasma density distribution, deposition of organic silicon film, and controlling the pretilt angle of liquid crystals (LCs).
The study was to investigate the driving frequency effects on the characteristics of atmospheric plasma jets system. The discharge gas is the helium. We change the power source frequency range from 10 MHz to 20 MHz. As the driving frequency is increased, we can observe the several phenomena. (1) gas breakdown voltage from 256 V down to 204 V, (2) plasma density from 0.798×〖10〗^12 〖cm〗^(-3) rose to 2.218×〖10〗^12 〖cm〗^(-3) and increase the current from 0.125 A to 0.224 A when the plasma state at highest α mode discharge, (3) sheath thickness decreased from 0.348 mm to 0.257 mm before discharge mode transition, (4) the electron excitation temperature dropped from 0.535 ev 0.316 ev when the plasma power of 25 W. Collectively, these results suggest that the high driving frequency help to improve the quality of plasma, enhance discharge efficiency, and make the atmospheric plasma jets systems have a wider application space.
From the results, the gas flow distribution became non-uniform at helium flow rate of 5 slm. By modifying the structure of nozzle, the gas flow distribution became more uniform so that film deposition became uniform. Because the uniformity of film deposition is related to the plasma density distribution, the gas flow distribution effected the plasma density distribution.
In study, the APPS was used to deposited the organic silicon film, HMDSO as the material. The process could control the structure and properties of the film. Results showed main bonds (Si–CH¬3 and Si–O–Si) can be controlled by molecular average energy (W/FM). The ratio of Si–O–Si increased when W/FM became large. The ratio of Si–CH¬3 was increasing with decreasing the W/FM. Si–O–Si are polar bonds, and Si–CH¬3 are non-polar bonds. Thus, if the ratio of Si–O–Si was higher than Si–CH¬3, the film became hydrophilic (surface energy could be 68 mJ/m2) and surface hardness became hard. If the ratio of Si–CH¬3 was higher than Si–CH¬3, the film became hydrophobic (surface energy could be 25 mJ/m2) and surface hardness became soft.
The pretilt angle of LCs could be controlled by adjusting the surface energy of the film. When the surface energy was smaller than 34 mJ/m2, the pretilt angle approached 90o. When the surface energy was larger than 60 mJ/m2, the pretilt angle approached 0o. Therefore, the pretilt angle could be controlled by the range of surface energy from 34 to 60 mJ/m2.

目　錄
第一章　緒論    1
1–1　前言    1
1–2　大氣電漿源簡介    1
1–3　有機矽膜簡介    7
1–4　液晶配向簡介    9
1–5　數值模擬軟體Comsol multiphysics簡介    11
1–6　研究目的    13
參考文獻    16

第二章　文獻回顧    22
2–1　大氣電漿    22
2–1–1　氣體游離過程    22
2–1–2　氣體崩潰機制    25
2–1–3　產生均勻放電的方法    31
2–1–4　氣流對電漿分佈的影響    36
2–2　液晶配向    39
2–2–1　配向的形成    40
2–2–2　配向的方法    46
2–2–3　預傾角    58
2–3　Hexamethyldisiloxane (六甲基矽氧烷，HMDSO)     60
2–4　Comsol multiphysics流體力學模型    64
2–4–1　連續方程式    64
2–4–2　動量傳輸方程式    65
2–4–3　能量傳輸方程式    66
參考文獻    67

第三章　實驗設備與分析方法    72
3–1　大氣電漿系統    72
3–2　各種分析儀器    77
3–2–1　物性分析儀器    77
(1)　橢圓偏光儀    77
(2)　傅立葉紅外線光譜儀    79
(3)　化學分析能譜儀    80
(4)　原子力顯微鏡    81
(5)　接觸角量測儀    82
(6)　鉛筆硬度測試機    85
3–2–2　液晶配向儀器    86
(1)　刷磨機    86
(2)　偏光顯微鏡    87
(3)　預傾角測量系統    88
3–2–3　電漿特性測量儀器    89
(1)　功率與電壓電流特性量測系統    89
(2)　電漿光譜量測系統    91
發射光譜強度分析    93
電子平均吸收能量    95
電子激發溫度計算    96
3–3　COMSOL模型建立    98
參考文獻    102

第四章　功率源頻率對大氣電漿束之影響    105
4–1　前言    105
4–2　電漿理論模型    106
4–3　實驗方法    110
4–4　頻率對功率傳遞效率分析    111
4–5　線型大氣電漿特性分析    114
4–5–1　線型大氣電漿束輝光放電現象    114
4–5–2　操作頻率對電漿放電特性之影響    117
4–5–3　操作頻率對電漿特性之影響    120
4–5–4　電漿光譜分析    124
4–5–5　不同操作頻率下He的特徵譜線    125
4–5–6　不同操作頻率下N2和N2+的特徵譜線    130
4–5–7　不同操作頻率下電子激發溫度    132
4–6　操作頻率改變電漿特性之原因    135
參考文獻    138

第五章　氣流對電漿分佈之影響    141
5–1　前言    141
5–2　實驗方法    142
5–3　氣流分佈對薄膜沉積的影響    144
5–3–1　市售風刀的氣流分佈模擬及對薄膜沉積的影響    144
(1)　氣流分佈模擬    146
(2)　薄膜厚度的均勻性    150
5–3–2　改善風刀結構對的氣流分佈及對薄膜沉積的影響    153
參考文獻    157

第六章　HMDSO薄膜特性與液晶配向之應用    158
6–1　前言    158
6–2　實驗流程    160
6–3　薄膜材料分析    163
6–3–1　薄膜結構分析    163
FTIR光譜分析    163
ESCA能譜分析    182
6–3–2　薄膜物理性質分析    218
表面能分析    218
硬度分析    230
表面粗糙度分析    233
6–3–3　薄膜沉積速率與折射率分析    239
6–3–4　Yasuda factor W/FM在本實驗扮演的角色    244
6–4　HMDSO薄膜在液晶配向之應用    247
表面形貌分析    248
HMDSO薄膜的配向效果    251
參考文獻    256

第七章　結論    259

 
圖目錄
圖1–1　介質屏障放電示意圖    2
圖1–2　暈光放電示意圖    3
圖1–3　電漿火炬示意圖    4
圖1–4　大氣電漿束示意圖    5
圖1–5　刷磨式配向法示意圖    9
圖1–6　大氣電漿源與刷磨式配向法的連續製程示意圖    14
圖2–1　Townsend breakdown的示意圖    26
圖2–2　電子崩的示意圖    29
圖2–3　電子崩對電場的影響    29
圖2–4　形成流光(streamer)的過程    31
圖2–5　Streamer coupling discharge示意圖    33
圖2–6　常用氣體的崩潰電壓與pd值的關係圖    35
圖2–7　不同氣壓下，放電電壓與氣流流速的關係圖    37
圖2–8　不同流速下，電壓與電流的關係圖    38
圖2–9　配向膜的溝槽結構    42
圖2–10　液晶分子與法線的夾角示意圖    45
圖2–11　氧化矽斜向蒸鍍法裝置圖    48
圖2–12　液晶分子在氧化矽表面的排列示意圖    48
圖2–13　刷磨式配向及各種參數的示意圖    51
圖2–14　刷磨前後的液晶分子排列示意圖    51
圖2–15　光異構的結構示意圖    53
圖2–16　光異構配向的液晶分子排列示意圖    53
圖2–17　光聚合反應的結構示意圖    53
圖2–18　光連結反應的結構示意圖    54
圖2–19　離子束配向的裝置示意圖    56
圖2–20　真空型電漿束配向示意圖    57
圖2–21　預傾角示意圖    58
圖2–22　外加電壓垂直於液晶分子的響示意圖    59
圖2–23　Tilt–reverse示意圖    59
圖2–24　Twist–reverse示意圖    59
圖2–25　HMDSO結構式    61
圖2–26　HMDSO的紅外線光譜圖    61
圖3–1　線型大氣電漿系統裝置示意圖    75
圖3–2　HMDSO的蒸氣壓與環境溫度關係圖    75
圖3–3　單體瓶裝置示意圖    76
圖3–4　風刀內部結構示意圖    76
圖3–5　橢圓儀測量示意圖    78
圖3–6　共振吸收的振動模式示意圖    79
圖3–7　光電子產生示意圖    80
圖3–8　原子間作用力與原子間距離的關係圖    82
圖3–9　接觸角測量示意圖    83
圖3–10　固、液、氣三相平衡示意圖    83
圖3–11　鉛筆硬度測試裝置與測量示意圖    85
圖3–12　刷磨式配向示意圖    87
圖3–13　POM測量示意圖    88
圖3–14　預傾角測量示意圖    88
圖3–15　功率量測系統    89
圖3–16　電漿光譜量測系統    92
圖3–17　氬氣放電的電子能量分布函數隨氣壓變化    94
圖3–18　氬氣中電子的電離、激發和彈性激發截面積    94
圖3–19　模擬的結構示意圖    99
圖3–20　實驗結構側視圖    98
圖4–1　線型大氣電漿束等效阻抗模型    107
圖4–2　功率傳遞效能隨操作頻率的變化    112
圖4–3　電漿放電損耗的比例隨操作頻率的變化    113
圖4–4　輝光放電照片前視圖(α模式放電現象)    114
圖4–5　氣流流速模擬圖    115
圖4–6　輝光放電照片側視圖    115
圖4–7　放電模式轉換圖    116
圖4–8　放電模式轉換圖    117
圖4–9　崩潰電壓與電流隨頻率的變化    118
圖4–10　放電模式轉換前的電壓與電流隨頻率的變化    118
圖4–11　放電模式轉換前電漿鞘層厚度與電漿密度隨頻率的變化    120
圖4–12　不同操作頻率下電壓與電流關係圖    121
圖4–13　不同頻率下電漿密度隨功率變化    122
圖4–14　不同頻率下電漿阻抗隨功率變化    122
圖4–15　不同頻率下電漿鞘層厚度隨功率變化    123
圖4–16　不同頻率下電漿鞘層電容隨功率變化    124
圖4–17　氦氣線型大氣電漿束放電過程中的特徵光譜    125
圖4–18　氦氣激發態譜線強度與電漿區功率的關係圖    126
圖4–19　氦氣激發態譜線強度與電漿區電壓的關係圖    127
圖4–20　不同頻率下氦氣激發態譜線強度    129
圖4–21　N_2  second positive system 的譜線強度與放電功率關係圖    130
圖4–22　N_2  first negative system 的譜線強度與放電功率的關係圖    131
圖4–23　電子激發溫度與放電電壓的關係圖    133
圖4–24　電子激發溫度與電漿區功率的關係圖    134
圖4–25　電子震盪振幅示意圖，電子移動時間示意圖    136
圖4–26　電子震盪振福與電子傳遞時間和操作頻率半周期比值隨頻率變化    137
圖5–1　Wafer表面顏色對氧化矽膜的厚度變化    143
圖5–2　實驗操作流程    143
圖5–3　市售風刀的外觀與內部結構    145
圖5–4　氣流模擬的模型    145
圖5–5　氣流的測量位置示意圖    145
圖5–6　氣流的向量分佈圖    147
圖5–7　氣流的速率分佈圖    148
圖5–8　噴氣口的氣流速率的分佈圖    149
圖5–9　氣壓分佈圖    149
圖5–10　經過沉積薄膜的Wafer表面顏色分佈隨著氦氣流量改變    150
圖5–11　經過沉積薄膜的Wafer表面顏色分佈隨著氦氣流量改變    151
圖5–12　將流量為2和3 slm的參數的掃描次數提高到40次    152
圖5–13　修改後的風刀結構    154
圖5–14　修改後的模擬結果    155
圖5–15　風刀經過修改後在出氣口的氣流速率分佈    156
圖5–16　使用修改後的風刀進行的薄膜沉積結果    156
圖6–1　實驗流程圖    162
圖6–2　HMDSO薄膜的紅外線吸收光譜    165
圖6–3　FTIR光譜，Power為變數    169
圖6–4　FTIR光譜，HMDSO流量為變數    173
圖6–5　FTIR光譜，Helium流量為變數    177
圖6–6　FTIR光譜，O2流量為變數    181
圖6–7　HMDSO薄膜的ESCA survey能譜    184
圖6–8　ESCA能譜，Power為變數    192
圖6–9　ESCA能譜，HMDSO流量為變數    200
圖6–10　ESCA能譜，Helium流量為變數    208
圖6–11　ESCA能譜，O2流量為變數    216
圖6–12　接觸角與表面能，Power為變數    222
圖6–13　接觸角與表面能，HMDSO流量為變數    226
圖6–14　接觸角與表面能，Helium流量為變數    227
圖6–15　接觸角與表面能，O2流量為變數    229
圖6–16　HMDSO薄膜的表面結構，Power    234
圖6–17　HMDSO薄膜的表面結構，HMDSO    235
圖6–18　HMDSO薄膜的表面結構，O2流量    237
圖6–19　基材經過電漿區的示意圖    240
圖6–20　Power對膜厚及沉積速率的影響    240
圖6–21　HMDSO流量對膜厚及沉積速率的影響    242
圖6–22　Helium流量對膜厚及沉積速率的影響    242
圖6–23　表面能在不同實驗參數中所對應的W/FM    246
圖6–24　未經刷磨的薄膜表面形貌    249
圖6–25　經過刷磨製程的薄膜表面形貌    250
圖6–26　液晶胞的配向狀況，HMDSO    253
圖6–27　液晶胞的配向狀況，Power    253
圖6–28　預傾角隨表面能的變化    254




 
表目錄
表1–1　大氣電漿源與低氣壓電漿源之崩潰電壓比較    6
表1–2　大氣電漿源與低氣壓電漿源之電漿密度比較    6
表2–1　在γ_c–hypothesis中，各種配向模式所對應的液晶表面能與基板表面能的關係圖    46
表3–1　鉛筆型號與硬度的關係圖    86
表4–1　He譜線相關數據    132
表6–1　HMDSO薄膜的鍵結振動模式    165
表6–2　HMDSO薄膜的各種鍵結的束縛能    184
表6–3　測量液體的表面能參數表    220
表6–4　Power對表面硬度的影響    231
表6–5　HMDSO流量對表面硬度的影響    232
表6–6　O2流量對表面硬度的影響    232
表6–7　不同Power下的表面粗糙度    234
表6–8　不同HMDSO流量下的表面粗糙度    235
表6–9　不同O2流量下的表面粗糙度    237
表6–10　Power對薄膜折射率的影響    241
表6–11　HMDSO流量對薄膜折射率的影響    242
表6–12　Helium流量對薄膜折射率的影響    243
表6–13　刷磨前和刷磨後的表面粗糙度    248



                                

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