臺灣博碩士論文加值系統

本文係利用噴射式大氣電漿鍍膜技術，將二氧化矽薄膜沉積在高分子材料聚碳酸酯(Polycarbonate，PC)表面，並探討不同特性的二氧化矽薄膜對阻燃性質提升的影響。電漿氣體為氦氣並在電源以射頻(Radio Frequency, RF)13.56 MHz來驅動電漿源。使用有機矽源的四乙氧基矽烷(tetraethoxysilane，TEOS)當作沉積二氧化矽薄膜的前驅物。改變不同的前驅物流量、功率大小及氧氣流量等實驗因子，來掌握二氧化矽薄膜的特性，了解薄膜孔洞性的變化。使用霍氏轉換紅外光譜儀(FTIR)、原子力顯微鏡(AFM)及掃描型電子顯微鏡(SEM)來分析二氧化矽薄膜的特性，同時以最低限氧指數(limiting oxygen index, LOI)的量測做為探討阻燃性的依據。
經大氣電漿所沉積的二氧化矽薄膜其孔洞性會受到成膜速率的影響，實驗結果發現二氧化矽薄膜的孔洞性隨著成膜速率的上升而增加，因此欲沉積緻密性較高的薄膜，應選擇成膜速率較低的參數。從最低限氧指數的量測發現，原本未沉積二氧化矽薄膜的最低限氧指數為22，鍍上孔洞性低的薄膜，可提升最低限氧指數至27，而相對地，孔洞性高的薄膜，對於阻燃性質的提升並無改善的現象。

Atmospheric pressure (AP) plasma chemical vapor deposition (CVD) process is utilized in this paper. We coated silica films on polycarbonate (PC) to enhance the flame retardant of PC. The AP apparatus is developed by ITRI. The plasma reactor operates by feeding helium gas between two electrodes driven by a Radio frequency (RF) power at 13.56 MHz at atmospheric pressure and near room temperature. The organic silicon source tetraethoxysilane (TEOS) was utilized as the precursor of silica films. With distinct experiment factors, such as the flow rate of precursor, power and flow rate of oxygen, we measure the thickness to calculate deposition rate, surface roughness, and porosity of the film. Moreover, the variation of the film’s properties were analyzed by Fourier-transform infrared spectrometer (FTIR), atomic force microscope (AFM) and scanning electron microscopy (SEM). The promotion of PC’s flame retardant is illustrated by limiting oxygen index.
The result presented the porosity of the silica film deposited by AP-PECVD increased with higher deposition rate. We should choose the lower deposition rate experiment parameter to get the denser film. The denser film coated on PC raised the LOI value from 22 to 27. However, the porous film can’t contribute any promotion to LOI value.

誌謝 I
摘要 II
Abstract III
目錄 IV
圖目錄 VI
表目錄 IX
第一章 緒論 1
1.1 前言 1
1.1.1 Silicone系阻燃 2
1.1.2 大氣電漿源 3
1.1.3 化學氣相沉積二氧化矽薄膜 7
1.2 研究動機與目標 11
第二章 文獻回顧 13
2.1 大氣電漿之基本特性 13
2.2 大氣電漿技術沉積二氧化矽薄膜 17
2.3 燃燒基礎理論[1,21,22] 24
2.3.1 燃燒的條件 24
2.3.2 高分子燃燒的過程 25
2.3.3 高分子的阻燃機制 28
2.4阻燃研究文獻回顧 30
第三章 實驗架構與設備 38
3.1 實驗架構 38
3.2實驗設備 39
3.2.1大氣電漿設備 39
3.2.2掃描式電子顯微鏡(SEM) 43
3.2.3原子力顯微鏡(AFM) 43
3.2.4霍氏轉換紅外光譜儀(FTIR) 46
3.2.5最低需氧指數試驗儀(LOI) 46
3.2.6著火時間量測裝置 48
3.3實驗材料準備 48
3.3.1 矽基板試片準備 48
3.3.2 PC基板準備 50
3.3.3 反應物單體準備 50
第四章 實驗結果與分析 52
4.1 實驗過程步驟 52
4.2薄膜性質分析 53
4.3薄膜性質量測結果 55
4.3.1 反應物單體流量實驗 55
4.3.2電源功率實驗 59
4.3.3氧氣流量實驗 62
4.3.4薄膜性質分析結果歸納 65
4.4阻燃性量測結果 69
4.4.1最低限氧指數量測結果 69
4.4.2燃燒過程觀察結果 71
4.4.3著火時間量測結果 73
4.4.4薄膜阻燃討論 74
第五章 結論與未來展望 77
5.1 結論 77
5.2 未來展望 78
參考文獻 80

[1]陸冠良, “無鹵阻燃劑在熱塑性彈性體SBS之研究” , 義守大學，碩士論文，2004年
[2]A. Que′de′, C. Jama, P. Supiot, M. Le Bras, R. Delobel, O. Dessaux, P. Goudmand, “Elaboration of fire retardant coatings on polyamide-6 using a cold plasma polymerization process” ,Surface and Coatings Technology, 151 –152 (2002) 424–428
[3]吳敏文等, “電漿源原理與應用之介紹,” 物理雙月刊, 廿八卷二期, pp. 440-452, 2006年4月.
[4]A. Kuwabara, Shin-ichi Kuroda, H. Kubota, “Preparation of a CVD thin film by an atmospheric pressure low temperature surface discharge plasma torch”, Plasma Sources Science and Technology, Vol. 15, pp.328-331, 2006.
[5]S. E. Babayan, J. Y. Jeongy, V. J. Tuy, J. Parkz, G. S. Selwynz, R. F. Hicks, “Deposition of silicon dioxide films with an atmospheric-pressure plasma jet”, Plasma Source Science and Technology, Vol. 7, pp.286-288, 1998.
[6]Zygmunt Rymuza, Maciej Misiak, Zenobia Rzanek-Boroch, Krzysztof Schmidt-Szalowski, Jadwiga Janowska, “The effects of deposition and test conditions on nanomechanical behaviour of ultrathin films produced by plasma-enhanced chemical vapour deposition process at atmospheric pressure”, Thin Solid Films, Vol. 466, pp.158-166, 2004.
[7]G. R. Nowling, M. Yajima, S. E. Babayan, M. Moravej, X. Yang, W. Hoffman, R. F. Hicks, “Chamberless plasma deposition of glass coatings on plastic”, Plasma Source Science and Technology, Vol. 14, pp.477-484, 2005.
[8]Volkmar Hopfe, Ralf Spitzl, Ines Dani, Gerrit Maeder, Liliana Roch, Daniela Rogler, Beate Leupolt, Bolko Schoeneich, “Remote Microwave PECVD for Continuous, Wide-Area Coating Under Atmospheric Pressure”, Chemical Vapor Deposition, Vol. 11, pp.497-509, 2005.
[9]A. Schutze, J. Y. Jeong, S. E. Babayan, J Park, G. S. Selwyn, R. F. Hicks, “The Atmospheric-Pressure Plasma Jet: A Review and Comparision to Other Plasma Sources”, IEEE Transactions on Plasma Science, Vol. 26, pp.1685-1694, 1998.
[10]Sergei E. Alexandrov, Michael L. Hitchman, “Chemical Vapor Deposition Enhanced by Atmospheric Pressure Non-thermal Non-equilibrium Plasmas”, Chemical Vapor Deposition, Vol. 11, pp. 457-468, 2005.
[11]http://web.mit.edu/6.777/www/matprops/
[12]莊達人, “VLSI 製程技術,” 高立出版社, 2006年6月.
[13]G. R. Nowling, M. Yajima, S. E. Babayan, M. Moravej, X. Yang, W. Hoffman, R. F. Hicks, “Chamberless plasma deposition of glass coatings on plastic”, Plasma Source Science and Technology, Vol. 14, pp.477-484, 2005.
[14]Zajickvoa, Bursikova and Janca, “Protection coatings for polycarbonates based on PECVD from organosilicon feeds” , Vacuum, Vol. 50, pp.19-21, 1998.
[15]Zajickvoa, Bursikova and Perina, “Plasma modification of polycarbonates”, Surface and Coatings Technology, pp.449-454, 2001.
[16]A. Bousquet, V. Bursikova, A. Goullet, A. Djouadi, L. Zajickova, A. Granier, “Comparison of structure and mechanical properties of SiO2-like films deposited in O2/HMDSO pulsed and continuous plasmas”, Surface and Coatings Technology, pp.6517-6521, 2006.
[17]A. Schutze, J. Y. Jeong, S. E. Babayan, J Park, G. S. Selwyn, R. F. Hicks, “The Atmospheric-Pressure Plasma Jet: A Review and Comparision to Other Plasma Sources”, IEEE Transactions on Plasma Science, Vol. 26, pp.1685-1694, 1998.
[18]Zygmunt Rymuza, Maciej Misiak, Zenobia Rzanek-Boroch, Krzysztof Schmidt-Szalowski, Jadwiga Janowska, “The effects of deposition and test conditions on nanomechanical behaviour of ultrathin films produced by plasma-enhanced chemical vapour deposition process at atmospheric pressure”, Thin Solid Films, Vol. 466, pp.158-166, 2004.
[19]G. R. Nowling, M. Yajima, S. E. Babayan, M. Moravej, X. Yang, W. Hoffman, R. F. Hicks, “Chamberless plasma deposition of glass coatings on plastic”, Plasma Source Science and Technology, Vol. 14, pp.477-484, 2005.
[20]Volkmar Hopfe, Ralf Spitzl, Ines Dani, Gerrit Maeder, Liliana Roch, Daniela Rogler, Beate Leupolt, Bolko Schoeneich, “Remote Microwave PECVD for Continuous, Wide-Area Coating Under Atmospheric Pressure”, Chemical Vapor Deposition, Vol. 11, pp.497-509, 2005.
[21]劉進昌, “無鹵素耐燃劑加入無毒高分子燃燒特性之研究”, 國立中正大學, 碩士論文, 2004年
[22]蔣繼廣, “廢偏光板與高密度聚乙烯摻合物之機械與耐燃性質研究”, 國立高雄第一科技大學, 碩士論文, 2006年
[23]Ping Wei, Zhidong Han, Xiaonan Xu, Zhanxiong Li, “Synergistic Flame Retardant Effect of SiO2 in LLDPE/EVA/ATH Blends”, Journal Of Fire Sciences, Vol. 24 – November 2006
[24]M. Iji, S. Serizawa, Y. Kiuchi, "New Environmentally Conscious Flame-Retarding Plastics for Electronics Products," ecodesign, p. 245, First International Symposium on Environmentally Conscious Design and Inverse Manufacturing, 1999
[25]Jun-wei Gu, Guang-cheng Zhang, Shan-lai Dong, Qiu-yu Zhang, Jie Kong, “Study on preparation and fire-retardant mechanism analysis of intumescent flame-retardant coatings”, Surface & Coatings Technology 201 (2007) 7835–7841
[26]L. Zajickvoa, V. Bursikova, Z. Kucerova, D. Franta, P. Dvorak, R. Smid, V. Perina and A. Mackova, “Deposition of protective coatings in rf organosilicon discharges”, Plasma Sources Science and Technology, Vol. 16, pp.123-132, 2007.
[27]X. Zhu, F. Arefi-Khonsari, C. Petit-Etienne, M. Tatoulian, “Open Air Deposition of SiO2 Films by an Atmospheric Pressure Line-Shaped Plasma”, Plasma Processes and Polymers, Vol. 2, pp. 407-413, 2005.
[28]S. E. Babayan, J. Y. Jeong, A. Schutze, V. J. Tu, M. Moravej, G. S. Selwyn, R. F. Hicks, “Deposition of silicon dioxide films with a non-equilibrium atmospheric pressure plasma jet”, Plasma Source Science and Technology, Vol. 10, pp. 573-578, 2001.
[29]Jenq-Shiuh Chou and Si-Chen Lee, “Effect of porosity on infrared-absorption spectra of silicon dioxide”, J. Appl. Phys., Vol. 77, No.4, 1995.
[30]Chih-Cheng Kuo, “Mechanical Properties of Silicon Dioxide Film Deposited by Atmospheric Pressure Plasma Chemical Vapor Deposition”, National Taiwan University, 2007.