本研究利用黃光微影製程，在聚乙烯對苯二甲酸酯(polyethylene terephthalate; PET)以及矽基板(silicon wafer)上製作具有底切(Under-cut)圖案化光阻，利用高頻電漿化學增強氣相沉積系統(VHF-PECVD)，以四甲基矽烷(Tetramethylsilane; TMS)單體為源氣體在底切圖案化光阻表面上預先沉積有機矽基厚膜，再利用射頻電漿增強化學氣相沉積系統（Plasma-enhanced chemical vapor deposition; PECVD），於低溫環境下，以四甲基矽烷-氧氣-氨氣混和氣體，沉積無機氮氧化矽薄膜及多對有機矽基/無機氮氧化矽薄膜結構，觀察經厚膜修飾後之氣體阻障層的階梯覆蓋性、水氣滲透率以及撓曲機械特性。
此外，在研究中亦探討氣體阻障結構在紫外光與太陽光照射下的結構與特性可靠性。研究結果顯示，在太陽光照射下對於氣體阻障結構內部鍵結未造成改變，而在紫外光照射下，氣體阻障結構內部鍵結產生光化學反應，造成薄膜性質的改變，使得水氣阻障能力劣化，為了進一步了解紫外光照射對於阻障層結構的影響，本研究更詳細分析，氣體阻障層結構在不同紫外光照射條件下之阻障特性老化趨勢，並觀察氣體阻障結構與特性可靠性變化機制。

In this study, a patterned photoresist with undercut was fabricated on polyethylene terephthalate (PET) and silicon wafer, using high frequency plasma chemical to enhance vapor deposition system (VHF-PECVD); TMS was used as the source gas to deposited organic silicon based thick film on the substrate patterned photoresist surface in advance, and then use RF plasma enhanced chemical vapor deposition system (PECVD) again; in low temperature environment, inorganic silicon nitride film and many pairs of organic silicon / inorganic silicon nitride film were deposited with tetramethylsilane oxygen ammonia gas mixture. The ladder coverage, water gas permeability and flexure mechanical properties of the gas barrier layer modified by thick film were observed.
Moreover, it also discussed the structure and characteristic reliability of gas barrier structure under ultraviolet and sunlight. The result shows that the internal bonding of gas barrier structure didn’t changed under the sun light, but under the ultraviolet light,the internal bonding of gas barrier structure produces photochemical reaction, resulting in the change of film properties, which leads to the deterioration of water vapor barrier ability. In order to further understand the impact of ultraviolet light on the structure of barrier layer, we analyze the gas barrier more detail. The aging trend of the barrier characteristics of the layer structure under different UV irradiation conditions, and the mechanism of the change of the barrier structure and the reliability of the characteristics were observed.

摘要.................i
Abstract............ii
誌謝................iii
目錄................iv
表目錄..............vi
圖目錄..............vii
第一章 緒論........1
1.1 前言........1
1.2 文獻回顧........2
1.2.1 氣體阻障層....2
1.2.2 階梯覆蓋性....2
1.2.2特高頻電漿化學氣相沉積系統(VHF-PECVD)......3
1.2.3 撓曲測試......3
1.2.4紫外光與太陽光水氣可靠性測試...............4
1.3研究動機.........4
第二 章理論基礎.......8
2.1 化學氣相沉積.....8
2.1.1 電漿理論.......8
2.1.2 化學氣相沉積之過程.....9
2.1.3 化學氣相沉積之種類.....10
2.1.4 化學氣相沉積之階梯覆蓋..10
2.2 薄膜成長原理.............11
2.3 軟性基板簡介.............12
2.4水氣滲透原理及機制.........12
2.5薄膜應力原理及機制.........14
第三章 實驗方法及步驟..........23
3.1 實驗流程..........23
3.2 薄膜製程系統.......23
3.2.1 真空抽氣系統.....23
3.2.2 腔體反應室系統...24
3.2.3 反應氣體源.......24
3.3 薄膜量測分析.......24
3.3.1 金相顯微鏡.......24
3.3.2 α-step 表面輪廓儀.....24
3.3.3附著度測試.............25
3.3.4水蒸氣滲過率測試儀......25
3.3.5場發射掃描式電子顯微鏡（FE-SEM）.......25
3.3.6傅立葉轉換紅外線吸收光光譜儀(Fourier transform infrared spectroscopy)..25
3.3.7太陽光模擬器...........25
3.3.8紫外光模擬器...........26
3.4薄膜撓曲測試.............26
3.4.1自製撓曲機.............26
3.5頂切以及底切光阻圖案化製作..............26
3.5.1 光阻圖案化..........................26
3.5.2底切圖案化之階梯覆蓋率................27
3.5.3 水氣滲透衰退率(WVTR degradation)....27
3.5.4 抵達角差異定義......................27
3.5.5 厚膜修飾抵達角差異性.................27
第四章 結果與討論..........................37
4.1氣體阻障層沉積於具有機矽機厚膜修飾之水氣阻障可靠性與機械撓曲特性分析........37
4.1.1 氣體阻障層沉積在具厚膜修飾之底切圖案化可靠性分析.......................38
4.1.2 氣體阻障層沉積於具有機矽基厚膜之機械撓曲可靠性分析.....................43
4. 2氣體阻障層結構在紫外光及可見光照射下之可靠性分析.........................48
4.2.1單層氮氧化矽薄膜與多層有機矽基/氮氧化矽氣體阻障層結構在可見光照下光的水氣滲透率分析........................48
4.2.2單層氮氧化矽薄膜與多層有機矽基/氮氧化矽氣體阻障層結構在紫外光照射下的水氣滲透率分析........................49
4.2.3氧化矽薄膜在紫外光與可見光不同時間照射下的水氣與可靠性分析...............50
4.2.4氮氧化矽薄膜在不同紫外光強度照射下之水氣阻障可靠性與鍵結分析.............51
第五章 結論...............................................................75
參考文獻..................................................................77
Extended Abstract.........................................................82

[1]. 田宏隆 200 4, 高阻氣高透明塗料材料技術與運用 工業材料雜誌 , 206 期pp . 87 102.
[2]. 王宗櫚 陳嬿羽 張弘達 , 摔不破的太陽能電池 科技發展雜誌 483 期 , 頁62 68.
[3]. T.N. Chen, D. S. Wuu, C.C. Wu, C.C. Chiang, Y.P.Chen and R.H. Horng., 2006,High Performance Transparent Barrier Films of SiOx/SiNx Stacks on Flexible Polymer Substrates”, J. Electrochem. Soc. Volume 153, pp . F 244 F 248.
[4]. 張秋萍 , 黃天恆 2004, 電漿技術應用於 OLED 阻氣膜介紹 化工資訊與商情 18 期 ,頁 53 58 , 12 月
[5]. J. Fahlteich, W. Schönberger, M. Fahland and N. Schiller., 2011, Characterization of reactively sputtered permeation barrier materials on polymer substrates”,Surface and Coatings Technology , Volume 205 pp. S141 S144 July.
[6]. T.N. Chen, D.S. Wuu, C.C. Wu, R.H . Horng, F. Wei, L. Y. Jiang, H. U . Lee and Y.Y.Chang., 2010, Deposition and characterization of ultra high barrier coatings for fle xible electronic applications”, Vacuum , Volume 84 , pp. 1444 1447 , June
[7]. S.R. Kim, M.H. Choudhury, W.H. Kim and G.H. Kim., 2010, Effects of argon and oxygen flow rate on water vapor barrier properties of silicond oxide coatings deposited on polyethylene terephthalate by plasma enha nced chemical vapor deposition”, Thin Solid Films , Volume 518, pp. 1929 1934 .
[8]. A. Heya, T. Minamikawa, T. Niki, S. Minami, A. Masuda, H. Umemoto, N.
Matsuo, H. Matsumura., 2008, “Coverage properties of SiNx films prepared by
catalytic chemical vapor deposition on trenched substrates below 80 °C”, Thin
Solid Films, Volume 516, pp. 3000-3004, March.
[9].V. Siriwongrungson, M.M. Alkaisi and S.P. Krumdieck., 2007, “Step coverage
of thin titanium films on patterned silicon substrate by pulsed-pressure MOCVD”,Surface and Coatings Technology, Volume 201, pp. 8944-8949, September.
[10].B. Pang, D. Cheung and W.G. Petro., 1991, “Improved step coverage of silanebased PECVD nitride and oxynitride passivation films”, Proc. IEEE VLSI
Multilevel Interconnection Conf, 423.
[11]..Hiromu. Takatsuka, Matsuhei. Noda, Yoshimichi. Yonekura, Yoshiaki. Takeuchi and Yasuhiro. Yamauchi., 2004, “Development of high efficiency large area silicon thin film modules using VHF-PECVD”, Solar Energy, Volume 77, pp.
951-960, December.
[12]..T. Takagi, K. Takechi, Y. Nakagawa, Y. Watabe and S. Nishida., 1998, “High rate deposition of a-Si:H and a-SiNx:H by VHF PECVD”, Vacuum, Volume 51,
78 pp. 751-755, December
[13].陳金鑫、黃孝文, 2009, OLED 夢幻顯示器, 五南出版社.
[14].B.M. Henry, A.G. Erlat, A. McGuigan, C.R.M. Grovenor, G.A.D. Briggs, Y.
Tsukahara, T. Miyamoto, N. Noguchi and T. Niijima., 2001, “Characterization of
transparent aluminium oxide and indium tin oxide layers on polymer substrates”,Thin Solid Films, Volume 382, pp. 194-201, February.
[15].F. Stahr, K. Schade, J. Kuske, S. Röhlecke and O.Steinke., 2005, “Large area VHF plasma polymerisation electrode system”, Surface and Coatings Technology,Volume 200, pp. 490-493, October
[16].C.C. Chiang, D.S. Wuu, H.B. Lin, Y.P. Chen, T.N. Chen, Y.C. Lin, C.C. Wu, W.C.Chen, T.H. Jaw and R.H. Horng., 2006, “Deposition and permeation properties of SiNx/parylene multilayers on polymeric substrates”, Surface and Coatings Technology, Volume 200, pp. 5843-5848, May.
[17].T.N. Chen, D.S. Wuu, C.C. Wu, C.C. Chiang, H.B. Lin, Y.P. Chen and R.H.
Horng., 2006, “Effects of plasma pretreatment on silicon nitride barrier films on polycarbonate substrates”, Thin Solid Films, Volume 514, pp. 188-192, August.
[18].M.C. Lin, C.H. Tseng, L.S. Chang and D.S. Wuu., 2007, “Characterization of the silicon oxide thin films deposited on polyethylene terephthalate substrates by radio frequency reactive magnetron sputtering”, Thin Solid Films, Volume 515, pp.4596-4602, April.
[19].T.N. Chen, D.S. Wuu, C.C. Wu, C.C. Chiang, Y.P. Chen and R.H. Horng., 2007,“Improvements of Permeation Barrier Coatings Using Encapsulated Parylene
Interlayers for Flexible Electronic Applications”, Plasma Process. Polym,
Volume 4, pp. 180-185.
[20].J. Shim, H.G. Yoon, S.H. Na, I. Kim and S. Kwak., 2008, “Silicon oxynitride gas barrier coatings on poly(ether sulfone) by plasma-enhanced chemical vapor deposition”, Surface and Coatings Technology, Volume 202, pp. 2844-2849,March.
[21].K.S. Ong, R.G.C. Ruey, E. Ou, Z. Zheng and D.L.M. Ying., 2010, “Interfacial and mechanical studies of a composite Ag–IZO–PEN barrier film for effective encapsulation of organic TFT”, Organic Electronics, Volume 11, pp. 463-466,March.
[22].G.H. Lee, J. Yun, S. Lee, Y. Jeong, J.H. Jung and S.H. Cho., 2010, “Investigation of brittle failure in transparent conductive oxide and permeation barrier oxide multilayers on flexible polymers”, Thin Solid Films, Volume 518, pp. 3075-3080,March.
[23].J. Lewis., 2006, “Material challenge for flexible organic devices”, Materials Today, Volume 9, pp. 38-45, April.79
[24].S. Grego, J. Lewis, E. Vick and D. Temple., 2005, “Development and evaluation of bendtesting techniques for flexible-display applications.”, Journal of the SID,13/7, pp. 575- 581.
[25].Hong Xiao 著.羅正忠,張鼎張譯., 2001, “半導體製程技術導論二版”,歐亞書局, chap 7.
[26].Michael. Quirk、Julian. Serda 著., 2005, 羅文雄、蔡榮輝、鄭岫盈譯, “半導體
製造技 術”, 滄海書局, chap. 11, 8 月.
[27].Sematech., 1994, “Deposition Processes”, in Furnace Processes and Related
Topics ”, 85 Austin, TX : SEMATECH., p.6.
[28].Michael Quirk、Julian Serda 著., 2005, 羅文雄、蔡榮輝、鄭岫盈譯, “半導體製造技 術”, 滄海書局, chap. 11, 8 月.
[29].Hong Xiao 著., 2014, “半導體製程技術導論三版”, 全華圖書, chap 10.
[30].莊達人, 2000, “VLSI 製造技術”, 高立圖書有限公司, chap. 5.
[31].L. Eckertova and T. Ruzicka., 1993, “Diagnostics and Applications of Thin Films”,Institute of Physics Publishing, chap. 1 & 2.
[32].田宏隆, 2004, “可撓式平面顯示器用基板材料”, 工業材料雜誌., 234 期, pp.144-152.
[33].K. Teshima, H. Sugimura, Y. Inoue and O. Takai., 2003, “Gas Barrier
Performance of Surface-Modified Silica Films with Grafted Organosilane
Molecules”, Langmuir, Volume 19, pp. 8331-8334, August.
[34].B.M. Henry, A.G. Erlat, A. McGuigan, C.R.M. Grovenor, G.A.D. Briggs, Y.
Tsukahara, T. Miyamoto, N. Noguchi and T. Niijima., 2001, “Characterization of
transparent aluminium oxide and indium tin oxide layers on polymer substrates”,Thin Solid Films., Volume 382, pp. 194-201, February.
[35].楊順文, 2002, “電漿碳氮層-TPX 複合膜氧氮分離效能之研究”, 私立中原大學碩士論文.
[36].S. da Silva Sobrinho, M. Latre`che, G. Czeremuszkin J.E. Klemberg Sapieha and M.R. Wertheimer., 1998, “Transparent barrier coatings on polyethylene
terephthalate by singleand and dual-frequency plasma-enhanced chemical vapor
deposition”, Journal of Vacuum Science & Technology A, Volume 16, pp. 3190-
3198.
[37].A.P. Roberts, B.M. Henry , A.P. Sutton , C.R.M. Grovenor , G.A.D. Briggs ,T.Miyamoto, M. Kano, Y. Tsukahara and M. Yanaka., 2002, “Gas permeation in
silicon-oxide/polymer (SiOx/PET) barrier films: role of the oxide lattice, nanodefects and macro-defects”, Journal of Membrane Science, Volume 208, pp. 75-88, October.
[38].R.W. Hoffman, C.H.S. Dupuy and A. Cachard., 1976, “Physics of nonmetallic
Thin Films“, Plenum Press: New York, pp. 273.
[39].K.L. Chopra., 1969, “Mechanical effects in thin films, in Thin Film Phenomena”,McGRAW –HILL : New York, pp. 266.
[40].J.W. Han, H.J. Kang, J.Y. Kim, G.Y. Kim and D.S. Seo., 2006, “Improvement of Permeation of Solvent-Free Multilayer Encapsulation of Thin Films on
Poly(ethylene terephthalate)”, Japanese Journal of Applied Physics, Volume 45,
pp. 9203.
[41].G.L. Graff, R.E. Williford and P.E. Burrows., 2004, “Mechanisms of vapor
permeation through multilayer barrier films lag time versus equilibrium
permeation.”, Journal of Applied Physics, Volume 96, pp. 1840.
[42].Tsai.Ning. Chen, Dong.Sing. Wuu, Chia.Cheng. Wu, Ray.Hua. Horng, Hsiao.Fen.Wei, Liang.You. Jiang, Hung.Uang. Lee and Yu.Yang. Chang., 2010, “Deposition and characterization of ultra-high barrier coatings for flexible electronic applications”, Vacuum, Volume 84, pp. 1444-1447, June.
[43].Sung.Ryong. Kim, Moinul. Haque. Choudhury, Won.Ho. Kim and Gon.Ho. Kim.,
2010, “Effects of argon and oxygen flow rate on water vapor barrier properties of silicond oxide coatings deposited on polyethylene terephthalate by plasma
enhanced chemical vapor deposition”, Thin Solid Films, Volume 518, pp. 1929-
1934, February
[44].J. Fahlteich, W. Schönberger, M. Fahland and N. Schiller., 2011,
“Characterization of reactively sputtered permeation barrier materials on polymer substrates”, Surface and Coatings Technology, Volume 205, pp. S141-S144, July.
[45].徐爵民, 2015, ”高度整合晶片技術發展藍圖”,台灣產業科技前瞻研究計畫,頁 50.
[46].P.T. Boyer, B. Hajji, J.L. Alay, J.R. Morante, A. Martinez., 1999, “Properties of SiOxNy films deposited by LPCVD from SiH4/N2O/NH3 gaseous mixture”,Sensors and Actuators A: Physical, Volume 74, pp. 52-55, April.
[47].R.K. Pandey, L.S. Patil, J.P. Bange, D.R. Patil, A.M. Mahajan, D.S. Patil and D.K.Gautam., 2004,“Growth and characterization of SiON thin films by using thermalCVD machine”, Optical Materials, Volume 25, pp. 1-7, February.
[48].D. Criado, I. Pereyra and M.I. Alayo., 2003, “Study of nitrogen-rich silicon oxynitride films obtained by PECVD”, Materials Characterization, Volume 50, pp.167-171, March.
[49].T. Oyaidu, Y. Ogawa, K. Tsurumaki, K. Ohdaira and H. Matsumura., 2008,
“Formation of gas barrier films by Cat-CVD method using organic silicon
compounds”, Thin Solid Films, Volume 516, pp. 604-606, January
[50].P.E. Burrows, G.L. Graff, M.E. Gross, P.M. Martin, M.K. Shi, M. Hall, E. Mast,C. Bonham, W. Bennett and M.B. Sullivan., 2001, “Ultra barrier flexble substrate for flat panel displays”, Displays, Volume 22, pp. 65-69, May.
[51].P.vandeWeijer,P.C.P.Bouten,S.Unnikrishnan,H.B.Akkerman,J.J.Michels,T.M.B.
van Mol“High-performance thin-film encapsulation for organic light-emitting
diodes”Org.Electron,44(2017),pp.94-98
[52].A.L.Briseno,R.J.Tseng,M.M.Ling,E.H.L.Falcao,Y.Yang,F.Wudl,Z.BaoHigh-
“performance organic single-crystal transistors on flexible substrates”Adv.
Mater,18(2006),pp.2320-2324
[53].P.G. Pai, S.S. Chao and Y. Takagi, 1985, “Infrared spectroscopic study of SiOx films produced by plasma enhanced chemical vapor deposition”, Journal of
Vacuum Science & Technology A, Volume 4, Issue 3, pp. 689-694, October.
[54].A.J. Choudhury, J. Chutia, H. Kakati, S.A. Barve, A.R. Pal, N.S. Sarma, D.Chowdhury and D.S. Patil, 2010, “Studies of radiofrequency plasma deposition
of hexamethyldisiloxane films and their thermal stability and corrosion
resistance behavior”, Vacuum, Volume 84, Issue 11, pp. 1327-1333,4 June.
[55].黃吉廷, 2014“可撓式塑膠基板上製備有機/無機氮氧化矽多層氣體阻障層及其機械撓曲特性之研究”, 國立虎尾科技大學碩士論文.
[56].陳順祺, 2016“氣體阻障層製備於具有連續沉積-蝕刻有機矽基覆蓋之圖案化表面之研究”, 國立虎尾科技大學碩士論文.
[57].廖藝澤,2011“濺鍍氮氧化矽薄膜以及氮氧化矽/矽多層膜之結構與發光性質研究”,國立台灣科技大學碩士論文.