臺灣博碩士論文加值系統

摘要
平面顯示器的實用化，顛覆了人類長久以來的使用習慣，目前朝向方便移動及新應用之趨勢不斷發展。以可撓曲性之塑膠基板材料取代現有之玻璃基板材料之平面顯示器，將成為未來發展之新趨勢。由於塑膠基板本身是無法有效抵擋水氣的滲透，容易造成內部顯示元件的損害，所以通常會在塑膠基板上鍍上一層氣體阻隔層。本研究將氮化鋁薄膜沉積在PET塑膠基材上研究氮化鋁薄膜對於阻隔水氣及氧氣的能力，期望將其應用在氣體阻隔層上能有很好的效果。氮化鋁薄膜是一種非常優良之薄膜材料，具有許多優良的性質；包含好的熱及化學穩定性，高密度，及具有良好的光學穿透性。
本實驗利用反應性射頻磁控濺鍍的技術以純鋁靶為靶材通入氮氣產生反應來製備氮化鋁薄膜，改變製程參數分別為射頻功率(300W、350W、400W)、氮/氬流量比率(80%、90%、100%)、基材偏壓(0V、-30V、-60V)。在未鍍膜的純PET基材，其水氣穿透率值為7.901 (g/m2-day)，氧氣穿透率值為27.924(c c /m2-day)，實驗的分析數據中得到，在固定工作腔壓1.2X10-2Torr，鍍膜時間30分鐘，在射頻功率400W、氮氣流量80%、基材偏壓0V時可得到最低的水蒸氣穿透率值為0.81(g / m2-day)。而在射頻功率400W、氮氣流量90%、基材偏壓-30V時可得到最低的氧氣穿透率值為2.3(c.c. / m2-day)。

Abstract
The utilization of the panel displays has convenient the daily living of people. The future trend has also turned it into focusing on the mobility and new applications, such as the substitutions of the glass substrates by flexible plastic substrates. However, since the plastic substrates can not effectively block the permeation of water vapor which leads into the damage of the internal circuits, a layer of gas barrier is used to deposit on the plastic substrates.
In this research, an AlN thin film was deposited on the PET substrate and its resistance capability against oxygen and water vapor was studied. Aluminum nitride thin film is an extraordinary film material, which possesses several excellent properties, includes good heat and chemical stability, high density and great optical permeability.
In this study the AlN thin film was deposited on PET by means of reactive RF magnetron sputtering equipped with the pure Al target in Ar/N2 atmosphere. The experiment parameters were sputtering power (300W、350W、400W), N2/Ar gas flow ratio (80%、90%、100%) and substrate bias (0V、-30V、-60V). The water vapor and oxygen permeability of original PET substrate are 7.901(g/m2-day) and 27.924(c.c./m2-day) respectively. The experiment results show that under the fixed working chamber pressure of 1.2X10-2Torr and 30 minutes depositing time, the lowest water vapor permeability of 0.81(c.c./m2-day) was obtained at the conditions as 400W sputtering power, N2 flow rate ratio 80% and substrate bias 0V. And we also can get the AlNx film with the lowest oxygen permeability 2.3(c.c./m2-day) of the conditions as 400W sputtering power, 90% N2 flow rate ratio and substrate bias -30V.

目錄
誌謝 I
摘要 III
Abstract IV
目錄 VI
表目錄 X
圖目錄 XI
第一章 緒論 1
1-1前言 1
1-2 研究目的 2
第二章 文獻回顧 7
2-1 氮化鋁的結構與特性 7
2-2 PET之性質與應用 7
2-3 濺鍍原理 8
2-4 射頻磁控濺鍍法之原理與特性 10
2-4-1 射頻濺鍍 11
2-4-2 磁控濺鍍 11
2-4-3 射頻與磁控濺鍍法之結合 12
2-5 射頻功率的影響 13
2-6 氮氣濃度的影響 13
2-7 基材偏壓的影響 14
2-8電漿預處理基板表面 14
2-9薄膜沉積之機制 16
2-9-1 薄膜沉積原理 16
2-9-2 薄膜沉積機構 17
2-10 薄膜微觀結構 18
2-11 滲透理論 19
2-12 田口法理論 21
第三章 實驗方法與步驟 35
3-1實驗規劃與流程 35
3-1-1 靶材與試片準備 35
3-2 薄膜沉積 35
3-2-1 鍍膜設備 35
3-2-2 鍍膜步驟 37
3-3 分析儀器及測試 38
3-3-1水蒸氣透過率測試儀 38
3-3-2氧氣透過率測試儀 39
3-3-3 X光光電子能譜儀 40
3-3-4可見光光譜儀 41
3-3-5場發射掃描式電子顯微鏡 41
3-3-6原子力顯微鏡 42
3-3-7 X光繞射儀 43
第四章 結果與討論 51
4-1 以田口法計算實驗參數之影響程度 52
4-2 改變射頻功率之影響 54
4-2-1 沈積速率之討論 54
4-2-2 微觀結構之分析 54
4-2-3 成分分析之討論 56
4-2-4 水蒸氣穿透率結果之討論 56
4-2-5 氧氣穿透率結果之討論 57
4-2-6 可見光光譜儀之分析 58
4-3 改變氮/氬流量比率之影響 59
4-3-1 沈積速率之討論 59
4-3-2 微觀結構之分析 60
4-3-3 成分分析之討論 61
4-3-4 水蒸氣穿透率結果之討論 61
4-3-5 氧氣穿透率結果之討論 62
4-3-6 可見光光譜儀之分析 62
4-4 改變基材偏壓之影響 63
4-4-1 沈積速率之討論 63
4-4-2微觀結構之分析 64
4-4-3 成分分析之討論 65
4-4-5 氧氣滲透率結果之討論 66
4-4-6 可見光光譜儀之分析 67
第五章 結論 122
參考文獻 124

參考文獻
[1] 曹義昌，”以電漿化學氣相沉積法在光學塑膠上成長多功能光學薄膜”，國立成功大學化學工程研究所碩士論文，1996。
[2] 蕭柏齡，”聚環烯高分子材料在平面顯示器之應用”，工業材料210期，2004.06，第174-182頁。
[3] 田宏隆、李宗銘，”平面顯示器可撓式塑膠基材技術”，電子與材料第19期，2003.08，第44-52頁。
[4] 王光龍，”從IDW2004看軟性顯示器之發展---應用各式軟性顯示器技術開發之產品已呼之欲出”，電子與材料25期，第111-125頁。
[5] 田宏隆，”軟性顯示器用塑膠基板材料發展與技術”， 工業材料210期，2004.06，第190-198頁。
[6] X. Li, Z. Xu, Z. He, H. Cao, W. Su, Z. Chen, F. Zhou and L. Song, in 35th Electronic Components Conference, Washington DC, USA, 20-22 May 1985, pp. 442-447
[7] X.Li, T.L. Sley and V.W.L. Chiu, Thin Solid Films, 250 (1994) 263-267
[8] S. Okamura, H. Nishi, T. Inada and H. Hashimoto, Appl. Phys. Lett., 40 (1992) 689
[9] Kazuo Tsubouchi and Nobuo Mikoshiba, IEEE Trans. Sonics Ultrason. SU-32, 5 (1985) 634
[10] A.F. Belyanin, L.L. Bouilov, V.V. Zhirnov, A.I. Kamenev, K.A. Kovalskij, Diamond and Related Materials, 8 (1999) 369-372
[11] Jipo Huang, Lian Wei Wang, Qin Wo Shen, Cheng Lu Lin and Mikael Osting, Journal of Electronic Materials, Vol. 28, No. 3, (1999) 225-227
[12] M. Ishiihara, S.J. Li, H. Yumoto, K. Akashi, Y. Ide, Thin Solid Films, 316 (1998) 152-157
[13] X. Li and T.L. Tansley, J. Appl. Phys., 68 (1990) 5369
[14] T. Shiosaki, T. Yamamoto, T. Oda and A. Kawabata, Appl. Phys. Lett. 36 (1980) 643
[15] J.S. Wang and K.M. Lakin, Appl. Phys. Lett. 40 (1982) 308
[16] M. Mortia, S. Isogai, K. Tsubouchi and N. Nikoshiba, Appl. Phys. Lett. 38 (1981) 50
[17] K.S. Stevens, M. Kinniburgh A.F. Schwartzman, A Ohtani and R. Beresford, Appl. Phys. Lett. 66 (1995) 3179
[18] G. Este, R. Surridge and W.D. Westwood, J. Vac. Sci. Technol. A4 (1986) 989
[19] R. Bensalem, A. Abid and B.J. Sealy, Thin Solid Films, 143 (1986) 141
[20] S. Ben Amor, G. Baud, M. Jacquent, G. Nansè, P. Fiox and M. Nardin, “XPS characterization of plasma-streated and alumina-coated PMMA”, Applied Surface Science 153 (2002) 172-182
[21] K. Koski, J. Hölsä, P. Juliet, Z.H. Wang, R. Aimo, K. Pischow, “characterization of aluminum oxide thin films deposition on polycarbonate substrate by reactive magnetron sputtering”, Material Science and Engineering B 65 (1999) 94-105
[22] Chaozong Liu, A.R. Gibbons, R.D. Arnell, J. tong, L. Ren, “Reactive deposition of aluminium oxide coatings on PTFE substrate”, Surf. Coat. Technol. 139 (2001) 111-117
[23] R. Cueff, G. Baud, J.P. Besse, M. Jacquet, “Study of thin alumina coatings sputtered on polyethylene terephthalate films”, Thin Solid Films 266 (1995) 198-204
[24] R. Cueff, G. Baud, M. Benmalek, J.P. Besse, J.R. Butruillo, M. Jacquet, “Alumina coatings on polyethylene terephthalate: characterization and X-ray photoelectron spectroscopy study”, Surf. Technol. 80 (1996) 96-99
[25] R. Cueff, G. Baud, M. Benmalek, J.P. Besse, J.R. Butruillo, H.M. Dunlop, M. Jacquet, “Characterization and adhesion study of thin alumina coatings sputtered on PET”, Thin Solid Films 270 (1995) 230-236
[26] G. Dennler, A. Moudayer, P. Raynand, Y. Segui, M. R. Wertheimer, “Characterization by RBS of hyper-thin SiO2 layers on various polymers”, Nuclear Instruments and Methods in Physics Research B 192 (2002) 402-428
[27] Ahmet G. Erlat, Bo-Chy Wang, Richard J. Spontak, Yelena Tropsha, Kevin D. Mar, David B. Montgomery, Erwin A. Vogler, “Morphology and gas barrier properties of thin SiOx coating on poly carbonate: correlations with plasma-enhanced chemical vapor deposition conditions”, J. Mater. Res. 15 (2000) 704-717
[28] C.S. Deny, H.E. Assender, F. Dinelli, O.V. Kolosov, G.A.D. Briggs, T. Miyamoto, Y. Tsukahara, “Nucleation and growth of gas barrier aluminum oxide on surface of poly(ethylene terephthalate, and polypropylene: effects of the polymer surface properties”, Journal of Polymer Science: Part B: Polymer Physics 38 (2003) 3151-3162
[29] 李宗銘，”下世代平面顯示器用可繞式塑膠基材技術”，工業材料169期，2001.01，第87-92頁。
[30] 田宏隆，”平面顯示器用可繞式塑膠基材技術與應用”，工業材料195期，2003.03，第156-162頁。
[31] M.T. Wauk and D.K. Winslow, Appl. Phys. Lett. 13 (1998) 286
[32] R.D. Vispute, Hong Wu and J. Narayan, Appl. Phys. Lett. 67(1995) 1549
[33] Miroshi Okano, Toshihrau Tanaka, Kenichi Shibata and Shoichi Nakano, Jpn. J. Appl. Phys. 31 (1992) 3017
[34] B. Wang, Y.N. Zhao and Z. He, Vacuum, Vol. 48, No. 5 (1997) 427-429
[35] A. Raveh, M. Weiss, M. Pinkas, D. Z. Rosen, G. Kimmel, Surface and Coating Technology, 114 (1999) 369-372
[36] D.C. Bertolet, Herng Liu and J.W. Rogers Jr., J. Appl. Phys. 75 (1994) 5385
[37] P. Bhattacharya and D. N. Bose, Jpn. J. Apply. Phys. 30 (10A) (1991) L1750
[38] R. Rodriguez-Clemente, B. Aspar, N. Azema, B. Armas, C. Combescure, J. Durand and A. Figueras, J. Crystal Growth, Vol. 133, pp. 59, 1993
[39] Eliseo Ruiz, Santigo Alvarez, Pere Alemany, Physical Review B., Vol. 49, pp. 7115, 1994
[40] 何朝仁，”氮化鋁壓電薄膜製作及特性化”，工業材料202期，2003.10，第94-99頁，
[41] Encyclopedia of polymer science and technology plastics, resins, rubber, fibers, supplement, Interscience Publishers, New York 1976.
[42] Ming-Ya Tang and Soojaa L. Kim, “Polylethylene terephthalate-Solvent Interaction: Gelation and Melting Point Depression”, Polymer Engineering and Science, 34, 1656 (1994)
[43] 田宏隆，”OLED用可繞式塑膠基材技術與現況”，電子與材料21期，2004.02，第50-58頁。
[44] 莊達人，”VLSI製造技術”，高立圖書，(2001) p559、p147
[45] 施敏著，張俊彥譯，”半導體元件物理與製作技術”，高立圖書，(1990) p429
[46] D.S. Richerby and A. Matthews, Advanced Surface Coating: A handbook of Surface Engineering, Chapman and Hall, New York, 1991, pp.92-100
[47] P.W. Atkin, “Physical Chemistry”, Oxford University press chapt. 31 (1986) 773
[48] Herman V. Boening, “Fundamentals of Plasma Chemistry and Technology”, Technomic, 1988
[49] R. Bruchhaus, “thin films for ferroelectric devices”, Ferroelectrics, 133 (1992) 73
[50] Donald L. Smith: Thin-Film Deposition Principles and Practice, the McGraw-Hill Companies, Inc. (1999) 483-499
[51] Milton Ohring: The Material Science of Thin Film, Acdamic Press, (1992) 121-123
[52] C.Y. Chang, Francis Kai: GaAs High-Speed Devices, John Wiley & Sons, Inc. (1994) 142-143
[53] John L. Vossen and Werner Kern, “Thin Film Process”, Academic Press, (1991) 134
[54] N. Danson, I. Safi, G. W. Hall, R. D. Howson, “Techniques for the sputtering of optimum indium-tin oxide films on to room-temperature substrates”, Surf. Coat. Technol. 99 (1998) 147-160
[55] R.S. Kumar, Mark Anch, Eric Ou, Guenther Ewald, Chus Soo Jin, “Low moisture permeation measurement through polymer substrates for organic light emitting devices”, Thin Solid Films 417 (2002) 120-126
[56] Donald L. Smith: Thin-Film Deposition Principles and Practice, the McGraw-Hill Companies, Inc. (1999) 157
[57] 莊達人，”VLSI製造技術”，高立圖書，(2001) p146-177
[58] D.M. Mattox, J. Vac. Sci. Technol. A7 (3) (1989) 1105
[59] “PERMATRAN-W Model 3/61 Operator’s Manual”, mocon
[60] “OX-TRAN 2/61 Modular System Operator’s Manual”, mocon
[61] 汪建民主編，”材料分析”，中國材料科學學會，1998
[62] 陳力俊等著，”材料電子顯微鏡光學”，行政院國家科學委員會精密儀器發展中心，1994
[63] A.S. da Silva Sobrinho, G. Czeremuszkin, M. Latreche, M.R. Wertheimer, “Defect-permeation correlation for ultrathin transparent barrier coatings on polymers”, J. Vac. Sci. Technol. A 18 (2000) 149-157
[64] William J. Koros, “Barrier Polymers and Structures”, American Chemical Society, Washington, 1990
[65] A. Sawada, A. Suzuki, T. Terai, T. Muroga, “Properties of AlN coatings produced by RF sputtering method”, Journal of Nuclear Materials 329-333 (2004) 1411-1413
[66] HaO Cheng, Peter Hing, ”The evolution of preferred orientation and morphology of AlN films under various RF sputtering powers”, Surface and Coatings Technology 167 (2003) 297-301
[67] B. Grycz, B. Gross and K. Miklossy, “Non-equilibrium processes in plasma technology”, American Elsevier publishing Co., Inc. N.Y., 1969
[68] S.V. Krishnaseamy, W.A. Hester, J.R. Shibata and S. Nakano, Jpn. J. Appl, Phys. 31 (1992) 3446
[69] K. Sugiyama, K. Taniguchi, K. Kiwabara, J. Mat. Sci. Lett. 9 (1990) 489
[70] 李怡德，”利用雙直交表智慧衍交型基因演算法之引子設計”，國立中山大學資訊工程學系研究所碩士論文，2002。
[71]田耀遠，”田口法應用於混凝土配比設計及交互作用之研究”，國立台灣科技大學營建工程系博士論文，2003。