有機發光二極體產業於近期內崛起，其特性為體積輕薄、大面積且可彎曲。然而當有機軟性元件被製作於塑膠基板上，材料將受到更嚴苛的挑戰。其中，有機半導體對水氣、氧氣十分敏感，元件易受水氣影響而產生暗點，此問題使目前影響有機發光二極體應用層面上存在極大的限制。為保護有機元件不受水氣影響而簡短使用壽命，製備極低水氣穿透率(<10-6 g/m2/day)及柔軟性佳之阻障層為開發有機發光二極體首要任務。本研究使用射頻磁控濺鍍有機單體HMDSO於PET基板上沉積含碳氧化矽薄膜阻障層及未完全斷鍵的HMDSO有機緩衝層交互堆疊。水氣阻障層是以磁控濺鍍槍、矽靶材及通入之有機單體HMDSO、氧氣在3 10-3torr腔體壓力下以電漿進行濺鍍，同時打斷HMDSO單體鍵結，與其共同反應聚合沉積高緻密性薄膜；而在有機緩衝層的鍍製過程中，採取提高HMDSO通量的方法提高有機薄膜當中線狀氧化矽結構比例，有助於薄膜附著在軟性基板，並提升薄膜可撓性。實驗以功率100W、6sccm氧氣、及0.4sccm HMDSO鍍製一緻密性高、孔洞性低、高光穿透率的水氣阻障薄膜，其中單層阻水膜水氣穿透率可低於10-2 g/m2/day，邃以100W功率、6sccm氧氣、及1sccm HMDSO鍍製結構中含甲基矽的柔軟緩衝層作為後續堆疊。研究發現經堆疊3對後薄膜水氣穿透率可降至原本約1/5，希望後續利用此有機無機薄膜堆疊方式沉積氧化矽多層膜，能符合有機元件阻水及可撓需求，應用於封裝產業。

The recent rise of flexible electronics industry aiming to deliver lightweight, flexible and large-area products has been extensively applied in the fields of display. However, many material and process-related challenges appear when flexible organic components are fabricated on polymer substrate. Among the challenges, moisture permeation could degrade and reduce the performance and durability of organic flexible organic light-emitting diode (OLED), making it difficult to be developed. In order to prolong OELD’s lifetime, water vapor transmittance rate (WVTR) must be below <10-6 g/m2/day. In this study, we used magnetron sputtering and hexamethyldisiloxane (HMDSO) to deposit SiO2:C buffer layer and SiO2 barrier film on PET substrate. Barrier film was deposited in high-density plasma produced by magnetron sputtering gun, oxygen, and fragmented HMDSO were mixed together under 1 10-3 torr to deposit dense films. Buffer layer was deposited in the same way as barrier film but rasing the HMDSO flow to improve the ratio of linear organic silicon oxide thin film structure which helps the film deposited on flexible substrate.In this study,we used 100 W RF power, 6sccm O2and 0.4 sccm HMDSO to deposit a film with low porosity and high transmittance. WVTR of the film reached the value of 0.05 g/m2/day, then we used100 W RF power, 6sccm O2and 1 sccm HMDSO to deposit a film which has rich methyl stack as buffer layer.In study we found three pairs of stacked film WVTR can be reduced to about 1/5 of single layer. It is believed that by combining organic and inorganic process, multilayer could meet OLED barrier requirement and will be used in OLED encapsulation industry in future.

[1] Chatham, H. "Oxygen diffusion barrier properties of transparent oxide coatings on polymeric substrates." Surface and Coatings Technology 78.1 (1996): 1-9.
[2] Lewis, J. Material challenge for flexible organic devices. Materials today, 9(4), 38-45. (2006).
[3] 呂孟謙. 六甲基二矽氮烷與氧氣製備之封裝膜阻水阻氣特性研究. 臺灣大學光電工程學研究所學位論文, 1-82. (2011).
[4] Liew, Y. F., Aziz, H., Hu, N. X., Chan, H. S. O., Xu, G., & Popovic, Z. Investigation of the sites of dark spots in organic light-emitting devices.Applied Physics Letters, 77(17), 2650-2652.J. (2000).
[5] Fahlteich, M. Fahland, W. Schonberger, N. Schiller, “Permeation barrier properties of thin oxide films on flexible polymer substrates”, Thin Solid Films, 517, pp.3075–3080, (2009).
[6] Park, J. S., Chae, H., Chung, H. K., & Lee, S. I. Thin film encapsulation for flexible AM-OLED: a review. Semiconductor science and technology, 26(3), 034001. (2011).
[7] Park, J. S., Chae, H., Chung, H. K., & Lee, S. I. Thin film encapsulation for flexible AM-OLED: a review. Semiconductor science and technology, 26(3), 034001(2011)..
[8] Grill, A. Cold plasma in materials fabrication (Vol. 151). IEEE Press, New York.. (1994).
[9] Brian Chapman, “Glow Discharge Process”, John Wiley & Sons, Canada,( 1980).
[10] 國科會精密儀器發展中心，真空技術與應用，國科會精密儀器發展中心，第71-79頁，台北，民國九十年。
[11] 國科會精密儀器發展中心，真空技術與應用，國科會精密儀器發展中心，第369-386頁，台北，民國九十年。
[12] M. Ohring, “The Material Science of the Thin Films”, Academic Press, (1992).
[13] Chen, T. N., Wuu, D. S., Wu, C. C., Chiang, C. C., Chen, Y. P., & Horng, R. H. High-performance transparent barrier films of SiO x∕ SiN x stacks on flexible polymer substrates. Journal of The Electrochemical Society, 153(10), F244-F248. (2006).
[14] Donald M. Mattox, Handbook of Physical Vapor Deposition (PVD) Processing,
Noyes Publications, Westwood, New Jersey, (1998).
[15] Seo, S. W., Jung, E., Chae, H., & Cho, S. M. Optimization of Al 2 O 3/ZrO 2 nanolaminate structure for thin-film encapsulation of OLEDs. Organic Electronics, 13(11), (2012).
[16] 楊士賢，「以脈衝式電漿輔助化學氣相沉積法製備氟化非晶薄膜之研究」，中原大學化學工程學系，碩士論文，民國94年。.
[17] Q. Xie, J. Xu, L. Feng, L. Jiang, W. Tang, X. Luo, C. Han, “Facile creation of a super-amphiphobic coating surface with bionic microstructure”, Adv. Mater., 16, pp.302-205, (2004).
[18] Dameron, Arrelaine A., et al. "Gas diffusion barriers on polymers using multilayers fabricated by Al2O3 and rapid SiO2 atomic layer deposition." The Journal of Physical Chemistry C 112.12 (2008): 4573-4580.B. M. Henry, A. G. Erlat, A. McGuigan, C. R. M. Grovenor, G. A. D. Briggs, Y. Tsukahara, T. Miyamoto, N. Noguchi, T. Niijima, Thin Solid Films, 382, pp. 194, (2001).
[19] C. Oehr, M. Muller, B. D. Hegemann, U. Vohree, Surf. Coat. Technol., 116-110, pp.25-35, (1999).
[20] H. Yasuda., T. Hirotsu, “Critical evaluation of condition of plasma polymerization”, J. Polym. Sci. Pol. Chem., 16, pp.743, (1978).
[21] Alexander, M. R., Jones, F. R., & Short, R. D.. Mass spectral investigation of the radio-frequency plasma deposition of Hexamethyldisiloxane. The Journal of Physical Chemistry B, 101(18), 3614-3619. (1997).
[22] M. Goujon, T. Belmonte, G. Henrion, “OES and FTIR diagnostics of HMDSO/O2 gas mixtures for SiOx deposition assisted by RF plasma”, Surface and Coatings Technology, 188 –189, pp. 756–761, (2004).
[23] Dameron, A. A., Davidson, S. D., Burton, B. B., Carcia, P. F., McLean, R. S., & George, S. M. Gas diffusion barriers on polymers using multilayers fabricated by Al2O3 and rapid SiO2 atomic layer deposition. The Journal of Physical Chemistry C, 112(12), 4573-4580. (2008).
[24] Granstrom, J., Gällstedt, M., Villet, M., Moon, J. S., & Chatterjee, T. High performance encapsulation structures utilizing Russian Doll architectures.Thin Solid Films, 518(18), 5282-5287.. (2010).
[25] Lay, E., Wuu, D. S., Lo, S. Y., Horng, R. H., Wei, H. F., Jiang, L. Y., ... & Chang, Y. Y. Permeation barrier coatings by inductively coupled plasma CVD on polycarbonate substrates for flexible electronic applications. Surface and Coatings Technology, 205(17), 4267-4273. (2011).
[26] Wu, C. Y., Liao, R. M., Lai, L. W., Jeng, M. S., & Liu, D. S. Organosilicon/silicon oxide gas barrier structure encapsulated flexible plastic substrate by using plasma-enhanced chemical vapor deposition. Surface and Coatings Technology, 206(22), 4685-4691.. (2012).
[27] Chen, T. N., Wuu, D. S., Wu, C. C., Chiang, C. C., Chen, Y. P., & Horng, R. H. Improvements of permeation barrier coatings using encapsulated parylene interlayers for flexible electronic applications. Plasma Processes and Polymers, 4(2), 180-185.. (2007).
[28] Wu, C. Y., Liao, R. M., Lai, L. W., Jeng, M. S., & Liu, D. S. Organosilicon/silicon oxide gas barrier structure encapsulated flexible plastic substrate by using plasma-enhanced chemical vapor deposition. Surface and Coatings Technology, 206(22), 4685-4691. (2012).
[29] Seo, S. W., Chae, H., Seo, S. J., Chung, H. K., & Cho, S. M. Extremely bendable thin-film encapsulation of organic light-emitting diodes.Applied Physics Letters, 102(16), 161908.. (2013).
[30] K. Teshima, H. Sugimura, Y. Inoue, O. Takai, A. Takano, “Gas barrier performance of surface-modified silica films with grafted organosilane molecules”, Langmuir, 19, pp.10624-10627, (2003).
[31] D. Hegemann, H. Brunner, C. Oehr, “Evaluation of deposition conditions to design plasma coatings like SiOx and a-C:H on polymers”, Surface and Coatings Technol., 174–175, pp.253–260, (2003).
[32] M. Schaepkens, T.W. Kim, A.G. Erlet, M. Yan, K. W. Flanagan, C.M. Heller, and P. A. MoConnelee, “Ultrahigh barrier coating deposition on polycarbonate substrates”, J. Vac. Sci. Technol. A, vol. 22, pp.1716-1722,( 2004).
[33] G. Erlat, B. M. Henry, J. J. Grovenor, G. A. D. Briggs, and Y. Tsukahara, “Characterisation of aluminium oxynitride gas barrier films”, Thin Solid Flims, vol. 388, pp. 78-86, (2001).
[34] J. H. Burroughs, D. D. C. Bradly, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friedn, P. L. Burn, and A. B. Holmes, “light emitting diodes based on conjugated polymers”, Nature, vol.347, pp.539-541, (1990).
[35] E. H. H. Jamieson and A. H. Windle, “Structure and oxygen-barrier properties of metallized polymer film”, J. Mater. Sci., vol. 18, pp.64-80, (2004).
[36] John Fahlteich, Matthias Fahland, Waldemar Schönberger, Nicolas Schiller, “Permeation barrier properties of thin oxide films on flexible polymer substrates”, Thin Solid Films, 517, pp.3075–3080, (2009).
[37] Tsai-Ning Chen, “Design, Fabrication and Applications of Gas Barrier Coatings on Polymer Substrates”, National Chung Hsing University, Degree of Doctor of Philosophy, (2009).
[38] S. R. Kim, M. H. Choudhurya, W. H. Kima, G. H. Kimb, “properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition”, Thin Solid Films, Volume 518, pp.1929–1934,( 2010).
[39] Yi. C. Lin, Q. K. Le, “Optimizing The Organic/Inorganic Barrier Structure For Flexible Plastic Substrate Encapsulation”, International Journal of Engineering and Technology Innovation, vol. 2, pp.184-194, (2012).
[40] Beadley Finnigan, Barrier polymers. December 8, 2011. Retrieved September, from http://packaging-technology.org/31-barrier-polymers.html. (2012,)
[41] A. S. da Silva Sobrinho, G. Czeremuszkin, M. Latrèche, and M. R. Wertheimer, “Defect-permeation correlation for ultrathin transparent barrier coatings on polymers”, J. Vac. Sci. Technol. A 18, pp.149, (2000).
[42] A. G Erlat, B. M Henry, J. J Ingram, D. B Mountain, A McGuigan, “Characterization of aluminum oxynitride gas barrier films”, Thin Solid Films, Vol. 388, pp.78–86, (2001).
[43] B. M Henry, A. G Erlat, A McGuigan, C. R. M Grovenor, G. A. D Briggs, “Chatacterization of transparent aluminuim oxide and indium tin oxide layers on polymer substrates”, Thin Solid Films, Vol. 382, pp.194–201, (2001).
[44] G. Kaltenpoth, W Siebert, F Stubhan, X Wang, L Luo, “Moisture barrier properties of plasma enhanced chemical vapor deposited SiCxNy films on polyethylene naphthalate sheets and epoxy molding compound”, Surface and Coatings Technol., Vol. 161, pp.96-101, (2002).
[45] W. Huang, X. Wang, M. Sheng, L. Xu, F. Stubhan, L. Luo, T. Feng, X. Wang, F. Zhang, and S. Zou, Mater., “Low temperature PECVD SiN/sub x/ films applied in OLED packaging”, Sci. Eng., B 98, pp.248,( 2003).
[46] K. Teshima, H. Sugimura, Y. Inoue, O. Takai, A. Takano, “Gas barrier performance of surface-modified silica films with grafted organosilane molecules”, Langmuir, 19, pp.10624-10627,( 2003).
[47] D. Hegemann, H. Brunner, C. Oehr, “Evaluation of deposition conditions to design plasma coatings like SiOx and a-C:H on polymers”, Surface and Coatings Technol., 174–175, pp.253–260, (2003).
[48] M. Schaepkens, T.W. Kim, A.G. Erlet, M. Yan, K. W. Flanagan, C.M. Heller, and P. A. MoConnelee, “Ultrahigh barrier coating deposition on polycarbonate substrates”, J. Vac. Sci. Technol. A, vol. 22, pp.1716-1722,( 2004).
[49] D. S. Wuu, W. C. Lo, C. C. Chiang, H. B. Lin, L. S. Chang, “Water and oxygen permeation of silicon nitride films prepated by plasma-enhanced chemical vapor deposition”, Surface & Coatings Technol., 198, pp.114-117,( 2005).
[50] D. S. Wuu, W. C. Lo, C. C. Chiang, H. B. Lin, L. S. Chang, “Transparent barrier coatings on flexible polyethersulfone substrates for moisture-resistant applications”, Mater. Sci. Forum., vol. 475-479, pp.4017-4020,( 2005).
[51] D. S. Wuu, T. N. Chen, C. C. Wu, C. C. Chiang, Y. P. Chen, R. H. Hirng, and F. S. Juang, “Transparent barrier coatings for flexible organic light-emitting diode applications”, Chem. Vap. Deposition, vol. 12, pp.220-224, (2006).
[52] John Fahlteich, Matthias Fahland, Waldemar Schönberger, Nicolas Schiller, “Permeation barrier properties of thin oxide films on flexible polymer substrates”, Thin Solid Films, 517, pp.3075–3080, (2009).
[53] Tsai-Ning Chen, “Design, Fabrication and Applications of Gas Barrier Coatings on Polymer Substrates”, National Chung Hsing University, Degree of Doctor of Philosophy, (2009).
[54] S. R. Kim, M. H. Choudhurya, W. H. Kima, G. H. Kimb, “properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition”, Thin Solid Films, Volume 518, pp.1929–1934,( 2010).
Yi. C. Lin, Q. K. Le, “Optimizing The Organic/Inorganic Barrier Structure For Flexible Plastic Substrate Encapsulation”, International Journal of Engineering and Technology Innovation, vol. 2, pp.184-194, (2012)
[55] Yi. C. Lin, Q. K. Le, “Optimizing The Organic/Inorganic Barrier Structure For Flexible Plastic Substrate Encapsulation”, International Journal of Engineering and Technology Innovation, vol. 2, pp.184-194, (2012).