以反應性射頻磁控濺鍍搭配HMDSO電漿聚合鍍製氧化矽摻碳薄膜阻障層之研究

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研究生：	魏敬倫 Chin-Lun Wei
論文名稱：	以反應性射頻磁控濺鍍搭配HMDSO電漿聚合鍍製氧化矽摻碳薄膜阻障層之研究 Investigation of SiOx:C barrier films deposited by RF reactive magnetron sputtering coupled with HMDSO/O2 plasma polymerization
指導教授：	李正中 Cheng-Chung Lee 郭倩丞 Chien-Cheng Kuo
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 光電科學與工程學系 Department of Optics and Photonics
論文出版年：	2012
畢業學年度：	101
語文別：	中文
論文頁數：	114
中文關鍵詞：	射頻磁控濺鍍、電漿聚合、HMDSO 、薄膜阻障層、氧化矽、軟性電子
外文關鍵詞：	Reactive magnetron sputtering, Plasma Polymerization, HMDSO, Barrier films, Silicon oxide, Flexible electronics
相關次數：	點閱：14 下載：0
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軟性電子產業於近期內崛起，其輕薄、可撓可攜、大面積之優點使其被廣泛應用於顯示器、照明、能源及生醫等領域中，並在未來十年內大幅改變人類生活型態。然而，當有機軟性元件被製作於塑膠基板上，許多材料及製程上的挑戰臨到。其中，有機半導體對水氣、氧氣十分敏感，其電性受氣體影響而迅速衰退，此乃可撓式有機發光二極體難以順利發展的原因之一。為提升有機元件壽命，製備極低水氣穿透率(WVTR)(<10^-6 g/m^2/day)及柔軟性佳之薄膜阻障層為首要之務。本研究使用射頻磁控濺鍍搭配有機單體HMDSO於PET基板上沉積氧化矽摻碳薄膜阻障層。磁控濺鍍槍、矽靶材及通入之氬氣、氧氣在2*10^-2 torr腔體壓力下以高密度電漿進行濺鍍，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。一般HMDSO電漿聚合製程中，薄膜內籠狀矽氧結構多於線狀矽氧結構；而本鍍膜系統中，矽靶逸出之矽原子少數與氧結合，多數與碳結合，形成較多線狀結構，因而沉積出孔洞性少且化學性質接近聚合物之薄膜。實驗以100W射頻能量、10sccm氧氣、30sccm氬氣及4sccm HMDSO成功鍍製一緻密性高、孔洞性低、光穿透率高於90%、膜厚50nm的薄膜阻障層，其水氣穿透率可達7.6*10^-2 g/m^2/day，約為目前以HMDSO製備氧化矽單層膜之WVTR最佳值0.3 g/m^2/day 的1/4。相信未來可用此有機無機材料混合方式沉積氧化矽多層膜，並符合有機元件阻水及可撓需求，以應用於OLED封裝產業。

The recent rise of flexible electronics industry aiming to deliver lightweight, flexible, portable and large-area products has been extensively applied in the fields of display, lighting and biomedical engineering and will be the next-generation lifestyle-changing electronic devices. 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 achieve OELD’s lifetime of thousands of hours, water vapor transmittance rate (WVTR) must be below <10^-6 g/m^2/day. In this study, magnetron sputtering and hexamethyldisiloxane (HMDSO) were used to deposit SiO2:C barrier film on PET substrate. In high-density plasma produced by magnetron sputtering gun, oxygen, silicon atoms and fragmented HMDSO were mixed together under 2*10^-3 torr to deposit dense films. During PECVD process, there were more cage silicon-oxide structures than linear silicon-oxide structures. By contraries, in our system, most escaping silicon atoms from target connected with carbon atoms instead of oxygen atoms, resulting in a polymer-like film with large amount of linear structure. 100 W RF power, 10sccm O2, 30sccm Ar and 4 sccm HMDSO were applied to deposit a 50-nm-thick film with low porosity and high transmittance above 90%. WVTR of the film reached the value of 7.6*10^-2 g/m^2/day, which is 4 times lower than the best WVTR value, 0.3 g/m^2/day, of films deposited by PECVD-HMDSO system. 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.

摘要......................I
Abstract................II
致謝....................III
總目錄....................V
圖目錄.................VIII
表目錄...................XI
第一章  緒論...............1
1-1  前言.................1
1-2  研究內容..............4
第二章  基礎理論與文獻回顧....6
2-1  反應性磁控濺鍍法........6
2-1-1   電漿基本原理.........6
2-1-2   濺鍍原理............8
2-1-3   磁控濺鍍...........13
2-1-4   反應性濺鍍..........14
2-2  電漿輔助化學氣相沉積.....15
2-2-1   電漿聚合............15
2-2-2   HMDSO碎裂反應.......18
2-3  氣體阻障層..............21
2-3-1   氣體穿透理論..........21
2-3-2   氣體阻障層製備與方法回顧.30
第三章  實驗方法與儀器原理.......37
3-1  實驗方法.................37
3-1-1   實驗流程..............37
3-1-2   鍍膜設備..............38
3-1-3   實驗步驟..............42
3-2  量測儀器原理..............44
3-2-1   可見光近紅外光光譜儀.....44
3-2-2   掃描式電子顯微鏡........45
3-2-3   傅立葉轉換紅外線光譜儀...46
3-2-4   X射線光電子能譜儀.......47
3-2-5   Mocon水氣透過率量測儀...48
第四章  結果與討論..............51
4-1  以矽靶材濺鍍搭配不同流量之HMDSO製備SiOx:C薄膜.....51
4-1-1   鍍率與光學穿透率分析.........................53
4-1-2   FTIR分析..................................56
4-1-3   XPS分析原子百分比及碳矽鍵結比例分析............63
4-2  以鈦靶材濺鍍搭配不同流量之HMDSO製備TiOx:C薄膜......72
4-2-1   光學穿透率分析..............................72
4-2-2   FTIR分析..................................72
4-2-3   XPS分析原子百分比及有機無機比例分析............74
4-3  於PET基材上鍍製氣體阻障層SiOx:C薄膜..............80
4-3-1   光學穿透率分析..............................80
4-3-2   不同HMDSO流量摻雜對水氣透過率(WVTR)之影響......82
4-3-3   不同膜厚對水氣穿透率(WVTR)之影響..............86
第五章  結論.......................................89
參考文獻...........................................91

                                

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