指導教授：蔡豐羽臺灣大學：材料科學與工程學研究所陳冠綸Chen, Guan-LunGuan-LunChen2014-11-262018-06-282014-11-262018-06-282014http://ntur.lib.ntu.edu.tw//handle/246246/262076本研究以原子層沈積(Atomic Layer Deposition, ALD)之聚醯胺(polyamide)薄膜性質，並探討有機無機混層簿膜之材料和結構對於薄膜氣體穿透率、抗撓曲程度的影響。本論文研究兩種高分子膜，分別是：(1)聚醯胺-32 (poly-N-(2-aminoethyl)-3-oxopropanamide, PA32) ，以丙二醯氯(malonyl chloride)與乙二胺(ethylene diamine)作為前趨物。(2)聚醯胺-42(poly-(E)-N-(2-aminoethyl)-4-oxobut-2-enamide, PA42)，以反丁烯二醯氯(fumaryl chloride)與乙二胺作為前趨物。PA32, PA42 聚醯胺膜可以分別在 75~125℃和 80℃成長。QCM 分析顯示薄膜擁有良好的自我限制(self-limiting)的特性，由 Alpha-step觀察可知高分子膜在 100 循環以下有著固定的成長率，以上則成長率漸減，Uv-vis圖譜顯示此膜的高透光度，SEM、AFM 結果則得知表面平整度高，易水解性則可以在儲存此膜於高溫高溼環境後觀察到。 另外我們對 PA42 薄膜作了感光性測試，但並不如預期有感光交聯之特性。最終，我們使用了新開發的氧化鋁/聚醯胺-32(Al2O3/PA32)與氧化鋁/氧化鉿/聚醯胺-32(AHO/PA32)等兩種混層系統製作可撓阻氣薄膜。在Al2O3/PA32 系統中，本研究發現在 5:20 的 Al2O3/PA32 比例下，薄膜擁有極佳的阻氣性質。此是由於 PA32 層在薄膜中有隔開無機層缺陷的效果，增長氣體的擴散路徑，進而提升薄膜的阻氣性質。在 AHO/PA32 的系統中，本研究發現加入了有機層後，薄膜的阻氣性質亦顯著提升。在水氣穿透率(WVTR)的量測中可達 1.3×10-6/m2/day，達到有機發光二極體(OLED)元件封裝的要求。此外，此薄膜具有穩定之阻氣效能，其阻氣效能經高溫(60℃)高溼(80RH)儲存超過 100 個小時或經過 200 次撓曲後，皆變化不大。本研究結果提供了一種可使用於軟性元件新的薄膜封裝方式。We studied the atomic layer deposition (ALD) processes of two polyamide films and their applications in flexible gas-permeation barriers. The two polyamides were: (1) poly-N-(2-aminoethyl)-3-oxopropanamide (PA32), deposited from malonyl chloride and ethylene diamide, and (2) poly-(E)-N-(2-aminoethyl)-4-oxobut-2-enamide (PA42), deposited from fumaryl chloride and ethylene diamide. The polyamide films showed ALD process temperature of 75~125Acknowledgement ............................................................................................................. i Abstract (Chinese) ............................................................................................................ ii Abstract (English) ............................................................................................................ iii Contents ........................................................................................................................... iv List of Tables ................................................................................................................... vi List of Figures ................................................................................................................. vii Chapter 1. Introduction .............................................................................................. 1 1.1 Motivation .................................................................................................... 1 1.2 Objective statement ...................................................................................... 3 Chapter 2. Background review ................................................................................... 5 2.1 The development of Atomic layer deposition (ALD) and Molecular layer deposition (MLD) ..................................................................................................... 5 2.2 Photosensitive polymers deposited by ALD ................................................. 9 2.2.1 The importance of photosensitive polymers ..................................... 9 2.2.2 Review of ALD photosensitive polymer film ................................ 10 2.3 Gas barrier films deposited by ALD ........................................................... 12 2.3.1 The importance of encapsulation technics...................................... 12 2.3.2 Review of encapsulation methods .................................................. 14 2.3.3 The development of ALD/MLD gas barrier technology ................ 18 Chapter 3. Experiment ............................................................................................. 20 3.1 Materials ..................................................................................................... 20 3.2 Atomic layer deposition/ Molecular layer deposition ................................ 22 3.3 Characterization of films ............................................................................ 28 3.3.1 Thickness measurement .................................................................. 28 3.3.2 UV illumination .............................................................................. 29 3.3.3 Element Component Analysis ........................................................ 29 3.3.4 Morphology Observation ................................................................ 30 3.3.5 Measurement of Optical Property................................................... 30 3.3.6 Helium Transmission Rate Measurement ....................................... 30 3.3.7 Water Vapor Transmission rate Measurement ................................ 33 3.3.8 Stabilities Test ................................................................................. 33 Chapter 4. Result and discussion ............................................................................. 34 4.1 Parameters of ALD deposition process ...................................................... 34 4.2 Characterization of Deposited Polymer structure ....................................... 40 4.3 Film characteristic ...................................................................................... 43 v 4.3.1 Linearly growth characteristic ........................................................ 43 4.3.2 Surface Morphology ....................................................................... 47 4.3.3 Optical Properties ........................................................................... 49 4.4 Characteristic of Al2O3 /PA32 multilayer films ........................................... 52 4.4.1 Deposition characteristic ................................................................ 52 4.4.2 Structure analysis ............................................................................ 55 4.4.3 Gas barrier property ........................................................................ 58 4.5 Characteristic of AHO/PA32 multilayer films ............................................ 61 4.5.1 Gas barrier property ........................................................................ 61 4.5.2 Bending test .................................................................................... 63 4.5.3 Storage in severe condition............................................................. 65 Chapter 5. Conclusions and Future Works ............................................................... 66 5.1 Conclusion .................................................................................................. 66 5.2 Future works ............................................................................................... 68 Chapter 6. Reference ................................................................................................ 692254338 bytesapplication/pdf論文公開時間：2019/08/25論文使用權限：同意有償授權(權利金給回饋本人)原子層沈積技術聚醯胺thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/262076/1/ntu-103-R01527028-1.pdf