ZrN/Zr Thin Film Gas Barrier on Flexible PET Substrate Deposited by Magnetron Sputtering

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研究生：	褚漢明 Chu, Han-Ming
論文名稱：	ZrN/Zr Thin Film Gas Barrier on Flexible PET Substrate Deposited by Magnetron Sputtering 利用磁控濺鍍法於軟性基材上製備含鋯介層之氮化鋯阻氣薄膜
指導教授：	喻冀平 Yu, Ge-Ping 黃嘉宏 Huang, Jia-Hong
口試委員:
學位類別：	碩士 Master
系所名稱：	原子科學院 - 工程與系統科學系 Department of Engineering and System Science
論文出版年：	2009
畢業學年度：	98
語文別：	英文
論文頁數：	102
中文關鍵詞：	氮化鋯、鋯介層、水氣穿透速率、堆積因子、片電阻
相關次數：	點閱：2 下載：0
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The objective of this study was to deposit a double-layer thin film of ZrN/Zr on flexible PET substrates with good water vapor impermeability, low sheet resistance and excellent adhesion. The ZrN/Zr thin films have been successfully deposited on PET substrates by magnetron sputtering technique. The respective deposition time of Zr and ZrN was the designate variable to study the effect of thickness of Zr or ZrN on the related properties of the deposited thin films. The water vapor transmission rate (WVTR) at various temperatures, activation energy (EA) of water vapor permeation, sheet resistance, adhesion and optical properties of the deposited thin films were systematically investigated. Experiment results showed that the adhesion of all Zr/PET, ZrN/PET and ZrN/Zr/PET was excellent. WVTR at 30 °C of the ZrN/Zr thin films decreased with increasing total film thickness and packing factor but increased as the total thickness reached the critical thickness of 150 nm. Besides, it was found that films with thicker Zr interlayer and total film thickness still preserved good water vapor impermeability at higher temperature. The adding of Zr interlayer could effectively increase the packing factor of ZrN thin films and hence decrease the sheet resistance and WVTR. The lowest values of WVTR at 30 °C and sheet resistance obtained in this study were 0.295 gm/m2/day and 38.0 Ω/□, respectively. The superior performance of the thin films nearly reached the requirements for the applications of flexible LCDs, inorganic solar cells, and thin film batteries.

本研究之主要目的係將氮化鋯/鋯介層之雙層結構鍍著在軟性聚對苯二甲酸乙二酯
基材上，並使其具備良好的阻水氣性質、低片電阻以及優異的附著性。實驗證實利用磁
控濺鍍技術可成功地將氮化鋯/鋯介層鍍著於聚對苯二甲酸乙二酯基板上。在本研究中分
別選擇氮化鋯薄膜及鋯介層之鍍著時間作為實驗設計變數以探討氮化鋯薄膜及鋯介層
之厚度對於薄膜相關性質之影響。討論中針對薄膜在不同溫度下的水氣穿透速率、激發
能、片電阻、附著性以及光學性質作有系統性的探討。由實驗結果得知鋯薄膜、氮化鋯
薄膜以及氮化鋯/鋯介層雙層結構對於聚對苯二甲酸乙二酯基材之附著性皆相當優異。在
攝氏30 度所量測的水氣透過速率隨著總膜厚以及堆積因子上升而下降，但是當總厚度
超過臨界厚度150 nm 時水氣透過速率會開始上升。此外，本研究也發現當薄膜擁有較
厚的鋯介層以及總厚度時，薄膜在高溫時仍有不錯的抗水氣透過性。鍍著鋯介層能有效
地增加氮化鋯薄膜的堆積因子並使得其水氣透過速率和片電阻下降。在本實驗中所量測
到在攝氏30 度的最低水氣透過速率為0.295 gm/m2/day，最低的片電阻為38.0 _/□，這
些優良的薄膜特性以近乎達到軟性液晶顯示器、軟性無機太陽能電池以及軟性薄膜電池
的要求。

謝誌.....i
摘要.....iii
Abstract.....iv
Content.....v
List of Tables.....vii
List of Figures.....viii
Chapter 1 Introduction.....1
Chapter 2 Literature Review.....5
2.1 Characteristics of Zirconium Nitride (ZrN) Barrier Thin Films.....5
2.2 Characteristics of Organic Polymer Substrates.....7
2.3 Deposition Methods.....8
2.4 Effects of Film Thickness on the Related Properties of Thin Films.....9
2.5 Effects of Interlayer on the Related Properties of Thin Films.....10
2.6 Effects of the Film/PET Interface on the Related Properties of Thin Films.....11
2.7 Mechanisms of Gas Permeation through Gas Barriers.....12
2.8 Theoretical Background of Activation Energy (EA) for Gas Permeation.....16
Chapter 3 Experimental Details.....19
3.1 Specimens Preparation and Deposition Process for ZrN/Zr Thin Films.....19
3.2 Characterization Methods.....22
3.2.1 Auger Electron Spectroscopy (AES).....22
3.2.2 Field-Emission Gun Scanning Electron Microscopy (FEG-SEM).....23
3.2.3 X-ray Photoelectron Spectroscopy (XPS).....23
3.2.4 Rutherford Backscattering Spectroscopy (RBS).....24
3.2.5 Grazing Incident X-ray Diffraction (GIXRD).....25
3.3 Properties Measurement.....25
3.3.1 Gas Anti-permeability Measurement and Activation Energy Calculation.....25
3.3.2 Adhesion.....27
3.3.3 Sheet Resistance.....28
3.3.4 Wettability.....28
3.3.5 Surface Roughness.....30
3.3.6 Light Transmittance.....31
3.3.7 Color (L*a*b*) and Reflectance.....31
Chapter 4 Experimental Results.....33
4.1 Chemical Compositions.....38
4.2 Structure.....41
4.2.1 GIXRD.....41
4.2.2 AES.....44
4.2.3 Packing Factor.....49
4.3 Properties.....50
4.3.1 Gas Permeability and Activation Energy (EA).....50
4.3.2 Sheet Resistance.....56
4.3.3 Adhesion and Wettability.....57
4.3.4 Transmittance.....57
Chapter 5 Discussion.....61
5.1 Review of Expected Properties in Experimental Objective.....61
5.2 The Distribution of Oxygen Content through the ZrN/Zr Thin Films.....62
5.3 Water Vapor Permeation.....64
5.3.1 The Mechanism of Water Vapor Permeation through ZrN/Zr Barrier Films.....64
5.3.2 Effects of Film Thickness, Packing Factor and Temperature on WVTR.....70
5.4 Effect of Zr Interlayer.....72
5.5 Deposition Window.....74
Chapter 6 Conclusions.....
References.....79
Appendix A Taguchi Method.....86
Appendix B Results of FESEM.....89
Appendix C Derivation of Film Thickness.....91
Appendix D Results of AFM.....93
Appendix E Color and Reflectance.....94
Appendix F Raw Data of Contact Angle.....99
Appendix G Effects of Thickness and Packing Factor on WVTR.....100

                                

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