此篇研究以仿生概念為發想，學習自然界的生物-鮑魚殼之殼層結構，藉由有機-無機多層複合結構，增進矽基薄膜負極材料之機械性質，並以此增進其作為鋰離子電池負極材料使用之電化學穩定性。本篇研究以複合物理濺鍍系統鍍製氧化矽-聚亞醯安之無機-有機多層薄膜，此濺鍍系統整合脈衝雷射以及磁控濺鍍至單一系統，以此方式可有效鍍製出無機-有機多層複合薄膜結構，此研究以此系統將氧化矽-聚亞醯安多層複合薄膜鍍製於銅箔上並研究其機械性質及電化學性質。實驗以高解析電子微探儀(EPMA)分析其成分組成，並以掃描式電子顯微鏡(SEM)觀察其多層結構。實驗結果顯示特定結構比例之氧化矽-聚亞醯安薄膜在第一圈充放電中具有較高之可逆效率且具有較好的充放電穩定性，以奈米壓痕試驗機(Nano-Indentation)定量薄膜之破裂韌性，結果顯示多層結構之薄膜材料具有較高之破裂韌性，使其具有較佳之充放電穩定性。

A new idea of bio-mimic organic-inorganic multilayer thin film has been introduced as a strategy to improve the mechanical and electrochemical performance of silicon-based anode materials. The organic-inorganic multilayer thin film composed of SiOx (nonstoichiometric silicon suboxides) and PI (polyimide) has been synthesized by a hybrid sputtering system combining reactive RF sputtering and pulsed laser deposition. SiOx/PI thin films were deposited on a copper foil to investigate its electrochemical properties. The chemical composition of as-deposited SiOx/PI coatings were measured by a FE-EPMA. The overall multilayered structure was observed by a Scanning Electron Microscopy. The SiOx/PI multilayer thin film anode with proper architecture control exhibits higher columbic efficiency during 1st charge/discharge cycle and better capacity retention as compared to pure SiOx thin film anode. The fracture toughness of SiOx/PI multilayer thin film anode was measured via nanoindentation as compared to the pure SiOx thin film anode. The results show that the multilayer structure reveals a higher
fracture toughness, leading to a better structure stability during the charge/discharge cycling.

Abstract………1
Chapter 1 Introduction………2
1.1 Background………2
1.2 Improvement Strategy………3
1.3 Learning from Mother Nature………3
1.4 Motivation and Objectives………4
Chapter 2 Literature Review………5
2.1 Introduction of Bio-Materials………5
2.1.1 Inspiration from Biological Materials………5
2.1.2 Abalone shells………7
2.2 Sputtering Technique………22
2.2.2 Reactive Magnetron Deposition………23
2.3 Pulsed Laser Deposition………26
2.3.1 Typical PLD System………26
2.3.2 Deposition of polymer films………27
2.4 Review of Multilayer Coatings………31
2.4.1 Strengthening Mechanisms………31
2.5 Mechanical Properties Evaluations and Characterizations………37
2.6 Fracture Toughness Evaluation………40
2.6.1 Nano-indentation Method………41
Chapter 3 Experimental Section………45
3.1 Hybrid Sputtering and PLD System………45
3.2 Deposition by the Hybrid PVD System………45
3.3 Material Characterization………46
Chapter 4 Results and Discussion………50
4.1 Phase Identification and Microstructure Analysis of SiOx-PI Multilayer Thin Film………50
4.2 Electrochemical Properties of SiOx-PI Multilayer Thin Film………54
4.3 Fracture Toughness of Multilayer Coatings………63
4.4 Dependence between Mechanical Properties and Thickness Ratio of Organic-Inorganic Layer………65
4.5 Strengthening Mechanisms of Multilayer Thin Film………66
Chapter 5 Conclusions………80
References………81

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