本實驗以反應式射頻磁控濺鍍法製備多元高熵碳化物及氮化物薄膜，探討薄膜成分含有不同碳原子及氮原子總量對薄膜微結構、附著性、抗玻璃沾黏性的影響。實驗結果顯示碳原子總量不同下，碳化物薄膜在 800 °C 熱循環前後均呈現 FCC 固溶結構，氮化物薄膜則根據氮含量多寡分別呈現混晶 (非晶∕FCC) 與 FCC 固溶結構，在 750 °C 熱循環後也仍保持相同結構，都具有優良的高溫熱穩定性。在碳化物及氮化物薄膜與鎢鋼基板附著性方面，碳化膜在熱循環前後都呈現最好的 HF1 等級，氮化膜則介於 HF2 至 HF3 之間的等級。針對碳化物薄膜在熱循環後與鎢鋼基板之間剝落的現象，本研究獲得解決方法，在工業上極具發展潛力。

Multi-element carbide and nitride coatings based on high-entropy alloys have received lots of attention. In this study, multi-element carbide and nitride films were designed and deposited at 350 °C and 150 V substrate bias on Si wafers and WC-Co substrates by RF reactive magnetron sputtering in the gaseous mixture Ar + CH4 and Ar + N2, separately. By changing carbon and nitrogen content of the coating, crystal structure, microstructure, adhesion and anti-sticking behavior between coating and glass have been investigated. The results of crystal structure indicate that all carbide coatings exhibit FCC structure before and after the 800 °C thermal cycling test. The structures of nitride coatings maintain amorphous + FCC mixed structure based on different nitrogen content before and after the 750 °C thermal cycling test. Thus, all the coatings have good thermal stability. The carbide coatings exhibit the best HF1 grade, and the nitride coatings exhibit the grade between HF2 and HF3. We also overcome the lift-off of the coatings from WC substrate during thermal cycling and thus show its potential in the glass molding industry.

摘要 I
Abstract II
致謝 III
目錄 VII
圖目錄 XII
表目錄 XXII
第一章 前言與研究目的 1
1.1 前言 1
1.2 研究目的 3
第二章 文獻回顧 5
2.1 精密光學玻璃模造製程技術 5
2.1.1 光學級模仁特性與要求 7
2.1.2 保護性鍍膜 8
2.2 薄膜鍍製技術 10
2.2.1 濺鍍原理 10
2.2.2 反應式濺鍍 11
2.2.3 直流濺鍍 14
2.2.4 磁控濺鍍 15
2.2.5 薄膜沉積與附著機制 18
2.2.6 薄膜微結構 20
2.3 高熵合金的發展與沿革 25
2.3.1 高熵合金的定義 25
2.3.2 高熵合金特點 27
2.3.3 高熵合金碳化膜及碳氮化物薄膜之研究 30
第三章 實驗步驟與方法 34
3.1 實驗設計 34
3.2 靶材製作 35
3.3 薄膜準備 39
3.3.1 基板 39
3.3.2 製程氣體 40
3.3.3 薄膜鍍製 41
3.4 高溫熱循環試驗 44
3.4.1 高溫爐真空石英封管熱循環試驗 44
3.4.2 真空快速熱退火 (RTA) 熱循環試驗 46
3.5 薄膜性質分析 49
3.5.1 成分分析 49
3.5.2 晶體結構分析 50
3.5.3 微結構分析 50
3.5.4 表面粗糙度分析 51
3.5.5 附著性分析 53
第四章 結果與討論 55
4.1 碳化物及氮化物薄膜之結構與性質 55
4.1.1 高熵合金靶材及鍍膜之成分分析 55
4.1.2 碳化物及氮化物薄膜之成分分析 57
4.1.3 碳化物及氮化物薄膜之晶體結構 61
4.1.4 碳化物及氮化物薄膜之表面形貌與截面形貌分析 66
4.1.5 碳化物及氮化物薄膜之附著性質 72
4.2 碳化物薄膜抗玻璃沾黏最佳化成分分析 76
4.2.1 高溫爐真空石英封管熱循環試驗之晶體結構分析 76
4.2.2 高溫爐真空石英封管熱循環試驗介面分析 83
4.2.2.1 650、750 °C 熱循環 83
4.2.2.2 800 °C 熱循環 97
4.2.2.3 850 °C 熱循環 101
4.2.3 碳化物薄膜最佳化成分 106
4.3 改善碳化物薄膜熱循環後薄膜剝落問題 107
4.3.1 兩種改善方法之薄膜成分分析 109
4.3.2 兩種改善方法之薄膜晶體結構分析 111
4.3.3 兩種改善方法之薄膜表面形貌與截面形貌分析 113
4.3.4 兩種改善方法之薄膜附著性質 116
4.4 改良之碳化物薄膜 RTA 熱循環試驗 118
4.4.1 RTA 熱循環試驗之晶體結構分析 119
4.4.2 RTA 熱循環試驗介面分析 122
4.4.2.1 800 °C 熱循環 122
4.4.2.2 750 °C 熱循環 130
4.4.2.3 薄膜與玻璃接觸區域黑色痕跡以及藍色區域分析 136
4.4.2.4 改良之碳化物薄膜熱循環後薄膜縱深分析 143
4.4.2.5 改良之碳化物薄膜熱循環後薄膜附著性質 152
4.5 氮化物薄膜抗沾黏性試驗 154
4.5.1 RTA 熱循環試驗之晶體結構分析 155
4.5.2 RTA 熱循環試驗介面分析 157
4.5.2.1 800 °C 熱循環 159
4.5.2.2 750 °C 熱循環 162
4.5.2.3 氮化物薄膜熱循環後薄膜附著性分析 165
4.6 RTA 熱循環前後之薄膜表面粗糙度分析 167
第五章 結論 176
第六章 研究貢獻 181
第七章 未來研究方向 182
第八章 參考文獻 183

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