本研究利用真空電弧熔煉製備非等莫耳 Al-B-Cr-Si-Ti-Zr 高熵合金靶材，並以反應式直流磁控濺鍍法鍍製高熵氮化膜，藉由調整氮氣流率、基板溫度和基板偏壓來探討在不同製程參數下薄膜晶體結構、微結構和接觸角等之影響，並對薄膜進行大氣退火以及真空退火處理，分析高熵氮化膜之抗氧化性與熱穩定性，最後選擇綜合表現較佳的薄膜鍍覆於不沾鍋材料 304 不鏽鋼和塑膠成型模具材料 P20 模具鋼上進行薄膜之附著和沾黏評估。
實驗結果發現在不同氮氣流率下，薄膜的晶體結構皆為非晶結構，並當氮氣流率為 30% 時，由於氮含量已達飽和，薄膜內部形成穩定鍵結，因此接觸角達最大值，而在施加基板溫度後，薄膜的晶體結構亦皆為非晶結構，由其微結構觀察可知薄膜的柱狀結構已有相當程度的緻密，然而，當施加基板偏壓至 -150V 後，薄膜開始析出 FCC 奈米晶，柱狀結構消失，表面形貌變得相當均勻且平整，但接觸角以基板偏壓 -50V 和 -150V 對照晶體結構為非晶和析出奈米晶時達最大值。在抗氧化性方面，薄膜在 900℃ 大氣退火兩小時後，氧化層厚度約為 250 nm，顯示氧化情形並不嚴重，具有良好的抗氧化性。而薄膜在 800℃ 真空退火一小時後，非晶結構才轉為非晶 + FCC 奈米晶的混合結構，並且原有混合結構薄膜也無晶粒粗大的現象發生，因此薄膜亦具有良好的熱穩定性。此外，刮痕附著試驗也指出不論鍍覆於 304 不鏽鋼或 P20 模具鋼基板上皆以自身合金作為中間層的附著效果最佳。最後在沾黏試驗中，以烹飪試驗來比較 304 不鏽鋼鍍膜前後的抗沾能力，結果顯示鍍覆高熵氮化膜的鍋具材料擁有優越的抗沾效果，並且本研究亦以熱熔膠沾黏試驗來比較 P20 模具鋼鍍膜前後的脫膠能力，鍍覆高熵氮化膜的模具材料確實亦具有較佳的脫膠表現，因此綜合以上特性顯示高熵氮化膜在鍋具和模具的應用上極具商用潛力。

High-entropy nitride films (Al-B-Cr-Si-Ti-Zr)100-XNX were sputter-deposited on silicon wafers. By the systematic variation of nitrogen flow ratio (RN), substrate temperature (TS) and substrate bias (VS), microstructure, crystal structure, contact angle and oxidation resistance have been investigated. Furthermore, P20 mold steels and 304 stainless steels deposited with optimal films were studied to estimate their anti-sticking performance.
The results of GIAXRD indicate that the films of different nitrogen flow ratio and substrate temperature all exhibit an amorphous structure. Furthermore, with the increasing substrate bias, the films precipitate FCC nano-crystals and possess denser microstructure. The films of VS = -50V and -150V have the highest contact angle. Besides, the films display excellent oxidation resistance and thermal stability. After air annealing at 900C for 2h, the oxidation layer is only 250 nm. In adhesion test, the films with 100 nm self-interlayer present the best adhesion property. In sticking test, the 304 stainless steels with optimal films have better anti-sticking property in actual cooking test, and the P20 mold steels with optimal films also have better degumming ability. This research demonstrates that the (Al-B-Cr-Si-Ti-Zr)100-XNX nitride films have a potential for the application in the cooking ware and plastic molding industry.

致謝 I
摘要 IV
Abstract VI
目錄 VIII
圖目錄 XII
表目錄 XVIII
壹、前言 1
貳、文獻回顧 4
2.1 薄膜鍍製技術 4
2.1.1 濺鍍原理 4
2.1.2 反應式濺鍍 5
2.1.3 直流濺鍍 7
2.1.4 磁控濺鍍 8
2.1.5 薄膜沉積與附著機制 11
2.1.6 薄膜微結構 13
2.2 薄膜種類與發展 18
2.2.1 薄膜發展概況 18
2.2.2 薄膜分類與介紹 19
2.2.3 薄膜硬化機制 24
2.3 高熵合金的發展與沿革 26
2.3.1 高熵合金定義 26
2.3.2 高熵合金特點 27
2.3.3 高熵氮化膜沿革 30
參、實驗流程 33
3.1 實驗設計 33
3.2 靶材製作 35
3.3 薄膜準備 37
3.3.1 基板準備 37
3.3.2 薄膜鍍製 38
3.4 薄膜基本性質分析 45
3.4.1 成份分析 45
3.4.2 晶體結構分析 46
3.4.3 微結構分析 46
3.4.4 表面粗糙度分析 47
3.5 薄膜電性分析 49
3.5.1 電阻率分析 49
3.6 薄膜機械性質分析 51
3.6.1 殘留應力分析 51
3.6.2 硬度和楊氏模數分析 53
3.6.3 接觸角分析 55
3.6.4 刮痕試驗 56
3.6.5 熱熔膠沾黏試驗 57
3.7 薄膜抗氧化性與熱穩定性分析 61
3.7.1 抗氧化性 61
3.7.2 熱穩定性 61
肆、結果與討論 62
4.1 氮氣流率變量對薄膜之影響 62
4.1.1 鍍率分析 62
4.1.2 成份分析 64
4.1.3 晶體結構分析 66
4.1.4 表面形貌與截面形貌分析 68
4.1.5 殘留應力分析 73
4.1.6 硬度和楊氏模數分析 75
4.1.7 表面粗糙度分析 78
4.1.8 接觸角值分析 82
4.1.9 電阻率分析 86
4.2 基板溫度變量對薄膜之影響 87
4.2.1 鍍率分析 87
4.2.2 成份分析 89
4.2.3 晶體結構分析 90
4.2.4 表面形貌與截面形貌分析 92
4.2.5 殘留應力分析 95
4.2.6 硬度和楊氏模數分析 98
4.2.7 表面粗糙度分析 101
4.2.8 接觸角值分析 104
4.2.9 電阻率分析 107
4.3 基板偏壓變量對薄膜之影響 108
4.3.1 鍍率分析 108
4.3.2 成份分析 110
4.3.3 晶體結構分析 111
4.3.4 表面形貌與截面形貌分析 113
4.3.5 殘留應力分析 118
4.3.6 硬度和楊氏模數分析 120
4.3.7 表面粗糙度分析 123
4.3.8 接觸角值分析 127
4.3.9 電阻率分析 134
4.4 薄膜抗氧化性分析 136
4.4.1 基板溫度變量薄膜的抗氧化性分析 136
4.4.2 基板偏壓變量薄膜的抗氧化性分析 140
4.5 薄膜熱穩定性分析 148
4.5.1 基板溫度變量薄膜的熱穩定性分析 148
4.5.2 基板偏壓變量薄膜的熱穩定性分析 156
4.6 薄膜附著性試驗 168
4.7 薄膜沾黏試驗 178
4.7.1 實際模擬烹飪試驗 178
4.7.2 熱熔膠沾黏試驗 188
伍、結論 194
陸、研究貢獻 198
柒、未來研究方向 199
參考文獻 200

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