本研究利用真空電弧熔煉法製備非等莫耳Al-Cr-Nb-Si-B-C之高熵合金靶材，再以反應式直流磁控濺鍍法鍍製高熵合金氮化物之薄膜(Al-Cr-Nb-Si-B-C)N。為達到薄膜性質的提升，藉由調整製程的氮氣流率、基板偏壓來控制薄膜成長之結構，目的是希望能提升其硬度、韌性、高溫抗氧化性及熱穩定性等，並探討薄膜的成長機制，以及不同鍍膜參數對於薄膜的微結構、機械性質、附著力、磨耗性質以及抗氧化能力之影響，最後針對不同的參數所得到結果進行綜合比較，再找出最佳化的薄膜，後續則以最佳參數之氮化物硬膜鍍覆於拋棄式三角銑刀上進行304不鏽鋼的切削測試。
由實驗結果發現，在不同氮氣流率 (RN) 的條件下，高熵合金膜及高熵氮化物薄膜之晶體結構皆呈現非晶的形態，然而，施加偏壓之後，從其截面的形貌觀察，有逐漸緻密化的趨勢，而當所施加基板偏壓 (Vs) 至-200 V時，其才有FCC晶體結構出現。在調變不同的參數變量後，當RN = 50% 及 Vs = -150V時，氮化物薄膜具有最高的硬度值23 GPa及最佳的抗氧化性，而由於在此參數下呈現非晶的結構，因此薄膜中的殘留應力不大，是因為在非晶的結構下可藉由混亂的原子排列使殘留應力得以舒緩。除此之外，相較於以往之高熵合金系統，抗氧化性質有顯著的突破，在1000°C/2h的退火後其氧化層厚度僅有79 nm，而此系統具有優異的抗氧化能力歸因於其表面由緻密的Cr2O3、Al2O3、SiO2及Nb2O5所組成的五層氧化層，可以有效的避免氧原子擴散進入薄膜當中。而在附著力試驗當中，不論鍍覆於M2工具鋼或是WC-Co基板上皆以Cr為中間層的附著力效果最佳。在切削試驗當中，對304不鏽鋼進行切削時，與工業上所使用的TiN及TiAlN鍍膜相比，縱使此系統的硬度不高於TiAlN，但在抗氧化性及附著力佳的貢獻下，其切削表現與TiAlN不相上下。由此可見，本研究所開發的高熵氮化膜 (Al-Cr-Nb-Si-B-C)N在工業應用上極具潛力。

High-entropy nitride films based on high-entropy alloys have received lots of attention. They have promising potential applications as compared to conventional nitride films. In the present study, high-entropy nitride films (AlCr1.5Nb0.5SiBC0.5)Nx were designed and deposited at 400°C on Si wafers by DC reactive magnetron sputtering in the gaseous mixture Ar+N2. By the systematic variation of nitrogen flow ratio (RN) and the substrate bias (Vs), microstructure, crystal structure, hardness and oxidation resistance have been investigated.
The results of GIAXRD indicate that the films of the different nitrogen flow ratio all exhibit an amorphous structure. Furthermore, with the increasing substrate bias, the crystal structure of the films converts to FCC structure gradually. In addition, the films possess denser microstructure and increasing hardness. The film of RN= 50% and Vs = -150 V has the highest hardness 22.5 GPa and Young’s modulus 193.5 GPa. Besides, the film displays excellent oxidation resistance. After the air annealing at 1000°C for 5h, the oxide layer is only 114 nm on the surface of the coating. The reason why it has such outstanding performance is because of its two amorphous layers and dense (Cr,Al)2O3 top layer in the oxidized 6-layer structure which effectively inhibits oxygen diffusion into the film.
In adhesion test, the optimized film is deposited on M2 and WC-Co substrates. The films with 100 nm Cr-interlayer present the best adhesion property. In the cutting test, the cutting tools coated with Cr-interlayer and optimized (Al-Cr-Nb-Si-B-C)N film perform better than commercial TiN-coated inserts but similar to TiAlN-coated ones. Though the hardness of (Al-Cr-Nb-Si-B-C)N is lower than TiAlN, the great oxidation resistance offsets the lower hardness. This research demonstrates the great potential of high-entropy (Al-Cr-Nb-Si-B-C)N coating for high temperature applications.

Abstract I
摘要 III
誌謝 V
目錄 IX
圖目錄 XV
表目錄 XXIII
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 6
2.1 表面鍍層的發展與研究 6
2.1.1 薄膜發展 6
2.1.2 薄膜硬化機制 13
2.1.3 氮化物硬膜發展 15
2.2 高熵合金的發展沿革 17
2.2.1 高熵合金定義 17
2.2.2 高熵合金的特點 17
2.2.3 高熵氮化膜 20
2.3 反應式直流磁控濺鍍 26
2.3.1 濺鍍原理 26
2.3.2 電漿理論 30
2.3.3 反應式濺鍍 (Reactive sputtering) 32
2.3.4 直流濺鍍 (Direct current sputtering) 33
2.3.5 磁控濺鍍 (Magnetron sputtering) 34
2.4 薄膜成長與微結構 37
2.4.1 薄膜成長機制 37
2.4.2 薄膜微結構 41
第三章、實驗步驟 46
3.1 實驗設計 46
3.2 靶材製備 48
3.3 薄膜製備 53
3.3.1 基板選擇 53
3.3.2 基板前處理 55
3.3.3 鍍製薄膜 55
3.4 薄膜基本性質分析 62
3.4.1 成分分析 62
3.4.2 晶體結構分析 63
3.4.3 表面形貌與微結構分析 63
3.4.4 鍵結分析 64
3.4.5 表面粗糙度分析 66
3.4.6 TEM微結構分析 68
3.5 電性分析 69
3.5.1 電阻率量測 69
3.6 機械性質分析 70
3.6.1 薄膜應力分析 70
3.6.2 硬度與楊氏係數分析 73
3.6.3 刮痕試驗 75
3.6.4 磨耗試驗 76
3.6.5 切削試驗 78
3.7 薄膜抗氧化性及熱穩定性分析 80
3.7.1 抗氧化性 80
3.7.2 熱穩定性 80
第四章、結果與討論 82
4.1 靶材結構與成分分析 82
4.2 氮氣流率變量 (RN) 對薄膜之影響 85
4.2.1 成分分析 85
4.2.2 晶體結構分析 87
4.2.3 鍍率分析 89
4.2.4 表面形貌與微結構分析 91
4.2.5 表面粗糙度分析 95
4.2.6 XPS鍵結分析 99
4.2.7 殘留應力分析 103
4.2.8 硬度及楊氏係數分析 106
4.2.9 電阻率分析 110
4.3 基板偏壓變量 (Vs)對薄膜之影響 111
4.3.1 成分分析 111
4.3.2 晶體結構分析 113
4.3.3 鍍率分析 116
4.3.4 表面形貌與微結構分析 118
4.3.5 表面粗糙度分析 122
4.3.6 XPS鍵結分析 126
4.3.7 殘留應力分析 128
4.3.8 硬度與楊氏係數分析 130
4.3.9 電阻率分析 134
4.4 (Al-Cr-Nb-Si-B-C)N之薄膜抗氧化性質分析-大氣退火 135
4.4.1 氮氣流率變量之薄膜抗氧化性分析 135
4.4.2 基板偏壓變量之薄膜抗氧化性分析 142
4.4.3 最佳參數 (Al-Cr-Nb-Si-B-C)N薄膜抗氧化性質 151
4.5 (Al-Cr-Nb-Si-B-C)N之薄膜熱穩定性質分析-真空退火 165
4.5.1 晶體結構分析 165
4.5.2 表面形貌與微結構分析 167
4.5.3 硬度與楊氏係數分析 169
4.6 最佳參數之氮化膜 (Al-Cr-Nb-Si-B-C)N附著力試驗 171
4.7 最佳參數之氮化膜 (Al-Cr-Nb-Si-B-C)N磨耗試驗 181
4.8 最佳參數之氮化膜 (Al-Cr-Nb-Si-B-C)N切削試驗 187
第五章、結論 194
第六章、本研究之貢獻 198
第七章、未來研究方向 199
第八章、參考文獻 200 

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