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研究生： 楊佩宜
Yang, Pei-I
論文名稱： 以反應式直流磁控濺鍍法製備高熵彩色薄膜之研究
Study on High-entropy Color Films Produced by DC Reactive Magnetron Sputtering
指導教授： 葉均蔚
Yeh, Jien-Wei
口試委員: 李紫原
洪健龍
曹春暉
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年： 2019
畢業學年度： 107
語文別： 中文
論文頁數： 245
中文關鍵詞： 反應式直流磁控濺鍍法 、高熵合金 、彩色薄膜 、材料科學
外文關鍵詞： High-entropy alloy, Color Films, DC Reactive Magnetron Sputtering, Material science
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    • 本研究利用真空電弧熔煉製作兩種非等莫耳比的靶材，並透過反應式直流磁控濺鍍機鍍製彩色薄膜。透過調整合金膜、氮化膜及氧化膜的厚度，以及氧氣流率的變量，來觀察兩種靶材產生的顏色變化，包含顏色的轉變過程及探討顏色容忍區間，並透過調整基板溫度及基板偏壓，期望達到更高硬度及耐刮的彩色鍍膜。
    整體而言，本研究之彩色薄膜的晶體結構為非晶，表面粗糙度為 2 nm，為粗糙度小且平滑之表面。而機械性質的部分，合金膜最佳硬度為10 GPa，氮化膜為17 GPa，而氧化膜則為11 GPa。並進行HRC附著性實驗，薄膜皆落在優良的 HF 1 及 HF 2 等級。同時也對彩色薄膜進行鹽水浸泡實驗，發現薄膜在兩個禮拜後皆無剝落情形，顯示其擁有優秀的耐蝕性。此外，彩色薄膜的抗菌實驗亦顯示大腸桿菌及金黃色葡萄球菌的抗菌值分別大於 4.6 及 4.2，抗菌率大於 99.99%，歸因於銅元素及非晶結構的共同效果使薄膜擁有優良的抗菌能力。
    本研究鍍製之彩色薄膜，未來有潛力應用於裝飾性鍍膜，包括手機外殼及各種配件，同時擁有優異光滑性、耐刮性、耐蝕性及抗菌性。

    In this study, two alloy targets were prepared by vacuum arc melting, and color films were deposited by reactive direct current magnetron sputtering. By adjusting the thickness of metal film, nitride film and oxide film, as well as the flow of oxygen, the color change and the width of the color tolerance are investigated. By the adjustment of deposition temperature and negative bias voltage, these color films could perform higher hardness and anti-scratch properties.
    The experimental results revealed that these color films exhibited an amorphous structure, and their roughness values were about 2 nm, which represented that these color films had smooth and small-roughness surface. As for its mechanical properties, the highest hardness of the metal film was 10 GPa, 17 GPa for nitride film and 11 GPa for oxide film, resepectively. These color films also exhibited great HF 1 and HF 2 grades in HRC adhesion test. Meanwhile, these color films had no chemical attack after immersing in 5% NaCl solution for two weeks, showing its great corrosion resistance. In the antibacterial test, both films showed high antibacterial activity values as 4.6 and 4.2 to E. coli and S. aureus, respectively. The high antibacterial ability which was above 99.99% could be attributed to the addition of copper and its amorphous structure.
    This research demonstrates that the high-entropy color films have great potential for the application of decorating films, such as smartphone 3C cases and various accessories, exhibiting smooth surface, anti-scratch property, high corrosion resistance and great antibacterial ability.

    誌謝 I 摘要 IV Abstract V 目錄 VII 圖目錄 XII 表目錄 XXII 壹、 前言 1 貳、 文獻回顧 3 2.1薄膜鍍製技術 3 2.1.1物理氣相沉積 3 2.1.2 濺鍍原理 4 2.1.3 反應式濺鍍 5 2.1.4 直流濺鍍 7 2.1.5 磁控濺鍍 8 2.1.6 薄膜沉積與附著機制 11 2.1.7 薄膜微結構 12 2.2 薄膜的發展與種類 18 2.2.1 薄膜發展概況 18 2.2.2 薄膜分類與介紹 20 2.2.3 薄膜硬化機制 30 2.3高熵合金的沿革 31 2.3.1 高熵合金之源起 31 2.3.2 高熵合金定義 32 2.3.3 高熵合金特點 35 2.4 彩色薄膜之原理 38 參、 實驗流程 45 3.1 實驗設計 45 3.2 靶材製作 47 3.3 薄膜準備 49 3.3.1 基板準備 49 3.3.2 薄膜鍍製 50 3.4 薄膜基本性質分析 67 3.4.1 成份分析 67 3.4.2 晶體結構分析 69 3.4.3 微結構分析 69 3.4.4 表面粗糙度分析 70 3.5 薄膜機械性質分析 71 3.5.1 硬度和楊氏模數分析 71 3.5.2 薄膜附著性分析 74 3.6 薄膜其他性質分析 77 3.6.1 薄膜顏色分析 77 3.6.2 鹽水耐蝕性分析 77 3.6.3 抗菌分析 78 肆、 結果與討論 80 4.1 高熵靶材-1 80 4.1.1 單層膜性質 80 4.1.1.1 鍍率分析 80 4.1.1.2 成分分析 82 4.1.1.3 晶體結構分析 84 4.1.1.4 表面形貌與截面形貌分析 86 4.1.1.5 硬度與楊氏模數分析 88 4.1.1.6 表面粗糙度分析 90 4.1.2 鍍層結構的發色性質 93 4.1.2.1 合金層厚度對彩色薄膜之影響 93 4.1.2.2 氮化層厚度對彩色薄膜之影響 100 4.1.2.3 氧化層厚度對彩色薄膜之影響 108 4.1.2.4 氧氣流率對彩色薄膜之影響 125 4.1.3 附著性分析 132 4.1.3.1 膠帶實驗 132 4.1.3.2 HRC附著性實驗 134 4.1.4 鹽水耐蝕性分析 140 4.1.5 抗菌分析 145 4.2 高熵靶材-2 147 4.2.1 單層膜性質 147 4.2.1.1 鍍率分析 147 4.2.1.2 成分分析 149 4.2.1.3 晶體結構分析 151 4.2.1.4 表面形貌與截面形貌分析 153 4.2.1.5 硬度與楊氏模數分析 155 4.2.1.6 表面粗糙度分析 162 4.2.2 鍍層結構的發色性質 165 4.2.2.1 合金層厚度對彩色薄膜之影響 165 4.2.2.2 氮化層厚度對彩色薄膜之影響 172 4.2.2.3 氧化層厚度對彩色薄膜之影響 180 4.2.2.4 氧氣流率對彩色薄膜之影響 200 4.2.3 附著性分析 207 4.2.3.1 膠帶實驗 207 4.2.3.2 HRC附著性實驗 211 4.2.4 鹽水耐蝕性分析 218 4.2.5 抗菌分析 229 4.3 彩色鍍膜成果展示 231 伍、 結論 234 陸、 本研究之貢獻 236 柒、 未來研究方向 237 參考文獻 238

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