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研究生： 曾之藩
Zhi-fan Zeng
論文名稱： 氮化鉻銅奈米複合薄膜之耐蝕、抗菌與熱處理性質
The corrosion resistance, antibacterial and annealing properties of Cr-Cu-N nanocomposites thin films
指導教授： 王朝正
Chaur-jeng Wang
口試委員: 李志偉
Jyh-wei Lee
周賢鎧
Shyan-kay Jou
學位類別： 碩士
Master
系所名稱： 工程學院 - 機械工程系
Department of Mechanical Engineering
論文出版年： 2008
畢業學年度： 96
語文別： 中文
論文頁數： 100
中文關鍵詞： 脈衝直流磁控濺鍍 、腐蝕 、抗菌 、退火熱處理 、Cr-Cu-N奈米複合薄膜
外文關鍵詞： Cr-Cu-N nanocomposite thin films, magnetron sputtering pulsed DC reactive, corrosion, antibacterial, annealing
相關次數： 點閱：199  下載：3 
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    • 摘要
    氮化鉻薄膜具有高硬度、較佳耐磨耗性與抗腐蝕能力，因此已在
    模具產業中廣泛被使用；而在氮化鉻薄膜中加入適量的銅元素又可以
    有效提高薄膜之機械性質。本研究採用反應式雙極非對稱脈衝直流磁
    控濺鍍法沉積含銅量範圍自1.6 at.%到24.1 at.%之Cr-Cu-N 奈米複合
    薄膜，並分別進行機械性質測試、氯化鈉水溶液中之抗腐蝕性、抑制
    大腸桿菌能力及退火熱處理之性質的研究。Cr-Cu-N薄膜在硬度分析
    中，可發現到含銅量15.3at.%時，其硬度值可達到最高值。抑菌實驗
    發現薄膜消滅大腸桿菌的能力隨著銅含量的增加而提高，主要是由於
    足夠多的Cu離子釋出所致。Cr-Cu-N薄膜在NaCl水溶液中因大量的銅
    造成薄膜局部的腐蝕，隨著薄膜中銅含量增加其抗腐蝕性會明顯的降
    低。Cr-Cu-N薄膜經退火熱處理後，其表面會有氧化生成物的產生，
    生成物與其薄膜中的含銅量及退火的溫度有所關，薄膜硬度值也會受
    到銅含量以及退火溫度的影響而變化。

    The CrN coating had high hardness, low scratch coefficient and
    good antibacterial properties. Therefore, the CrN coatings have been used
    widely in the molding industrial. The addition of Cu into the CrN thin
    film will further improve the mechanical properties of coating effectively.
    In this work, the Cr-Cu-N nanocomposite thin films with Cu content
    ranging from 1.6 to 24.1 at.% have been deposited by a bipolar
    asymmetric pulsed DC reactive magnetron sputtering system. The
    mechanical properties, corrosion behavior and antibacterial test of
    Cr-Cu-N thin films with different Cu content were investigated. A
    combination of high hardness for the Cr-Cu-N coating containing 15.2
    at.%. It was observed that the antibacterial rate increased with the
    increasing Cu content in the coating, which was due to sufficient amount
    of Cu ions released. The corrosion resistance of Cr-Cu-N thin films is
    decreased as the Cu content increased in the NaCl aqueous solution. The
    copper oxide is produced on the surface of thin film after annealed. The
    hardness is also effected with different Cu contain and annealing
    temperature after annealed

    目錄 第一章 序論........................................................1 1.1前言.......................................................1 1.2研究動機與目的.......................................................2 第二章 文獻回顧.......................................................3 2.1氮化鉻薄膜特性.......................................................3 2.2氮化鉻銅奈米複合薄膜的特性.......................................................5 2.3薄膜抗菌研究.......................................................9 2.4薄膜電化學腐蝕......................................................12 第三章 實驗方法......................................................16 3.1實驗流程......................................................16 3.2鍍膜方法與步驟......................................................19 3.2.2基材試片處理......................................................19 3.2.3濺鍍薄膜步驟......................................................19 3.3.2表面及截面型態分析......................................................22 3.3.3晶相結構分析......................................................23 3.3.4硬度分析......................................................23 3.3.5殘留應力分析......................................................26 3.4 抑菌實驗分析......................................................26 3.5電化學腐蝕分析......................................................27 3.6退火改質實驗......................................................29 第四章 結果與討論......................................................31 4.1不同銅含量之Cr-Cu-N奈米複合薄膜性質分析......................................................31 4.1.1相及微結構分析......................................................31 4.1.1.2相分析......................................................34 4.1.1.3微結構分析......................................................36 4.1.2機械性質......................................................45 4.1.2.1硬度......................................................45 4.1.2.2殘留應力......................................................46 4.1.3 抑菌實驗分析 ...............................................47 4.1.4電化學腐蝕實驗...................................................... 51 4.2 Cr-Cu-N薄膜在不同溫度下退火處理後性質分析............................ 63 4.2.1晶相及微結構的分析.................................................. 64 4.2.1.1微結構分析........................................................ 64 4.2.1.1.2 450 ℃退火處理................................................. 67 4.2.1.1.3 500 ℃退火處理................................................. 70 4.2.1.2表面形貌分析...................................................... 73 4.2.1.3相及成分分析...................................................... 81 4.2.2硬度試驗............................................................ 88 第五章 結論.............................................................. 90 參考文獻................................................................. 92 圖目錄 圖2-1、CrN薄膜其氮氣流率與硬度關係圖......................................5 圖2-2、奈米複合薄膜之結構示意圖.......................................... .7 圖2-3、(a)Cr-Cu-N奈米複合薄膜的硬度與基材偏壓的關係(b) Cr-Cu-N奈米複合薄 膜的晶粒尺寸與基材加熱溫度的關係圖....................................... .7 圖2-4、Cr-Cu-N奈米複合薄膜的硬度與銅含量的關係........................... .7 圖2-5、Ta-Cu-N奈米複合薄膜的硬度與銅含量的關係........................... .8 圖2-6、Al-Cu-N複合薄膜截面圖............................................. .8 圖2-7、(○)Ti1-xAlxN與(□)Ti1-x-yAlxSiyN其晶粒尺度與硬度關係圖........... .9 圖2-8、Ti-Cu-N、Mo-Cu-N與Cr-Cu-N磨耗速率比較............................. .9 圖2-9、Ti-Cu-N薄膜抑菌實驗............................................... 11 圖2-10、Cr-Cu-N薄膜抑菌率結果............................................ 11 圖2-11、CrN與Cr2N動電位極化曲線圖........................................ 14 圖2-12、Ti-Al-N複合薄膜電化學腐蝕表面.................................... 14 圖2-13、TiN複合薄膜電化學腐蝕機制示意圖.................................. 15 圖3-1、鍍膜時靶材與試片位置示意圖........................................ 16 圖3-2、實驗流程圖........................................................ 17 圖3-3、脈衝直流磁控濺鍍機台.............................................. 18 圖3-4、脈衝直流磁控濺鍍機台腔體配置圖.................................... 18 圖3-5、Berkovich探針幾何形狀............................................. 25 圖3-6、典型加卸載曲線.................................................... 25 圖3-7、電化學實驗示意圖.................................................. 29 圖3-8、退火溫度示意圖.................................................... 30 圖4-1、鍍覆於矽基板之Cr-Cu-N薄膜元素比例圖............................... 33 圖4-2、鍍覆於矽晶片不同銅含量之Cr-Cu-N薄膜X光繞射圖...................... 35 圖4-3、鍍覆於矽晶片之Cr-Cu-N薄膜的晶粒尺度與銅含量關係圖................. 36 圖4-4、A1試片表面(a)二維及(b)三維形貌.................................... 37 圖4-5、A2試片表面(a)二維及(b)三維形貌.................................... 37 圖4-6、A3試片表面(a)二維及(b)三維形貌.................................... 38 圖4-7、A4試片表面(a)二維及(b)三維形貌.................................... 38 圖4-8、A5試片表面(a)二維及(b)三維形貌.................................... 39 圖4-9、A5試片表面(a)二維及(b)三維形貌.................................... 39 圖4-10、Cr-Cu-N薄膜表面粗糙度與銅含量關係圖.............................. 40 圖4-11、A1試片薄膜截面型態............................................... 42 圖4-12、A2試片薄膜截面型態............................................... 42 圖4-13、A3試片薄膜截面型態............................................... 43 圖4-14、A4試片薄膜截面型態............................................... 43 圖4-15、A5試片薄膜截面型態............................................... 44 圖4-16、A6試片薄膜截面型態............................................... 45 圖4-17、Cr-Cu-N硬度及彈性係數與銅含量關係圖.............................. 46 圖4-18、Cr-Cu-N薄膜殘留應力與銅靶功率關係圖.............................. 48 圖4-19、Cr-Cu-N薄膜菌落與抑菌率比較圖.................................... 50 圖4-20、A3試片於抑菌實驗後表面成分分析區域............................... 51 圖4-21、A1薄膜在0.89 wt.%NaCl水溶液中之開路電位曲線圖.................... 53 圖4-22、A2薄膜在0.89 wt.%NaCl水溶液中之開路電位曲線圖.................... 54 圖4-23、A3薄膜在0.89 wt.%NaCl水溶液中之開路電位曲線圖.................... 54 圖4-24、A4薄膜在0.89 wt.%NaCl水溶液中之開路電位曲線圖.................... 55 圖4-25、A5薄膜在0.89 wt.%NaCl水溶液中之開路電位曲線圖.................... 55 圖4-26、A6薄膜在0.89 wt.%NaCl水溶液中之開路電位曲線圖.................... 56 圖4-27、A1薄膜在0.89 wt.%NaCl水溶液中之動電位極化曲線圖.................. 56 圖4-28、A2薄膜在0.89 wt.%NaCl水溶液中之動電位極化曲線圖.................. 57 圖4-29、A3薄膜在0.89 wt.%NaCl水溶液中之動電位極化曲線圖.................. 57 圖4-30、A4薄膜在0.89 wt.%NaCl水溶液中之動電位極化曲線圖.................. 58 圖4-31、A5薄膜在0.89 wt.%NaCl水溶液中之動電位極化曲線圖.................. 58 圖4-32、A6薄膜在0.89 wt.%NaCl水溶液中之動電位極化曲線圖.................. 59 圖4-33、Cr-Cu-N薄膜在0.89 wt.%NaCl水溶液中之開路電位曲線圖............... 59 圖4-34、Cr-Cu-N薄膜在0.89 wt.%NaCl水溶液中之動電位極化曲線............... 60 圖4-35、Cr-Cu-N薄膜經電化學腐蝕後之表面形態，薄膜含銅量(a) 1.6 at.% (b) 5.3 at.% (c)10.2 at.%(d)15.6 at.%(e)22.1at.% (f)24.1 at.%................ 61 圖4-36、Cr-Cu-N薄膜腐蝕機制圖............................................ 62 圖4-37、A6試片於電化學腐蝕後表面成份分析區域............................. 63 圖4-38、CrCuN薄膜經400 ℃退火後表面形貌(a)試片A1，銅含量1.6 at.% (b)試片A2，銅含量5.3 at.% (c)試片A3，銅含量10.2 at.%(d)試片A6，銅 含量24.1 at.%............................................................ 65 圖4-39、CrCuN薄膜經400 ℃退火後薄膜截面形貌(a)試片A1，銅含量1.6 at.% (b)試片A2，銅含量5.3 at.% (c)試片A3，銅含量10.2 at.%(d)試片A6，銅 含量24.1 at.%............................................................ 66 圖4-40、CrCuN薄膜經450 ℃退火後表面形貌(a)試片A1，銅含量1.6 at.% (b)試片A2，銅含量5.3 at.% (c)試片A3，銅含量10.2 at.%(d)試片A6，銅含 量24.1 at.%.............................................................. 68 圖4-41、CrCuN薄膜經450 ℃退火後薄膜截面形貌(a)試片A1，銅含量1.6 at.% (b)試片A2，銅含量5.3 at.% (c)試片A3，銅含量10.2 at.%(d)試片A6，銅含量 24.1 at.%................................................................ 69 圖4-42、CrCuN薄膜經500 ℃退火後表面形貌(a)試片A1，銅含量1.6 at.% (b)試 片A2，銅含量5.3 at.% (c)試片A3，銅含量10.2 at.%(d)試片A6，銅含量 24.1 at.%................................................................ 71 圖4-43、CrCuN薄膜經500 ℃退火後薄膜截面形貌(a)試片A1，銅含量1.6 at.% (b)試片A2，銅含量5.3 at.% (c)試片A3，銅含量10.2 at.%(d)試片A6，銅含量 24.1 at.%................................................................ 72 圖4-44、A1試片經400 ℃退火後之表面(a)二維及(b)三維形貌................... 74 圖4-45、A2試片經400 ℃退火後之表面(a)二維及(b)三維形貌................... 74 圖4-46、A3試片經400 ℃退火後之表面(a)二維及(b)三維形貌................... 75 圖4-47、A6試片經400 ℃退火後之表面(a)二維及(b)三維形貌................... 75 圖4-48、A1試片經450 ℃退火後之表面(a)二維及(b)三維形貌................... 76 圖4-50、A3試片經450 ℃退火後之表面(a)二維及(b)三維形貌................... 77 圖4-51、A6試片經450 ℃退火後之表面(a)二維及(b)三維形貌................... 77 圖4-52、A1試片經500 ℃退火後之表面(a)二維及(b)三維形貌................... 78 圖4-53、A2試片經500 ℃退火後之表面(a)二維及(b)三維形貌................... 78 圖4-54、A3試片經500 ℃退火後之表面(a)二維及(b)三維形貌................... 79 圖4-55、A6試片經500 ℃退火後之表面(a)二維及(b)三維形貌................... 79 圖4-56、Cr-Cu-N薄膜經退火處理後表面粗糙度與退火溫度、銅含量關係圖........ 80 圖4-57、Cr-Cu-N經400 ℃退火處理之X光繞射圖............................... 82 圖4-58、Cr-Cu-N經450 ℃退火處理之X光繞射圖............................... 83 圖4-59、Cr-Cu-N經500 ℃退火處理之X光繞射圖............................... 84 圖4-60、A3試片經450 ℃退火處理後表面成分分析區域......................... 85 圖4-61、A6試片經450 ℃退火處理後表面成分分析區域......................... 86 圖4-62、A6試片經500 ℃退火處理後表面成分分析區域......................... 87 圖4-63、Cr-Cu-N薄膜經退火處理後硬度與銅含量關係圖........................ 89 表目錄 表3-1、脈衝頻率參數表.................................................... 21 表3-2、濺鍍參數.......................................................... 22 表4-1、Cr-Cu-N奈米複合薄膜元素定量分析表................................. 32 表4-2、Cr-Cu-N奈米複合薄膜氮化鉻與銅之體積比例表.........................32 表4-3、Cr-Cu-N薄膜平均粗糙度與最大粗糙度................................. 40 表4-4、CrCuN薄膜之抑菌率................................................. 50 表4-5、抑菌實驗後A4試片表面成分分析...................................... 51 表4-6、CrCuN薄膜在0.89 wt.%NaCl抗腐蝕量測結果參數........................ 60 表4-7、電化學腐蝕實驗過後A6試片鍍膜表面成分分............................ 63 表4-8、Cr-Cu-N薄膜經退火處理後之表面平均粗糙度值......................... 80 表4-9、450 ℃退火處理後A3試片表面成分分析................................ 85 表4-10、450 ℃退火處理後A6試片表面成分分析............................... 86 表4-11、500 ℃退火處理後A6試片表面成分分析............................... 87

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