臺灣博碩士論文加值系統

本研究分為兩階段，並採用陰極電弧蒸鍍系統(Cathode Arc Evaporation, CAE)鍍製鋁鈦氧薄膜，鍍膜後再施以電漿氧化處理，預期可以強化薄膜，並在表面產生一層Al2O3與TiO2相，其目的在增強薄膜的抗高溫氧化與耐蝕性。第一階段改變鋁鈦氧薄膜製程的時間(15s、30s、60s)鍍膜後再施以氧電漿處理600V，並以ZrN薄膜做為對照組，探討薄膜的微結構、表面型貌、機械性質是否會有所變化。第二階段利用鋁鈦氧薄膜(60s)鍍後施以不同功率(400W、800W、1200W)之氧電漿處理，並以未使用氧電漿之鋁鈦氧薄膜做比對，並以SEM、 XRD等儀器做微結構分析，觀察其斷面、膜層厚度、表面型態、 結晶相。物理性質分析使用色度計分析彩度並比較改變鋁鈦氧薄膜的製程時間與不同功率的電漿技術處理之顏色差異度。化學性質使用ESCA、腐蝕電化學；機械性質使用奈米壓痕、磨耗 試驗等。
第一階研究結果顯示，隨著鋁鈦氧薄膜製程時間的增加，鋁鈦氧薄膜的色澤會導致試片本身由金黃色變化為紫紅色，薄膜表面產生許多白色的團聚物，而薄膜厚度差異不大，從XRD與XPS分析顯示，鋁鈦氧薄膜是含Al2O3與TiO2微晶的非晶結構組成。
第二階研究結果顯示，改變氧電漿的能量確實可以減少表面微粒的產生，從SEM與表面粗度儀分析顯示氧電漿的功率越大，表面粗度越小，從XRD與XPS分析顯示，鋁鈦氧薄膜是Al2O3與TiO2的非晶結構組成，氧電漿功率的改變無法造成薄膜結構上的改變，磨耗試驗中，改變氧電漿功率確實可以降低摩擦係數至0.6-0.5之間，從TGA分析中氧電漿功率的增加可以提高耐高溫氧化行為。

The study focused on the AlTiOx thin films deposited by cathode arc evaporation plasma deposition, and then the as-deposited films were subjected to plasma oxidation treatment. We expected to strengthen the properties of the films and to obtain the surface layer of Al2O3 and TiO2 phase. Zirconium nitride (ZrN) as the reference coating, our research expected the characterization of the ZrN coating could be enhanced when the structure composed of the ZrN and AlTiOx thin film in field of high-temperature oxidation and corrosion resistance properties. The process is thus designed for enhancing the film's high temperature oxidation and corrosion resistance. The optical, chemical composition, microstructure and mechanical properties, including wear resistance and anti-oxidation at high temperature, were investigated by using scanning electron microscopy (SEM), X-ray photo-electron spectroscopy (XPS), X-ray diffraction (XRD), (TGA) and nano-indentation. There are two parts in this study. In Part 1, on top of the ZrN coating, the aluminum-titanium oxide, denoted AlTiOx, has been grown via cathode arc evaporation plasma deposition method (CAE) with various depositional time 15 s, 30 s and 60 s, and then subjected to post deposition treatment by plasma oxidation treatment (with bias voltages 600V). Experimental results indicate that the optical, chemical composition, microstructure, and mechanical properties, but not include the thickness, heavily depend on the depositional time. By changing the time, AlTiOx film turned the gold colour into carmine. The chemical composition and microstructure properties of the AlTiOx coatings were strongly influenced by the noncrystal structure composed of Al2O3 and TiO2. The oxidation behavior exams showed the coatings have a well high-temperature oxidation resistance.
In Part 2, the AlTiOx coatings were deposited with different target input power (400 W, 800 W and 1200 W), and compared the microstucture, surface morphology and mechanical properties with the as-deposited AlTiOx. Experimental results indicate that the optical, chemical composition, microstructure, and mechanical properties, but not include the thickness, heavily depend on the depositional time. By changing the time, AlTiOx film turned the gold colour into carmine. The chemical composition and microstructure properties of the AlTiOx coatings were strongly influenced by the noncrystal structure composed of Al2O3 and TiO2. The oxidation behavior exams showed the coatings have a well high-temperature oxidation resistance.

Abstract II
總目錄 VI
圖目錄 IX
表目錄 XII
第一章 前言 1
第二章 文獻回顧 4
2-1陰極電弧沉積技術與原理 4
2-2裝飾鍍 6
2-3 ZrN薄膜[16-32] 9
2-4 AlTiN、AlTiN-O 薄膜 11
2-5 ( Al、La、Ti、Cr)Ox 13
2-6電漿技術處理 [41-43] 15
2-7彩度、明度[44-46] 18
第三章 實驗方法 22
3-1鍍膜系統 22
3-2試片前處理 24
3-3膜層設計與製程參數 26
3-4實驗流程圖 29
3-5實驗分析方法 30
3-5-1 場發射掃描式電子顯微鏡（Field Emission Scanning Electronic Microscope，FE-SEM） 30
3-5-2 能量散佈光譜儀（Energy Dispersive Spectrometer，EDS）【47】 32
3-5-3 XRD（X-ray diffract meter） 34
3-5-4 磨耗分析 36
3-5-5 奈米壓痕試驗 38
3-5-6 腐蝕試驗[48-49] 40
3-5-7 化學電子光譜儀分析（Electron Spectroscopy for Chemical Analysis ESCA） 44
3-5-8熱重/熱差分析( TGA / DSC )【50】 45
3.5.9分光色差儀 47
第四章 結果與討論 48
4-1氧電漿600V下對鋁鈦氧薄膜不同製程時間之影響 49
4-1-1 SEM形貌分析 49
4-1-2 SEM膜厚量測 52
4-1-3 EDS 54
4-1-4 X-ray繞射分析 57
4-1-5 XPS 59
4-1-6縱深分析 63
4-1-7奈米壓痕 65
4-1-8磨耗試驗 67
4-1-9分光色差值 71
4-1-10腐蝕試驗 74
4-2不同氧電漿功率對鋁鈦氧薄膜之影響 76
4-2-1 SEM形貌分析 76
4-2-2 SEM膜厚量測 79
4-2-3 EDS 81
4-2-4 X-ray繞射分析 83
4-2-5 XPS 85
4-2-6縱深分析 89
4-2-7磨耗試驗 90
4-2-8分光色差值 93
4-2-9水接觸角 97
4-2-10耐久度測試 98
4-2-11腐蝕試驗 102
4-2-12 TGA 熱重分析試驗 104
4-3鍍厚之鋁鈦氧薄膜應用端 109
4-3-1 鋁鈦氧薄膜XRD 109
4-3-2 4.3.2增加AlTi-O薄膜之厚度，並實際應用於玻璃壓鑄模具 110
第五章 結論 111
參考文獻 113

[1] Y.Y. Guu, J.F. Lin, C.F. Ai, The tribological characteristics of titanium nitride, titanium carbonitride and titanium carbide coatings ,Thin Solid Films 302 (1997) 193–200.
[2] R.L. Boxman, P.J. Martı′n, D.M. Sandaers (Eds.), Handbook of Vacuum Arc Science and Technology, Noyes Publications, 1995.
[3] R. Miyano, K. Kimura, K. Izumi, H. Takikawa, T. Sakakibara, Preparation of metal nitride and oxide thin films using shielded reactive vacuum arc deposition ,Vacuum 59 (2000) 159.
[4]E. Budke *, J. Krempel-Hesse, H. Maidhof, H. Schu, 63450 Hanau, Decorative hard coatings with improved corrosion resistance, Surface and Coatings Technology 112 (1999) 108–113.
[5] R.L. Boxman, P.J. Martin, D.M. Sanders (Eds.), Handbook of Vacuum Arc Science and Technology, Noyes, 1995.
[6] S. Ramalingam, C.B. Qi, K. Kim, US Patent 4,673,477 (1987).
[7] P.D. Swift, J. Phys. D: Appl. Phys. 29 (1996) 2025.
[8] A.I. Vasin, A.M. Dorodnov, V.A. Petrosov, Sov. Tech. Phys. Lett. 5 (1979) 634.
[9] M. Ellrodt, H. Mecke, Surf. Coat. Technol. 74y75 (1995) 241.
[10] K. Kimura, H. Takikawa, T. Sakakibara, Appl. Plasma Sci. 7 (1999) 3, win Japanesex.
[11] I.I. Aksenov, V.A. Belous, V.G. Padalka, V.M. Khoroshikh, Sov. J. Plasma Phys. 4 (1978) 425.
[12] R.L. Boxman, Z. Zhitomirsky, B. Altertop, E. Gidalevich, I. Beilis, M. Keidar, et al., Surf. Coat. Technol. 86y87 (1996) 243.
[13]Raymond Constantin *, Rue Louis-Chevrolet 19, CH 2301 La Chaux de Fonds, France.
[14]Ph. Roquiny *, F. Bodart, G. Terwagne Laboratoire d’Analyses par Reactions Nucleaires, Faculte′s
[15]S. Niyomsoan, W. Grant, D.L. Olson, B. Mishra, Variation of color in titanium and zirconium nitride decorative thin films , Thin Solid Films 415 (2002) 187–194.
[16] C.P. Constable, J. Yarwood, W.D. Mu‥nz, Surf. Coat. Technol. 116 (1999) 155.
[17] W.D. Sproul, Very high rate reactive sputtering of TiN, ZrN and HfN ,Thin Solid Films 107 (1983) 141.
[18] P. Panjan, B. Navinsˇek, A. Cvelbar, A. Zalar, I. Milosˇev, Thin Solid Films 298 (1996) 281.
[19] P. Honer, R. Sanjines, F. Levy, Surf. Coat. Technol. 94/95 (1997) 398.
[20] J.W. Lim, J.S. Park, S.W. Kang, J. Appl. Phys. 87 (9) (2000) 4632.
[21] J. Vetter, R. Rochotzki, Thin Solid Films 192 (1990) 253.
[22] W.D. Sproul, J. Vac. Sci. Technol. A 4 (6) (1986) 2874.
[23] S. Kanamori, Thin Solid Films 136 (1986) 195.
[24] K. Hinode, Y. Homma, M. Horiuchi, T. Takhashi, J. Vac. Sci. Technol. A 15 (4) (1997) 2017.
[25] B. Karlsson, R.P. Shimshock, B.O. Serphin, Phys. Scr. 25 (1982) 775.
[26] C.G. Ribbing, A. Roos, SPIE 3133 (1997) 148.
[27] A. Mumtaz, W.H. Class, J. Vac. Sci. Technol. 20 (3) (1982) 345.
[28] M. Nose, T. Nagae, M. Yokota, S. Saji, M. Zhou, M. Nakada, Surf. Coat. Technol. 116–119 (1999) 117.
[29] I. Milosev, H.H. Strehblow, B. Navinsel, Thin Solid Films 303 (1997) 246.
[30] H. Yanagisawa, K. Sasaki, H. Miyake, Y. Abe, Jpn. J. Appl. Phys. 39 (2000) 5987.
[31] M.B. Takeyama, A. Noya, K. Sakanishi, J. Vac. Sci. Technol., B 18 (2000)1333.
[32] D. Pillouda, J.F. Pierson, A. Cavaleiro, M.C. Marco de Lucas, Thin Solid Films 492 (2005) 180.
[33] E.W. Niu, L. Li, G.H. Lv, H. Chen, W.R. Feng, S.H. Fan, S.Z. Yang, X.Z. Yang, Materials Science and Engineering A 460–461 (2007) 135–139.
[34] Yan Liu,Yunshan Dong, Wenji Zhao, Geyang Li.，Microstructure and mechanical properties of (Al, Ti)(O,N)coatings prepared by reactive sputtering.
[35] K. To‥nshoff, B. Karpuschewski, A. Mohlfeld , T. Leyendecker, G. Erkens, H.G. Fußb, R. Wenke.，Performance of oxygen-rich TiALON coatings in dry cutting applications.
[36]薛旭宏，陰極電弧蒸鍍沉積高硬質薄膜AlTiON薄膜特性研究，明道大學碩士論文(2008).
[37]B.Navinsek,P.Panjan,I.Milosev,Industrial applications of CrN(PVD) coatings, deposited at high and low temperatures, Surface and Coatings Technology, 97(1997)182.
[38]楊淙顯 反應性氧氣對陰極電弧沉積AlTiN/CrN奈米級多層薄膜製程與特性之影響 明道大學碩士論文(2009).
[39]詹慕萱 陰極電弧沉積二氧化鈦多層膜之製程與特性研究 明道大學碩士論文(2006).
[40]V. Mikhelashvili *, G. Eisenstein, Thin Solid Films 515 (2006) 346 – 352.
[41]簡昭欣、呂正傑 氧電漿處理對BST高介電薄膜的影響 國家毫微米元件實驗室.
[42]陳宣克 電子束微影製作三維非平面微結構及結構表面改質 國立中央大學.
[43] W.Petasch, B.Kegel, H.Schmid,K.Lendenmann,H.U.Keller, Surface and Coating Technology 97(1997) 176-181.
[44] American Society for Testing Materials, Symposium on Color,ASTM, Philadelphia, PA, 1941, p. 3.
[45]色彩理論與數位影像 鄭柏左 新文京開發出版有限公司.
[46]圖解色彩管理的實踐 MD 研究會.
[47]www.elearning.stut.edu.tw/caster/3/no7/7-2.htm.
[48]楊聰仁，腐蝕電化學分析，材料基礎實驗(二)腐蝕電化學實驗 3.
[49]N.G.Fontana, N.D.Greene, Corrosion Engineering, 3rd edition, McGraw-Hill, (1986).
[50]NCKU Micro-Nano Technology Center&Southern Region MEMS Center.
[51] JCPDF card #895269.
[52]H. Jiménez, E. Restrepo, A. Devia, Thin Solid Films 502 (2006) 188 – 192.
[53]D.F. Arias, Y.C. Arango, A. Devia, Applied Surface Science 253 (2006) 1683–1690.
[54] 成霖企業股份有限公司.
[55]Youngsoo Kim, Beom Jin Yoo, R. Vittal , Yeonhee Lee ,Nam-Gyu Park, Kang-Jin Kim, Journal of Power Sources 175 (2008) 914–919.
[56] JCPDF card #897716