臺灣博碩士論文加值系統

鎳磷合金薄膜具有良好的機械性質、抗腐蝕性以及耐磨耗等特性，並廣泛地
運用在工業用途上。經由適當的處理，性質會因為鎳以及鎳磷的化合物析出而得
到強化，相對的，過度的熱處理會造成晶粒成長，而使得機械性質下降，因此，
如何提升鎳磷合金薄膜的熱穩定性及機械強度為重要的課題之一。
在本研究當中，以鎳磷合金與釕金屬靶材搭配磁控濺鍍技術，將第三元素釕
添加於二元鎳磷基膜層中，使其成為三元Ni-Ru-P 鍍層，藉此探討鎳釕磷三元合
金膜層之熱穩定性、機械性質及特性變化。經由濺鍍時靶材輸出功率的變化，成
功地將鎳釕磷合金薄膜中之釕含量控制在3.3 至64.6 at.%之間。藉由相鑑定分析
可得知鎳磷的相轉變溫度會因第三元素的添加延緩至500oC，同時，添加超過52.7
at.% 釕含量的鍍膜，在初鍍狀態就可發現結晶相Ni + Ru +Ru2P 的生成。同時，
透過薄膜表面形貌之觀察，可發現不同釕含量之三元鎳釕磷薄膜具有不同的微結
構。在機械性質方面，硬度值隨釕含量的增加而隨之增加，並且在釕含量添加超
過 52.7 at.%時，有了最大的10.4 GPa 之硬度值，在氧化測試中，也具有良好之
抗氧化性，使表面氧化深度小於20 nm。並且此三元鎳釕磷合金材料能有效改善
抗腐蝕性，但由於退火過程後晶界的生成導致抗腐蝕性下降。本論文亦研究與分
析Ni-Ru、Ni-Ru-P 與Ni-P-X 系統間之差異，會將不同薄膜系統間之微結構、特
性作一深入討論。

In the study, the ternary Ni-Ru-P alloy coatings are fabricated by magnetron
dual-gun co-sputtering technique. The chemical composition variation of the coatings in terms of sputtering parameters, including input power, process temperatures and Ar gas flow rate are investigated. The Ni-Ru-P coatings with a Ru content <38.9 at.% remain an amorphous/nanocrystalline feature under a vacuum annealing temperature up to 500oC. On the other hand, Ni(Ru) and Ni-P precipitation phases form as annealing temperature is raised to 550oC. With Ru content >52.7 at.%, the as-fabricated Ni-Ru-P coating shows crystallized Ni + Ru + Ru2P mixed phases. Such phase distribution for high Ru-content ternary Ni-Ru-P is stable under annealing temperature up to 600oC. The crystallized Ni + Ru + Ru2P phases are also responsible for the slight increase in surface roughness. The hardness for low Ru contents as-deposited films distributed around 7.2 to 8.1 GPa. The coatings with crystallized Ru and Ru2P phases possess a higher hardness value of 10.4 GPa. Limited oxide penetration less than 20 nm at Ni29.5Ru64.6P5.9 coating surface is confirmed. The Ni + Ru + Ru2P phases distribution resulted from high content Ru co-sputtering is beneficial to oxidation resistance. The introduction of high Ru concentration significantly strengthens the mechanical and anti-oxidation behaviors of Ni-P-based coating. The Ru can improve the corrosion resistance of binary Ni-P coating from the electrochemical analysis. The effect of W, Al and Ru elements in Ni-P-based coating on their mechanical properties and characteristics are discussed.

Contents
Contents ................................................................I
Table List ……………………………………………………………………………VI
Figure Caption ………………………………………………………………………IX
Abstract ……………………………………………………………………………XIX
Chapter 1 Introduction ……………………………………….1
1.1 Background ………………………………………………………………………1
1.2 Coating Material Systems ……………………………………………….………1
1.3 Characteristic and Application of Ni-P-based Coating ………………………..2
1.4 Critical Issues …………………………………………………………………….2
1.5 Objectives ………………………………………………………………………...3
Chapter 2 Literature Review ………………………………...5
2.1 Surface Engineering ……………………………………………………………..5
2.1.1 Surface Treatments ………………………………………………………...5
2.1.2 Surface Coatings …………………………………………………………...6
2.2 Sputtering Technique ……………………………………………………………7
2.2.1 Sputtering ………………………………………………………………….7
2.2.2 Magnetron Sputtering ……………………………………………………...8
2.2.3Co-sputtering ……………………………………………………………….8
2.3 Binary Ni-P Deposits …………………………………………………………….9
2.3.1 Fabrication Methods of Ni-P Deposits …………………………….………9
2.3.2 Microstructure and Phase Characteristics …………………………………9
2.3.3 Mechanical Properties ……………………………………………………..9
2.3.4 Corrosion Behavior ………………………………………………………10
2.4 Ni-P-based Coating ……………………………………………………………..10
2.4.1Ternary Ni-P-X Alloy Coating ……………………………………………10
2.4.1.1 Ni-W-P ………………………………………………………….………11
2.4.1.2 Ni-Al-P …………………………………………………………………12
2.4.2 Ni-P-ceramics Coating …………………………………………………...13
2.4.2.1 Ni-P-Al2O3 ……………………………………………………………..14
2.4.2.2 Ni-P-CNT ………………………………………………………………15

Chapter 3 Experimental Procedures ……………………….35
3.1 Sputtering Deposition of Alloy Thin Films ……………………………………35
3.2 Heat Treatment Process ………………………………………………………..37
3.3 Measurements and Analysis …………………………………………………...37
3.3.1 Composition Analysis …………………………………………………….37
3.3.2 Phase Identification and Microstructure Investigation …………………...38
3.3.3 Mechanical Evaluation …………………………………………………...38
3.3.4 Surface Roughness Measurement ………………………………………..39
3.3.5 Oxidation Test …………………………………………………………….40
3.3.6 Electrochemical Test ……………………………………………………...41

Chapter 4 Results and Discussion ………………………….53
4.1 Composition Evaluation of Coatings ………………………………………….53
4.2 Microstructure Evaluation and Phase Identification ………………………...55
4.2.1 Effect of Input Powers and post annealing treatment ……………………55
4.2.2 Phase distribution of ternary Ni-Ru-P coatings …………………………..59
4.3Morphological Characteristics of Coatings …………………………………...61
4.3.1 Effect of Composition ……………………………………………………61
4.3.2 Effect of Post Annealing Treatment ……………………………………...62
4.3.3 Effect of Substrate Deposition Temperatures …………………………….65
4.4 Mechanical Properties Evaluation …………………………………………….65
4.4.1 Effect of Composition ……………………………………………………66
4.4.2 Effect of Annealing Treatment …………………………………………...67
4.4.3 Effect of Substrate Deposition Temperatures …………………………….69
4.5 Oxidation Behavior Investigation ……………………………………………..70
4.6 Corrosion Behaviors ……………………………………………………………72
4.6.1 Effect of Composition ……………………………………………………72
4.6.2 Effect of Post Annealing Treatment and process heating ………………...75
4.6.3 Equivalent Circuit Models ………………………………………………..78
4.6.4 Corrosion surface observation ……………………………………………79
4.7 Comparison in Ni-Ru-P and Ni-Ru Coatings …………………………………80
4.7.1 Composition of Ni-Ru Coatings ………………………………………….80
4.7.2 Surface Morphology and Hardness Evaluation …………………………..80
4.7.3 Corrosion Behavior of Ni-based Coatings ……………………………….81
4.8 Comparison in Ni-W-P, Ni-Al-P and Ni-Ru-P Deposits ……………………...82
4.8.1 Composition of Ni-P-based Coatings …………………………………….82
4.8.2 Crystallization Behavior of Sputtered Ni-P-based deposits ……………...83
4.8.3 Surface Morphology and Hardness Evaluation …………………………..86
4.8.4 Oxidation Properties Test ………………………………………………...87
4.8.5 Corrosion Behavior of Ternary Ni-P-based Coatings …………………….88

Chapter 5 Conclusions ……………………………………..187

References …………………………………………………..190
Appendixes …………………………………………………195

References
[1] D. S. Rickerby and A. Matthews, Advanced Surface Coatings: a handbook of
surface engineering, Glasgow, Blackie, (1991).
[2] Y. Chiba, T. Omura, H. Ichimura, J. Mater. Res. 8 (1993) 1109.
[3] H. Hellock, J. Vac. Sci. Technol. A4 (6) (1986) 2661.
[4] R. Behrisch (ed.), Sputtering by Particle bombardment. Springer (1981), Berlin.
[5] P. Sigmund, Nucl. Instr. Meth. Phys. Res. B. "Mechanisms and theory of physical
sputtering by particle impact". Nuclear Instruments and Methods in Physics Research
Section B Beam Interactions with Materials and Atoms (1987).
[6] R. Behrisch and W. Eckstein (eds.), Sputtering by Particle bombardment:
Experiments and Computer Calculations from Threshold to Mev Energies, Springer
(2007) Berlin.
[7] Aleksandras Iljinas, Darius Milcˇius, Julius Dudonis, Vacuum 81 (2007) 1213.
[8] H. K. Kim, T. Y. Seong, Y. S. Yoon, Journal of Power Sources 112 (2002) 67.
[9] Z.G. Li, S. Miyake, M. Kumagai, H. Saito, Y. Muramatsu, Surf. Coat. Technol.
183 (2004) 62.
[10] Daniel Nilsson, Fredrik Svahn, Urban Wiklund, Sture Hogmark, Wear 254 (2003)
1084.
[11] G.O. Mallory, J.B. Hajdu (Eds.),Electroless Plating: Fundamentals and
Applications, AESF Publishing, Orlando, FL, 1990, p.261.
[12] P. Nash, Phase Diagrams of Binary Nickel Alloys, ASM International, June (1991)
235.
[13] R.C. Agarwala, S. Ray, Zeitschrift fur Metallkunde, 79 (1988) 472.
[14] R. C. Agarwala and S. Ray, "Variation of Structure in Electroless Ni-P Films with
Phosphorus Content", Z. Metallkunde, 79 (1988) 472.
[15] Jiann-Shiung Chen, Jenq-Gong Duh, Fan-Bean Wu, Surf. Coat. Technol. 150
(2002) 239.
[16] J. A. Sue and T. P. Chang, Surf. Coat. Technol. 76-77 (1995) 61.
[17] G. Lu, G. Zangari, Electrochimica Acta 47 (2002) 2969.
190
[18] Y.Y. Tsai, F.B. Wu, Y.I. Chen, P.J. Peng, J.G. Duh, S.Y. Tsaic, Surf. Coat. Technol.
146 –147 (2001) 502.
[19] J.A. Sue, T.P. Chang, Surf. Coat. Technol. 76–77 (1995) 61.
[20] F.B. Wu, S.K. Tien, Y.Z. Tsai, J.G. Duh, Thin Solid Films 494 (2006) 151.
[21] F.B. Wu, Y.M. Su, Y.Z. Tsai, J.G. Duh, Surf. Coat. Technol. 202 (2007) 762.
[22] Y. Liu, Q. Zhao, Applied Surface Science, Issues 1-4, (2004), 57.
[23]B. Veeraraghavan, H. Kim and B. Popov, Electrochimica Acta, Volume 49, Issue
19, (2004), 3143.
[24] Y.H. Chou, Y. Sung, Y.M. Liu, N.W. Pu, M.D. Ger, Surf. Coat. Technol. 203
(2009) 1020.
[25] F.B. Wu, Y.I Chen, P.J. Peng, Y.Y. Tsai, J.G. Duh, Surf. Coat. Technol. 150
(2002) 232.
[26] X.H. Huang, J.P. Tu, , B. Zhang, C.Q. Zhang, Y. Li, Y.F. Yuan and H.M. Wu,
Journal of Power Sources 161 (2006) 541.
[27] Yuehua Cui, Huidong Zhang, Hengyong Xu, Wenzhao Li, Applied Catalysis A:
General 331 (2007) 60.
[28] S.P. Sharma, D.K. Dwivedi and P.K. Jain, Wear 267 (2009) 853.
[29] Shusheng Zhang, Kejiang Han and Lin Cheng, Surf. Coat. Technol. 202 (2008)
2807.
[30] Gao Jiaqiang, Liu Lei, Wu Yating, Shen Bin and Hu Wenbin, Surf. Coat. Technol.
200 (2006) 5836.
[31] Guoqing Xiao, Quncheng Fan, Meizhuan Gu, Zihong Wang, Zhihao Jin,
Materials Science and Engineering A 382 (2004) 132.
[32] Z.D. Liu, J. Tian, B. Li, L.P. Zhao, Materials Science and Engineering A 527
(2010) 3898.
[33] J.N. Balaraju, V. Ezhil Selvi and K.S. Rajam, Materials Chemistry and Physics
120 (2010) 546.
[34] A. Abdel Aal, M. Bahgat, M. Radwan, Surf. Coat. Technol. 201 (2006) 2910.
[35] T.Z. Zou, J.P. Tu, S.C. Zhang, L.M. Chen, Q. Wang, L.L. Zhang, D.N. He,
Materials Science and Engineering A 426 (2006) 162.
[36] A. Abdel Aal, H.A. Gobran, F. Muecklich Journal of Alloys and Compounds 473
(2009) 250.
[37] Q. Zhao, Y. Liu, H. Mu¨ller-Steinhagen, G. Liu, Surf. Coat. Technol. 155 (2002)
279.
[38] M.D. Ger and B. J. Hwang, Materials Chemistry and Physics 76 (2002) 38.
[39] M.D. Ger, K.H. Hou, B.J. Hwang, Materials Chemistry and Physics 87 (2004)
102.
[40] Z. Abdel Hamid, S.A. El Badry, A. Abdel Aal, Surf. Coat. Technol. 201 (2007)
5948.
[41] Boz˙ ena Łosiewicz, Materials Chemistry and Physics 128 (2011) 442.
[42] C. León, E. García-Ochoa, J. García-Guerra, J. González-Sánchez, Surf. Coat. Technol.
205 (2010) 2425.
[43]M. Nova´k, D. Vojteˇch, T. V ı´tu˚, Applied Surface Science 256 (2010) 2956.
[44] Iijima S. Helical microtubules of graphite carbon. Nature 1991;354:56.
[45] Z. Yang, H. Xu, Y.L. Shi, M.K. Li, Y. Huang, H.L. Li, Materials Research
Bulletin 40 (2005) 1001.
[46] Arman Zarebidaki, Saeed-Reza Allahkaram, Journal of Alloys and Compounds
509 (2011) 1836.
[47] L.Y. Wang, J.P. Tu, W.X. Chen, Y.C. Wang, X.K. Liu, Charls Olk, D.H. Cheng,
X.B. Zhang, Wear 254 (2003) 1289.
[48] Z.H. Li, X.Q. Wang, M. Wang, F.F. Wang, H.L. Ge, Tribology International 39
(2006) 953.
[49] E.S. Berkovich, "Three-Faceted Diamond Pyramid for Studying Microhardness
by Indentation," Zavodskaya Laboratoria Vol. 13 #3 (1950) 345.
[50] W.C. Oliver, G.M. Pharr, . Mater. Res., 7(1992) 1564.
[51] T.R. Thomas, Rough Surfaces, 2nd Edition, Imperial College Press, London,
(1999), Chap. 2 21.
[52] J.M. Bennett and L. Mattsson, Introduction to Surface Roughness and Scattering,
Optical Society of America, Washington, D.C., (1989), Chap. 4 39.
[53] J.C. Vickerman Ed., "Surface Analysis: The Principle Techniques, " John Wiley
& Sons, Chichester, UK, (1997) 393.
[54] W. Stephen Tait, “An Interoduction to Electrochemical Corrosion Testing for
Practicing Engineers and Scientists”, 1994.
[55] I. Miloˇsev, T. Kosec, H.-H. Strehblow, Electrochimica Acta 53 (2008) 3547.
[56] Evgenij Barsoukou, J. Ross Macdonald (ed), Impedance spectroscopy Theory,
Experimental, and Application (2005).
[57]K.P. Gupta, Journal of Phase Equilibria and Diffusion Vol. 25 No. 5 (2004)
[58] C.C. Wu and F.B. Wu, Surf. Coat. Technol. 204 (2009) 854.
[59] B. Hugh; O. Hiroaki, ASM Handbook, Volume 03 - Alloy Phase Diagrams
[60] C.I. Merzbacher, J.G. Barkerb, K.E. Swiderc, D.R. Rolisonc, Adv. Colloid
Interface Sci. 76-77 (1998) 57.
[61] Y.-I. Chen, Surf. Coat. Technol. 204 (2009) 860.
[62] C.I. Merzbacher, J.G. Barkerb, K.E. Swiderc, D.R. Rolisonc, Adv. Colloid
Interface Sci. 76-77 (1998) 57.
[63] A. Vela´zquez-Palenzuela, International Journal of Hydrogen Energy 35 (2010)
11591.
[64] Y.I Chen, L.C. Chang, R.T. Huang, B.N. Tsai, Y.C. Kuo, Thin Solid Films 518
(2010) 3819.
[65] J. Shin, A. Waheed, W.A. Winkenwerder, H.W. Kim, K. Agapiou, R. A. Jones,
G.S. Hwang, J. G. Ekerdt, Thin Solid Films 515 (2007) 5298.
[66] J. Shin, Growth and Characterization of CVD Ru and Amorphous Ru-P Alloy
Films for Liner Application in Cu Interconnect, PhD Dissertation, University of Texas
at Austin, (2007) 113.
[67] H.H. Huang, Microstructure, Mechanical Properties and Electrochemical
Behaviors of Sputtered NiP/CrN and NiAl/CrN Multilayer Coatings, Master
Dissertation, National United University, (2010) 119.
[68] Evgenij Barsoukou, J. Ross Macdonald (ed), Impedance spectroscopy Theory,
Experimental, and Application (2005).
[69] C. Liu, Q. Bi, A. Leyland, A. Matthews, Corrosion Science 45 (2003) 1243.
[70] C. Liu, Q. Bi, A. Leyland, A. Matthews, Corrosion Science 45 (2003) 1257.