本實驗採用非平衡磁控濺鍍方式，於高速鋼、矽晶片、車刀等基材，濺鍍一系列ZrN與Zr-Ti-N鍍膜。首先調整氮氣流量及其他濺鍍參數來披覆一系列的ZrN，於其中選出性質較佳之一組參數；以此參數為基礎，添加不同比例之Ti成為Zr-Ti-N薄膜後，研究其基本特性、磨耗性能及應用於實際加工之可能性。

　　實驗規劃以三階段進行：第一、二階段嘗試各組參數之變化，以獲得一對應於較佳性質參數之ZrN鍍膜。第三階段則以前二階段獲得之最佳參數為基礎，添加一Ti靶，改變供應Ti靶之電流量，以製備出不同Ti含量之Zr-Ti-N鍍膜。

　　第一、二階段的結果顯示，ZrN之氮含量隨氮氣流量之上升而增加，於對應氮氣流量24sccm之參數，有最高硬度、黏附強度，以及最佳抗磨性能。第三階段的Zr-Ti-N，隨著Ti含量的增加，硬度也隨之增加，在Ti含量於18.7 at.%時呈現出最高的硬度值，達HK0.015278。主要在於添加Ti於鍍膜後所引起的固溶強化機制以及相伴隨的壓應力，使硬度呈現上升趨勢。藉由磨耗實驗發現，在Ti含量於16.5 at.%時，有著最佳之抗磨性能。車削的結果，顯示相同趨勢，而於微鑽削實驗加以驗證，顯示可比TiN有更降低之磨耗量。

　　In this experiment, a dc unbalanced magnetron sputtering system was employed to prepare a series of ZrN and Zr-Ti-N coatings on various substrates, including HSS steel, Si wafer and cutting inserts, etc. At first, the nitrogen gas flow and other process parameters were subject to adjusting to deposit ZrN coatings, and then a set of parameter corresponding to better properties was determined. Using the set of parameter and a Ti target, a group of Zr-Ti-N coatings with addition of varying content of Ti was obtained. Subsequently, their fundamental properties, wear performance, and feasibility of machining applications were studied.

　　The study was carried out through 3 stages: Stages 1 and 2
tried to vary the parameter combinations to obtain the one bettering off. Stage 3 used this as the basic to add Ti element by the Ti target. Changing the current of Ti target to prepare a series of Zr-Ti-N coatings.

　　The results of stage 1,2 revealed that the rising up of nitrogen gas flow increase the N2 content. The parameter corresponding to 24sccm had the highest hardness, adhesion strength and wear resistance. Following the increasing of Ti content, hardness of stage 3 Zr-Ti-N was up. At the Ti content 18.7 at.% had the highest hardness HK0.015278 because of the solution mechanism due to Ti adding and accompanied compressed stress. The result of wear test showed the Zr-Ti-N coating of Ti content 16.5 at.% had the best wear resistance, and the machining test displayed the same tendency. Comparing to the micro drilling could prove that Zr-Ti-N has lower wear quantity than TiN.

1.D. J. Cheng, W. P. Sun, M. H. Hon, ”The morphology and structure of chemically vapour-deposited Ti(C, N) coatings”, Thin Solid Films, 146 (1) (1987) 45-53
2.B. E. Jacobson, C. V. Deshandey, H. J. Doerr, A. A. Karim, R. F. Bunshah, “Microstructure and hardness of Ti(C, N) coatings on steel prepared by the activated reactive evaporation technique”, Thin Solid Films, 118 (3) (1984) 285-292
3.M.B.Peterson, S.Ramalingam, ” Coatings for tribological application, fundumentals of friction and wear of materials”, ASM ohio, (1981)331
4.J. -E. Sundgren, ”Structure and properties of TiN coatings”, Thin Solid Films, 128 (1985) 21-44
5.許博淵,”反應濺鍍TiAlN薄膜的製程參數及性質之研究”,國立成功大學材料科學及工程研究所博士論文,民國八十五年六月.
6.Y.L. Su, W.H. Kao, “Optimum multilayer TiN-TiCN coatings for wear resistance and actual application”, Wear, 223 (1998) 119-130
7.S. Niyomsoan, W. Grant, D.L. Olson, B. Mishra, “Variation o color in titanium and zirconium nitride decorative thin films”, Thin Solid Films, 415 (2002) 187-194
8.Y.H. Shin, S. Yukihiro, “Diffusion barrier property of TiN and TiN/Al/TiN films depositied with FMCVD for Cu interconnection in ULSI”, Science and Technology of Advanced Materials, 5(2004) 399-405
9.W.J. Chou, G.P. Yu, J.H. Huang, “Corrosion resistance of ZrN films on AISI 304 stainless steel substrate”, Surface & Coating Technology, 167 (2003) 59-67
10.K.A. Gruss, T. Zheleva, R.F. Davis, T.R. Watkins, “Characterization of zirconium nitride coatings depositied by cathodic arc sputtering”, Surface & Coating Technology, 107 (1998) 115-124
11.L.Pichon, T. Girardeau, A. Straboni, F. Lignou, P. Guerin, J.Perriere, “Zirconium nitrides depositied by dual ion beam sputtering:physical properties and growth modeling”, Applied Surface Science, 150 (1999) 115-124
12.F. Vaz, L. Rebouta, M. Andritschky, M.F. da Silva, J.C. Soares, “The effect of the addition of Al and Si on the physical and mechanical properties of titanium nitride”, Journal of Materials Processing Technology, 92-93 (1999) 169-176
13.C. Mitterer, P. H. Mayrhofer, M. Beschliesser, P. Losbichler, P. Warbichler, F. Hofer, P. N. Gibson, W. Gissler, H. Hruby, J. Musil, J. Vlček, “Microstructure and properties of nanocomposite Ti-B-N and Ti-B-C coatings”, Surface & Coatings Technology, 120-121 (1999) 405-411
14.J. Musil, F. Regent, “Formation of nanocrystalline NiCr-N films by reactive dc magnetron sputtering”, Journal of Vacuum Science and Technology A, 16(6) (1998) 3301-3304
15.L.C. Stearns, J. Zhao, M.P. Harmer, “Processing and Microstructure Development in Al2O3-SiC Nano Composities”, J. Euro. Cera. Soc., 10 (1992) 473-477
16.F. Regent, J.Musil, “Magnetron sputtered Cr-Ni-N and Ti-Mo-N films: comparison of mechanical properties”, Surface & Coating Technology, 142-144 (2001) 146-151
17.F. Vaz, L. Rebouta, Ph. Goudeau, T. Girardeau, J. Pacaud, J.P. Riviere, A. Traverse, ”Structural transitions in hard Si-based TiN coatings：the effect of bias voltage and temperature”, Surface & Coatings Technology, 146-147 (2001) 274-279
18.F. Vaz, L. Rebouta, P. Goudeau, J. Pacaud, H. Garem, J.P. Riviere, A. Cavaleiro, E. Alves, ”Chsrscterisation of Ti1-xSixNy nanocomposite films”, Surface & Coatings Technology, 133-134 (2000) 307-313
19.F. Levy, P. Hones, P.E. Schmid, R. Sanjines, M. Diserens, C. Wiemer, “Electronic states and mechanical properties in transition metal nitrides”, Surface & Coatings Technology, 120–121 (1999) 284–290
20.R. Nowak, C.L. Li, “Evaluation of HfN thin films considered as diffusion barriers in the Al/HfN/Si system”, Thin Solid Films, 305 (1997) 297-303
21.Y. Ando, I. Sakamoto, I. Suzuki, S. Maruno, “Resistivity and structural defects of reactively sputtered TiN and HfN films”, Thin Solid Films, 343-344 (1999) 246-249
22.柯賢文，“表面與薄膜技術”，課程講義
23.P.J. Kelly, R.D. Amell, “Magnetron sputtering: a review of recent developments and applications”, Vacuum, 56 (2000) 159-172
24.Lili Hu, Dejie Li, Guojia Fang, “Influence of N2：(N2 + Ar) flow ratio and substrate temperature on the properties of zirconium nitride films prepared by reactive dc magnetron sputtering”, Applied Surface Science, 220 (2003) 367-371
25.Henry J. Ramos, Nicomedes B. Valmoria, “Thin-film deposition of ZrN using a plasma sputter-type negative ion source”, Vacuum, 73 (2004) 549-554
26.L.-J. Meng, M.P. Dos Santos, “Characterization of titanium nitride films prepared by d.c. reactive magnetron sputtering at different nitrogen pressures”, Surface & Coating Technology, 90 (1997) 64-70
27.T. Yotsuya, M. Yoshitake, T. Kodama, “Low-Temperature thermometer using sputtered ZrNx thin film”, Cryogenics, 37 (1997) 817-822
28.B. Mayumi, T. Itoi, Eiji Aoyagi, Atsushi Noya, “High performance of thin nano-crystalline ZrN diffusion barriers in Cu/Si contact systems”, Applied Surface Science, 190 (2002) 450-454
29.M. Takeyma, S. Kagomi, A. Noya, K. Sakanishi, “Application of amorphous Cu-Zr binary alloy as a diffusion barrier in Cu/Si Systems”, J. Appl. Phys., 80 (1996) 569-573
30.W.J. Chou, G.P. Yu, J.H. Huang, “Bias effect of ion-plated zirconium nitride film on Si (100)”, Thin Solid Films, 405 (2002) 162-169
31.K.A. Gruss, T. Zheleva, R.F. Davis, T.R. Watkins, “Characterization of zirconium nitride coatings depositied by cathodic arc sputtering”, Surface & Coating Technology, 107 (1998) 115-124
32.M. Del Re, R. Gouttebaron, J.-P. Dauchot, P. Leclere, G. Terwagne, M. Hecq, “Study of ZrN layers depositied by reactive magnetron sputtering”, Surface & Coating Technology, 174-175 (2003) 240-245
33.L. Krusin-Elbaum and M. Wittmer, “Oxidation kinetics of ZrN thin films”, Thin solid films, 107 (1983) 111-117
34.H. N. Al-Shareef, X. Chen, D.J. Lichtenwalner, A.I. Kingon, “Analysis of the oxidation kinetic and barrier layer properties of ZrN and Pt/Rn thin films for DRAM application”, Thin Solid films, 280 (1996) 265-270
35.P. Panjan, B. Navinsek, A. Zabker, V. Marinkovic, D. Mandrino, J. Fiser, “Structural analysis of Zr-N and Ti-N films prepared by reactive plasma beam deposition”, Thin Solid films, 228 (1993) 233-237
36.I. Penttinen, J.M. Molarius, A.S. Korthonen, “Structure and composition of ZrN and (Ti, Al)N coatings”, Journal of Vacuum Science and Technology A, 6 (1988) 2158-2161
37.Chuan-Pu Liu, Heng-Ghieh Yang, ”Systematic study of the evolution of texture and electrical properties of ZrNx thin films by reactive DC manetron sputtering”, Thin Slid Films, 444 (2003) 111-119
38.H.M. Benia, M. Guemaz, G. Schmerber, A. Mosser, J. -C. Parleas, “Investigations on non-stoichiometric zirconium nitrides”, Applied Surface Science, 200 (2002) 231-238
39.D. Pilloud, A.S. Dehlinger, J.F. Pierson, A. Roman, L. Pichon, “Reactively sputtered zirconium nitride coatings: structural, mechanical, optical and electrical characteristics”, Surface & Coating Technology, 174-175 (2003) 338-344
40.Chuan-Pu Liu, Heng-Ghieh Yang, “Deposition temperuture and thickness effects on the characteristics of dc-sputtered ZrNx films”, Materials Chemistry and Physics, 86 (2004) 370-374
41.T. Mae, M. Nose, M, Zhou, T. Nagae, K. Shimamura, “The effects of Si addition on the structure and mechanical properties of ZrN thin films deposited by an r.f. reactive sputtering method”, Surface & Coating Technology, 142-144 (2001) 954-958
42.J. Musil, H. Poláková, “Hard nanocomposite Zr-Y-M coatings, correlation between hardness and structure”, Surface & Coating Technology, 127 (2000) 99-106
43.P. Karvánková, H.-D. Männling, C. Eggs, S. Veprek, “Thermal stability of ZrN-Ni and CrN-Ni superhard nanocomposite coatings”, Surface & Coating Technology, 146-147 (2001) 280-285
44.S.B. Sant, K.S. Gill, “Growth and characterization of cathodic arc evaporated CrN, (TiAl) N and (TiZr) N films”, Surface & Coating Technology, 68-69 (1994) 152-156
45.M.B. Takeyama, T. Itoi, E. Aoyagi, A. Noya, “Diffusion barrier properties of nano-crystalline TiZrN films in Cu/Si contact systems”, Applied Surface Science, 216 (2003) 181-186
46.V.V. Uglov, V.M. Anishchik, V.V. Khodasevich, Zh.L. Prikhodko, S.V. Zlotski, G. Abadias, S.N. Dub, “Structural characterization and mechanical properties of Ti-Zr-N coatings, deposited by vacuum arc”, Surface & Coating Technology, 180-181 (2004) 519-525
47.L.A. Donohue, J. Cawley, J.S. Brooks, “Deposition and characterization of arc-bond sputter TixZryN coatings from pure metallic and segmented targets”, Surface & Coating Technology, 72 (1995) 128-138
48.J.L. He, C.K. Chen, M.H. Hon, “Wear of Ti-Si-N coated ceramic cutting inserts”, Wear, 181-183 (1995) 189-193
49.P. Zeman, R. Cerstvy, P.H. Mayrhofer, C. Mitterer, J. Musil, “Structure and properties of hard and superhard Zr-Cu-N nanocomposite coatings”, Materials Science and Engineering A, 289 (2000) 189-197
50.J. Musil, P. Karvánková, J. Kasl, “Hard and superhard Zr-Ni-N nanocomposite films”, Surface & Coating Technology, 139 (2001) 101-109
51.J.J. Nainaparampil, J.S. Zabinski, A. Korenyi-Both, “Formation and characterization of multiphase film properties of (Ti-Cr) N formed by cathodic arc deposition”, Thin Solid Films, 333 (1998) 88-94
52.J.D. Bressan, R. Hesse, E.M. Silva Jr., “Abrasive wear behavior of high speed steel and hard metal coated with TiAlN and TiCN”, Wear, 250 (2001) 561-568
53.S.K. Wu, H.C. Lin, P.L. Liu, “An investigation of unbalanced-magnetron sputtered TiAlN films on SKH51 high-speed steel”, Surface & Coating Technology, 124 (2000) 97-103
54.C. Héau, N. Guillon, R.Y. Fillit, J. Machet, “Ultra-hard Ti-B-N coatings obtained by magnetron sputtering”, Surface & Coating Technology, 97 (1997) 60-65
55.T. Arai, H. Fujita, M. Watanabe, “Evaluation of adhesion strength of thin hard coatings”, Thin Solid Films, 154 (1987) 387-401
56.P. J. Burnett, D. S. Rickerby, ”The relationship between hardness and scratch adhesion”, Thin Solid Films, 154 (1987) 403-416
57.F. Ramos, M.T. Vieira, “Adhesion improvement of RF-sputtered alumina coatings as determined by the scratch test”, Journal of Adhesion Science Technology, 7(8) (1993) 801-811
58.K. Dieter, “Semiconductor material and device characterization”, Chapter 1 (1990) 2-5
59.張啟釗，”滲雜銀、鎢元素之氮化鈦陶瓷薄膜磨潤性質研究”，國立成功大學機械工程學系，碩士論文，中華民國93年。
60.I.Milosev, H.-H. Strehblow, B. Navinsek, “Comparison of TiN, ZrN and CrN hard nitride coatings :Electrochemical and thermal oxidation” Thin Solid Films 303 (1997) 246-254