The interfacial reactions between AlN and Ti have been examined by using SEM/EDS and TEM/EDS after annealing at 1000o-1500oC. As a result, the following conclusions have been obtained:
1. After annealing at 1000oC, a δ-TiN layer was initially formed in the reaction zone between AlN and Ti, and the α2-Ti3Al layer subsequently developed between δ-TiN and Ti. A twinned α2-Ti3Al structure was observed on annealing on 1000°C, while an ordered cubic τ1-Ti3AlN was precipitated from the twinned α2-Ti3Al during cooling. The orientation relationships between τ1-Ti3AlN and α2-Ti3Al(N) were
[ 111 ]
τ1−Ti3AlN//[ 0001 ]
α2−Ti3Al(N) and2. A sequence of phases was observed at the interface consisted of δ-TiN, τ2-Ti2AlN, τ1-Ti3AlN, α2-Ti3Al, and a two-phase (α2-Ti3Al + α-Ti) region After annealing at 1300oC. The α2-Ti3Al region revealed equiaxed and elongated morphologies with
[ 0001 ]
equiaxed// [ ] 1 100
elongated and( )
1010 equiaxed //( )
1122 elongated. In the two-phase (α2-Ti3Al + α-Ti) region, α2-Ti3Al and α-Ti were found to satisfy the following orientation relationship: Ti TiAl2 3
3. After annealing at 1400oC, the γ-TiAl and a lamellar two-phase (γ-TiAl+α2-Ti3Al) structure, instead of τ1-Ti3AlN, were found in between τ2-Ti2AlN and α2-Ti3Al. The orientation relationship of γ-TiAl and α2-Ti3Al in the lamellar structure was identified to be as follows:
[ 011 ]
γ−TiAl//[ 2 1 1 0 ]
α2−Ti3Al andAl TiAl
//( 01 1 0 )
2 Ti3) 1 1 1
(
γ− α − . Compared with the reaction zone after annealing at 1400ºC, the γ-TiAl was not found at the interface after annealing at 1500oC.5. After AlN was bonded with a Ti foil at 1400ºC for up to 1 h, a chopped fiber-like τ2-Ti2AlN precipitated in the matrix of γ-TiAl, with
AlN Ti TiAl
//[ 11 2 0 ]
2 2]
110
[
γ− τ − and( 1 1 1 )
γ−TiAl//( 1 1 0 3 )
τ2−Ti2AlN, by substituting N atoms for one-half Al atoms after annealing at 1400oC for 1 h. The released Al atoms, due to the precipitation of τ2-Ti2AlN, resulted in an ordered Al-rich γ-TiAl or Ti3Al5. Furthermore, the α-Ti (Al, N) was nitridized into a lamellar layer (δ-TiN + α-Ti) with[ 110 ]
δ−TiN//[ 11 2 0 ]
α−Ti and( 111 )
δ−TiN//( 0001 )
α−Ti.References
1. L. M. Sheppard, "Aluminum Nitride: A Versatile but Challenging Material,"
Am. Ceram. Soc. Bull., 69 [11] 1801-12 (1990).
2. N. Iwase, A. Tsuge, and Y. Sugirua, "Development of A High Thermal Conductive AlN Ceramic Substrate Technology," Int. J. Hybrid Microelectronics, 7 [4] 49-53 (1984).
3. P. Villars, A. Prince, and H. Okamoto, Handbook of Ternary Alloy Phase
Diagrams, ASM International, Materials Part, OH, 1994.
4. J. L. Murray, Phase Diagrams of Binary Titanium Alloys, ASM International, Metals park, Ohio, 1987.
5. J. Braun and M. Ellner, "Phase Equilibria Investigations on the Aluminum-Rich Part of the Binary System Ti-Al," Met. Trans. A, 32A 1037-47 (2001).
6. V. Raghavan, "Al-Ti(Aluminum-Titanium)," J. Phase Equilibria and
Diffusion, 26 [2] 171-72 (2005).
7. X. He, K. Tao, and Y. Fan, "Solid-State Reaction of Ti and Ni Thin Film with Aluminum Nitride," J. Vac. Sci. Technol., 14 [4] 2564-69 (1996).
8. C. Tsai, J. Tseng, and C. His, "Interfacial Adhesion and Microstructure of Thick Film Metallized Aluminum Nitride Substrates," Ceram. Inter., 28 23-28 (2002).
9. M. Borowski and J. P. Dallas, "Structural Characterization of Ti Implanted AlN," J. Mater. Res., 12 [10] 3136-42 (1995).
10. K. Komeya, "Development of Nitrogen Ceramics," Am. Ceram. Soc. Bull., 63 [9] 1158-59 (1984).
11. N. Kuramoto, H. Taniguchi, and I. Aso, "Translucent AlN Ceramic Substrate," IEEE Trans. Compon., Hybrids, Manuf. Technol, CHMT-9 [4]
386-90 (1986).
12. Y. Imanaka and M. R. Notis, "Interfacial Reaction between Titanium Thin
Films and Aluminum Nitride Substrates," J. Am. Ceram. Soc., 82 [6] 1547-52 (1999).
13. X. He, Si-Ze Yang, K. Tao, and Y. Fan, "Investigation of the Interface Reactions of Ti Thin Films with AlN Substrate," J. Mater. Res., 12 [3] 846-51 (1997).
14. M. Pinkas, N. Frage, N. Froumin, J. Pelleg, and M. P. Dariel, "Early Stages of Interface Reactions between AlN and Ti Thin Films," J. Vac. Sci. Technol., 20 [3] 887-96 (2002).
15. T. Yasumoto, K. Amakawa, N. Iwase, and N. Shinsawa, "Reaction between AlN and Metal Thin Films during High Temperature Annealing," J. Ceram. Soc.
Jpn., 101 [9] 969-73 (1993).
16. R. Yue, Y. wang, C. Chen, and C. Xu, "Interface Reaction of Ti and Mullite Ceramic Substrate," Appl. Surf. Sci., 126 255-64 (1998).
17. M. H. El-Sayed, M. Naka, and J. C. Schuster, "Interfacial Structure and Reaction Mechanism of AlN/Ti Joints," J. Mater. Sci., 32 2715-21 (1997).
18. Y. S. Han, K. B. Kalmykov, S. F. Dunaev, and A. I. Zaitsev, "Phase Equilibria in the Ti-Al-N System at 1273K," Dok. Phy. Chem., 396 [2] 134-37 (2004).
19. Y. Paransky, A. Berner, and I. Gotman, "Microstructure of Reaction Zone at the Ti-AlN Interface," Mater. Let., 40 180-86 (1999).
20. Y. Paransky, A. Berner, I. Gotman, and E. Gutmanas, "Phase Recognition in AlN-Ti System by Energy Dispersive Spectroscopy and Electron Backscatter Diffraction," Mikrochim. Acta, 134 171-77 (2000).
21. Y. Paransky, I. Gotman, and E. Y. Gutmanas, "Reactive Phase Formation at AlN-Ti and AlN-TiAl Interfaces," Mater. Sci. Eng., A277 83-94 (2000).
22. C. H. Chiu and C. C. Lin, "Microstructural Characterization and Phase Development at the Interface Between Aluminum Nitride and Titanium After Annealing at 1300o-1500oC," J. Am. Ceram. Soc., 89 [4] 1409-18 (2006).
23. Y. Paransky, A. Berner, and I. Gotman, "Microstructure of Reaction Zone at
the Ti-AlN Interface," Mater. Let., 40 180-86 (1990).
24. L. Hultman, "Thermal Stability of Nitride Thin Films," Vacuum, 57 1-30 (2000).
25. J. C. Schuster and J. Bauer, "The Ternary System Titanium-Aluminum-Nitrogen," J. Solid State Chem., 53 [2] 260-65 (1984).
26. R. Yue, Y. Wang, Y. Wang, and C. Chen, "Study on Interfacial Reaction of Ti/AlN by SIMS, RBS and XRD," Surf. Interface Anal., 27 98-102 (1999).
27. J. Magnan, G. C. Weatherly, and M. C. Cheynet, "The Nitriding Behavior of Ti-Al Alloys at 1000oC," Metall. Mater. Trans. A, 30A 19-29 (1999).
28. H. Xiao, I. M. Robertson, and H. K. Birnbaum, "Deuterium Driven Phase Transitions in the Ti3Al Intermetallic," Acta Mater., 50 3671-82 (2002).
29. P. Villars, A. Prince, and H. Okamoto, Handbook of Ternary Alloy Phase
Diagrams, ASM International, Materials Part, OH, 1995.
30. C. A. Slack, "Nonmetallic Crystals with High Thermal Conductivity," J.
Phys. Chem. Solids, 34 321-35 (1973).
31. N. Iwase, K. Anzai, and K. Shinozaki, "Aluminum Nitride Substrates Having High Thermal Conductivity," Toshiba Review, 153 49-53 (1985).
32. P. Martineau, R. Pailler, M. Lahaye, and R. Naslain, "SiC Filament/Titanium Matrix Composites Regarded as Model Composites. II.--Fiber/Matrix Chemical Interactions at High Temperatures," J. Mater. Sci., 19 2749-70 (1984).
33. J. C. Feng, M. Naka, and J. C. Schuster, "Reaction Mechanism between SiC Ceramic and Titanium Foil in Solid State Bonding," J. Japan Inst. Metals, 59 978-83 (1995).
34. W. J. Whatley and F. E. Wawner, "Kinetics of the Reaction between SiC(SCS-6) Filaments and Titanium(6Al-4V) Matrix," J. Mater. Sci. Let., 4 [2]
173-75 (1985).
35. D. Travessa and M. Ferrante, "The Al2O3-Titanium Adhesion in the View of the Diffusion Bonding Process," J. Mater. Sci., 37 4385-90 (2002).
36. E. Faran, I. Gotman, and E. Y. Gutmanas, "Experimental Study of the
Reaction Zone at Boron Nitride Ceramic-Ti Metal Interface," Mater. Sci. Eng., A288 66-74 (2000).
37. K. L. Lin and C. C. Lin, "Ti2ZrO Phases Formed in the Titanium and Zirconia Interface After Reaction at 1550oC," J. Am. Ceram. Soc., 88 [5]
1268-72 (2005).
38. P. A. Janeway, "Making the Grade in Demanding Electronic Application,"
Ceram. INd., 137 28-32 (1991).
39. J. A. Chediak, "Ceramic Engineers in the 21st Century," Am. Ceram. Soc.
Bull., 75 [1] 52-55 (1996).
40. T. B. Jackson, A. V. Virkar, K. L. More, R. B. Dinwiddie, and R. A. Cutler,
"High-Thermal-Conductivity Aluminum Nitride Ceramics: the Effect of Thermodynamic, Kinetic and Microstructural Factors," J. Am. Ceram. Soc., 80 [6] 1421-35 (1997).
41. S. Nakahata, K. Sogabe, T. Matsuura, and A. Yamakawa, "One Role of Titanium Compound Particles in Aluminum Nitride Sintered Body," J. Mater.
Sci., 32 1873-76 (1997).
42. H. D. Lee, Phase Chemistry, Thermodynamic and Kinetic Characterization
of Interfacial Reaction Between Aluminum Nitride and Titanium, ; Ph.D.
Dissertation, Arizona State University, Tempe, AZ, 1993.
43. A. D. Westwood and M. R. Notis, "Analytical Electron Microscopy Study of AlN Substrates and Metallization Interfaces," Adv. Ceram, 26 171-87 (1989).
44. A. D. Westwood and M. R. Notis, "An Issue in Thermal Management:
Metallizing High Thermal Conductivity Ceramic Substrates in Microelectronics," J. Miner. Met. Mater. Soc., 43 [6] 10-15 (1991).
45. A. H. Carim and R. E. Loehman, "Microstructure at the Interface between AlN and A Ag-Cu-Ti Braze Alloy," J. Mater. Res., 5 [7] 1520-29 (1990).
46. R. E. Loehman, "Interfacial Reactions in Ceramic-Metal Systems," Ceram.
Bull., 68 [4] 891-96 (1989).
47. R. E. Loehman and A. P. Tomsia, "Reactions of Ti and Zr with AlN and
Al2O3," Acta Metall. Mater., 40 [suppl.] S75-S83 (1992).
48. K. L. Lin and C. C. Lin, "Zirconia-Related Phases in the Zirconia/Titanium Diffusion Couple After Annealing at 1000o-1550oC," J. Am. Ceram. Soc., 88 [10]
2928-34 (2005).
49. M. A. Pietzka and J. C. Schuster, "Phase Equilibria in the Quaternary System Ti-Al-C-N," J. Am. Ceram. Soc., 79 [9] 2321-30 (1996).
50. A. Dutta and D. Banerjee, "Superplastic Behaviour in A Ti3Al-Nb Alloy,"
Scripta Metall. Mater., 24 [7] 1319-22 (1990).
51. J. M. Kim, C. G. Park, T. K. Ha, and Y. W. Chang, "Microscopic Observation of Superplastic Deformation in A 2-Phase Ti3Al-Nb Alloy," Mater.
Sci. Eng., A269 197-204 (1999).
52. B. D. Cullity, Elements of X-Ray Diffraction, Addison-Wesley Publishing Company, Inc., California, 1978.
53. J. Raisanen, A. Anttila, and J. Keinonen, "Diffusion of Aluminum in Ion-Implanted a-Ti," J. Appl. Phys., 57 [2] 613-14 (1985).
54. A. Anttila, J. Raisanen, and J. Keinonen, "Diffusion of Nitrogen in a-Ti,"
Appl. Phys. Lett., 42 [6] 498-500 (1983).
55. J. C. Viala, N. Peillon, L. Clochefert, and J. Bouix, "Diffusion Paths and Reaction Mechanisms in the High-Temperature Chemical Interaction between Carbon and Titanium Aluminides," Mater. Sci. Eng., A203 222-37 (1995).
56. I. Barin, Thermochemical Data of Pure Substances,, VCH, Weinheim, Germany, 1989.
57. Y. Paransky, L. Klinger, and I. Gotman, "Kinetics of Two-Phase Layer Growth during Reactive Diffusion," Mater. Sci. Eng., A270 231-36 (1999).
58. B. Zhao, J. Sun, J. S. Wu, and Z. X. Yuan, "Gas Nitriding Behavior of TiAl Based Alloys in an Ammonia Atmosphere," Scripta Mater., 46 581-86 (2002).
59. W. H. Tian and M. Nemoto, "Precipitation Behavior of Nitrides in L1o-ordered TiAl," Intermetallics, 13 1030-37 (2005).
60. J. C. Pivin, P. Zheng, and M. O. Ruault, "Transmission Electron Microscopy
Investigation of the Structural Transformations in Titanium or TiAl Implanted with Nitrogen, Carbon, Oxygen and Boron," Mater. Sci. Eng., A115 83-88 (1989).
61. A. B. Kloosterman and J. Th. M. De Hosson, "Microstructural Characterization of Laser Nitrided Titanium," Scripta Metal. Mater., 33 [4]
567-73 (1995).
62. K. Saito and T. Matsushima, "Nitrogen Ion Implantation into the Intermetallic Compound TiAl," Mater. Sci. Eng., A115 355-59 (1989).
63. G. Cliff and G. W. Lorimer, "The Quantitative analysis of thin specimens,"
Journal for Microscopy, [103] 203-07 (1975).
64. Q. Chen and B. Sundman, "Thermodynamic Assessment of the Ti-Al-N System," J. Phase Equilibria, 19 [2] 146-60 (1998).
65. M. Inoue, M. Nunogaki, and K. Suganuma, "Chemical Reaction of TiAl Intermetallics wiht a Nitrogen Plasma," J. Solid State Chem., 157 339-46 (2001).
66. P. Villars and L. D. Calvert, Pearson's Handbook of Crystallographic Data
for Intermetallic Phases, ASM International, Materials Park, OH, 1991.
67. M. Doi, T. Koyama, T. Taniguchi, and S. Naito, "Morphological Changes of the Ti3Al5 Phase Formed by Phase-decomposition of TiAl Intermetallics," Mater.
Sci. Eng., A329-331 891-97 (2002).
68. G. Sattonnay and O. Dimitrov, "Long-Range Order Relaxation and Phase Transformation in g-TiAl Alloys," Acta Mater., 47 [7] 2077-88 (1999).
69. T. Nakano, A. Negishi, K. Hayashi, and Y. Umakoshi, "Ordering Process of Al5Ti3, h-Al2Ti and r-Al2Ti with F.C.C.-Based Long-Period Superstructures in Rapidly Solidified Al-Rich TiAl Alloys," Acta Mater., 47 [4] 1091-104 (1999).
70. C. L. Fu and M. H. Yoo, "Bonding Mechanisms and Point Defects in TiAl,"
Intermetallics, 1 59-63 (1993).
71. S. Swaminathan, I. P. Jones, A. W. S. Johnson, and H. L. Fraser,
"Debye-Waller Factors in off-stoichiometric TiAl: Effect of Ording of Excess Al Atoms on Ti Sites," Philo. Maga. Let., 73 [6] 319-30 (1996).
72. D. Vujic, Z. Li, and S. H. Whang, "Effect of Rapid Solidification and Alloying Addition on Lattice distortion and Atomic Ordering in L10 TiAl Alloys and Their Ternary Alloys," Metall. Trans. A, 19A [10] 2445-55 (1988).
73. W. Lu, C. L. Chen, F. H. Wang, J. P. Lin, G. L. Chen, and L. L. He, "Phase Transformation in the Nitride Layer during the Oxidation of TiAl-based Alloys,"
Scripta Mater., 56 773-76 (2007).
74. R. Yu, S. Zhang, L. L. He, W. T. Wu, and H. Q. Ye, "Metal/Ceramic Interface in An in Situ Synthesized Ti/TiCP Compostie Coating by Laser Processing," J. Mater. Res., 16 [1] 9-12 (2001).
75. Z. J. Lin, M. J. Zhuo, Y. C. Zhou, M. S. Li, and J. Y. Wang, "Microstructural Characterization of Layered Ternary Ti2AlC," Acta Mater., 54 1009-15 (2006).
List of Publications
1. Chia-Hsiang Chiu and Chien-Cheng Lin, “Microstructural Characterization and Phase Development at the Interface Between Aluminum Nitride and Titanium After Annealing at 1300o-1500oC,” J. Am. Ceram. Soc., 89 [4]
1409-1418(2006).
2. Chia-Hsiang Chiu and Chien-Cheng Lin, “Microstructural Development of the AlN/Ti Diffusion Couple Annealed at 1000oC,” J. Am. Ceram. Soc., 91 [4]
1273-1280(2008).
3. Chia-Hsiang Chiu and Chien-Cheng Lin, “Formation mechanisms and atomic configurations of nitride phases at the interface of aluminum nitride and titanium,” J. Mater. Res., in press.