Abstract
Solid-solid diffusion couples assembled with disks of copper, tin and intermetallics (Cu3Sn and Cu6Sn5) were employed to investigate the Kirkendall effect in the copper-tin system at the temperature of 200 °C. In the Cu(99.9%)/Sn diffusion couple, inert alumina particles used as markers were identified in the Cu6Sn5 phase, while microvoids were observed at the Cu/Cu3Sn interface. The Cu(99.9%)/Sn and Cu(99.9%)/Cu6Sn5 diffusion couples annealed at 200 °C for 10 days were analyzed for intrinsic diffusion coefficients of Cu and Sn in the Cu6Sn5 and Cu3Sn phases, respectively with due consideration of changes in molar volume. Interdiffusion, integrated and effective interdiffusion coefficients were also calculated for the intermetallic phases. Diffusion couples annealed at 125-400 °C for various times were analyzed for the kinetic parameters such as growth rate constants and activation energies for the formation of Cu3Sn and Cu6Sn5 phases. Uncertainties in the calculated intrinsic diffusivities of Cu and Sn arise mainly from the non-planar morphologies of the interfaces and the non-planar distribution of the markers. Intrinsic diffusion coefficients based on average locations of the marker plane indicate that Cu is the faster diffusing component than Sn in both the Cu3Sn and Cu6Sn5 phases.
Similar content being viewed by others
References
Q. Xu and A. Van der Ven, First-Principles Investigation of Migration Barriers and Point Defect Complexes in B2-NiAl, Intermetallics, 2009, 17(5), p 319-329
R.S. Kejun Zeng, T.-C. Chiu, D. Edwards, K. Ano, and K.N. Tu, Kirkendall Void Formation in Eutectic SnPb Solder Joints on Bare Cu and Its Effect on Joint Reliability, J. Appl. Phys., 2005, 97(2), p 024508-8
Th. Massalski, Ed., Binary Alloy Phase Diagrams, American Society for Metals, Metals Park, OH, 1986
P. Borgesen and D.W. Henderson, Fragility of Lead-Free Solder Joints, Binghamton University, New York, 2004
L. Xu and J.H.L. Pang, Effect of Intermetallic and Kirkendall Voids Growth on Board Level Drop Reliability for SnAgCu Lead-Free BGA Solder Joint, 56th Electronic Components and Technology Conference and Proceedings, 2006, p 275-282
Z. Mei, M. Ahmad, M. Hu, and G. Ramakrishna, Kirkendall Voids and Cu/Solder Interface and Their Effects on Solder Joint Reliability, 55th Proceedings of Electronic Components and Technology Conference, 2005, p 415-420
P. Borgesen, L. Yin, P. Kondos, D.W. Henderson, G. Servis, J. Wang, and K. Srihari, Sporadic Degradation in Board Level Drop Reliability—Those Aren’t All Kirkendall Voids, 57th Electronic Components and Technology Conference and Proceedings, 2007, p 136-146
C.A. Handwerker, E. Erk, A. Hess, A. Squire, and M. Yarbrough, Void Formation: Emerging Issues in Materials Compatibility and Reliability of PB-Free Assembllies, Going Green Care Innovation, Vienna, Austria, 2006
Y. Liu, J. Wang, P. Kondos, P. Borgesen, D.W. Handerson, E.J. Cotts, and N. Dimitrov, Influence of Plating Parameters and Solution Chemistry on the Voiding Propensity at Electrodeposited Copper-Solder Interface, J. Appl. Electrochem., 2008, 38(12), p 1695-1705
S. Kumar, C.A. Handwerker, X. Nie, J. Smetana, D. Love, J. Watkowski, R. Martinez, and R. Parker, Microvoid Formation at Electrodeposited Copper-Solder Interfaces during Annealing: A Preliminary Study of the Root Cause, SMTA International Conference and Proceedings, Orlando, Vol 10, 2008, p 544-553
A.G. Guy, Kirkendall Effect in Cu-Sn Alloys, Scripta Metall., 1983, 17(7), p 967-968
K. Hoshino, A.Y. Iijima, and K.I. Hirano, Inter-Diffusion and Kirkendall Effect in Cu-Sn Alloys, Trans. Jpn. Inst. Met., 1980, 21(10), p 674-682
L.C.C. Dasilva and R.F. Mehl, Interface and Marker Movements in Diffusion in Solid Solutions of Metals, J. Met., 1951, 3(2), p 155-173
M. Onishi and M. Fujibuchi, Reaction-Diffusion in the Cu-Sn System, Trans. Jpn. Inst. Met., 1975, 16, p 539-547
A. Paul, The Kirkendall Effect in Solid State Diffusion, Laboratory of Materials and Interface Chemistry, Eindhoven University of Technology, 2004
A. Paul, C. Ghosh, and W.J. Boettinger, Diffusion Parameters and Growth Mechanism of Phases in the Cu-Sn System, Metall. Mater. Trans. A, 2011, 42A, p 952-963
Properties and Selection: Nonferrous Alloys and Pure Metals, Metal Handbooks, Vol 2, 9th ed., ASM, 1979
P. Villars and L.D. Calvert, Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, American Society for Metals, Metals Park, OH, 1985
Z.S. Mei, A.J. Sunwoo, and J.W. Morris, Analysis of Low-Temperature Intermetallic Growth in Copper-Tin Diffusion Couples, Metall. Trans. A, 1992, 23, p 857-864
L. Boltzmann, Wiedemanns Ann. Phys., 1894, 53, p 959
C. Matano, The Relation Between the Diffusion Coefficients and Concentrations of Solid Metals, Jpn. J. Phys., 1933, 8, p 109-113
F.J.A. den Broeder, A General Simplification and Improvement of the Matano-Boltzmann Method in the Determination of the Interdiffusion Coefficients in Binary Systems, Scripta Metall., 1969, 3(5), p 321-325
F. Sauer and V. Freise, Diffusion in Binaren Gemischen Mit Volumenanderung, Zeitschrift Fur Elektrochemie, 1962, 66(4), p 353-363, in German
F.J.J. Van Loo, On the Determination of Diffusion Coefficients in a Binary Metal System, Acta Metall., 1970, 18(10), p 1107-1111
A.G. Guy, Treatment of Diffusion Considering Changes in Atomic Volume, Scripta Metall., 1971, 5(4), p 279-281
C. Wagner, Evaluation of Data Obtained with Diffusion Couples of Binary Single-Phase and Multiphase Systems, Acta Metall., 1969, 17(2), p 99-107
S. Kumar, K. Kulkarni, C. Handwerker, M. Dayananda, Diffusion Analysis of Cu-Sn System, Materials Science and Technology Conference and Proceedings, Detroit, MI, 2007, p 493-504
A.G. Guy, R.T. deHoff, and C.B. Smith, ASM Trans. Quart., 1968, 61, p 314-320
R.L. Fogelson, Fizika metallov i metallovedeni, 1965, 19, p 212-217, in Russian
T. Heumann, Z. Physik. Chem., 1952, 201, p 168-189, in German
M.A. Dayananda, Average Effective Interdiffusion Coefficients in Binary and Multicomponent Alloys, Defect Diffus. Forum, 1993, 95-98, p 521-536
R.J. Schaefer, F.S. Biancaniello, and R.D. Jiggetts, Intermetallic Compounds Formed in Solder Joints—Preparation of Single Phase Samples, Metal Science of Joining, Proceedings of TMS Symposium, Cincinnati, 1991
P.G. Shewmon, Diffusion in Solids, McGraw-Hill Book Company, Inc, New York, 1963
M.A. Dayananda and C.W. Kim, Zero-Flux Planes and Flux Reversals in Cu-Ni-Zn Diffusion Couples, Metall. Trans. A, 1979, 10(9), p 1333-1339
M.A. Dayananda, Atomic Mobilities in Multicomponent Diffusion and Their Determination, Trans. Met. Soc. AIME, 1968, 242, p 1369-1372
J. Philibert, Atom Movements: Diffusion and Mass Transport in Solids, Monographies de physique, Les Ulis, France, 1991, p 238
L.S. Darken, Diffusion, Mobility, and Their Interrelation Through Free Energy in Binary Metallic Systems, Trans. Met. Soc. AIME, 1948, 175, p 184-201
P.C. Tortorici and M.A. Dayananda, Growth of Silicides and Interdiffusion in the Mo-Si System, Metall. Mater. Trans. A, 1999, 30A, p 545-550
I. Kawakatsu and T. Osawa, Wettability of Liquid Tin on Solid Copper, Trans. JIM, 1973, 14, p 114-119
E. Starke and H. Wever, Z. Metallk., 1964, 55, p 107-113
Acknowledgments
The support of the High Density Packaging User Group (HDPUG) International for this research is gratefully acknowledged, as is the generosity of William Boettinger and Maureen Williams of NIST for providing the bulk, single phase intermetallic materials and of William Boettinger, C. Ghosh and Aloke Paul in sharing a preprint of their paper.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Kumar, S., Handwerker, C.A. & Dayananda, M.A. Intrinsic and Interdiffusion in Cu-Sn System. J. Phase Equilib. Diffus. 32, 309–319 (2011). https://doi.org/10.1007/s11669-011-9907-9
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11669-011-9907-9