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Characterization Of Creep Behaviours Of Soldered Joints Of A Nano- Composite Solder And Of Lead-Free Sn-Ag-Bi And Sn60Pb40 Solders X. P. Zhang 1,2), Y. W. Mai 2, Y. W. Shi 3 and L. Ye 2 1 School of Mechanical Engineering, South China University of Technology, Guangzhou 510640, China 2 Centre for Advanced Materials Technology, School of Aerospace, Mechanical & Mechatronic Engineering, the University of Sydney, NSW 2006, Australia 3 School of Materials Science and Engineering, Beijing Polytechnic University, Beijing 100022, China ABSTRACT: Creep performance of soldered connections is significant to the reliability evaluation and lifetime prediction of microelectronic and optoelectronic/photonic packaging systems. In this work, creep behaviours of a tin-based composite solder reinforced by nano-sized metal particles and a lead-free Sn-Ag-Bi solder were characterized, with a comparison to Sn60Pb40 solder. The results show that the nano-composite solder has much better creep resistance than Sn60Pb40. The lead-free Sn-Ag-Bi solder has superior creep performance to both Sn60Pb40 and nano-composite solders. The creep fractography analysis shows that a progressive shear deformation occurred as the main creep fracture mechanism. Sn60Pb40 solder joints deform dominantly by transgranular sliding, while Sn-Ag-Bi and nano-composite solder joints creep by intergranular mechanism through grain boundary sliding and boundary voids growth. The mechanism of enhancing the creep resistance of nano-composite solder joints is that uniformly dispersed nano-sized particulates provide effective resistance by impeding grain boundary sliding and dislocation movement, besides the alloying effect of increasing elasticity modulus of the solder. 1 INTRODUCTION Creep resistance and thermal fatigue performance of soldered connections are critical reliability concerns for microelectronic and optoelectronic packaging systems, as well as for photonic packages. In applications, soldered joints are under both electrical and mechanical interconnections, and thus subjected to a combined load of electrical, mechanical and thermal. It has been commonly agreed that creep and creep fracture resistance as well as thermal fatigue performance of soldered connections/joints are key reliability issues. In particular, in recent years the requirement on increased functionality and miniaturisation of modern electronic and optoelectronic components, where the operational temperatures and stresses increase the demands of mechanical property on soldered joints, has put forward a challenge on development of the solders with excellent anti-creep property. Especially, the creep resistance of solders and connections is critical for optoelectronics and photonics packaging where size stability and geometry alignment are highly demanded. Therefore, characterization of creep fracture behaviour of solders and their joints is significant to the reliability evaluation and lifetime prediction of the packaging systems. Moreover, recently, traditional tin-lead eutectic systematic solders meet another serious challenge, that is, the increasing global concern on the environment and health, which is bringing regulatory and consumer pressure on the electronic and communication industry in developed countries to reduce or completely eliminate the use of toxic lead in most products [Plumbridge, 1996; Shangguan et al., 1997; Hua et al., 1997; Richards et al., 1999; Dorn et al., 2000; Bradley et al., 2001; Chen et al., 2002; Tu et al., 2003]. Thus, the research in replacing conventional Pb-contained solders has drawn more attention, Corresponding author. Fax: 086-20-87114484; Emails: mexzhang@scut.edu.cn or xzhang@aeromech.usyd.edu.au

not only from the science and engineering community, but also from the public. For solders, lead (Pb) is a major constituent of traditional solders which have very good soldering process performance and satisfied joint properties. However, toxicity is the main reason for Pb to be eliminated from many applications. The possibility of removing the constituent Pb from tin-lead based solders has highlighted a whole series of questions associated with professional knowledge and technical expertise, as well as dissemination of existing information, materials availability, soldering technology and equipment, implementation of any new technology, added costs and competitiveness etc [Richards et al., 1999; Chen et al., 2002; Tu et al., 2003; Zhang et al., 2004a]. As known, Sn-Ag and Sn-Sb alloy systems are the most likely candidates for the substitution of Sn- Pb solders. Currently in optoelectronics and photonics packaging, Au-based solders (such as a binary eutectic solder 80Au-20Sn, with a melting-point of 278 C) are widely employed to solder the joints or interconnections to ensure the dimensional stability (or alignment) of the devices or systems [Shi, 2000; Elger et al.,2002]. With offering excellent creep resistance, however, the high soldering temperatures of these solders can deteriorate the properties of optical fibers and other optoelectronic or photonic components besides the high cost of Au-based solders. Therefore, it is expected to develop the solders with excellent creep resistance while lead-free. In this work, the creep behaviour of a newly developed nano-composite solder reinforced by nano-sized metallic particulates and a lead-free Sn-Ag-Bi alloy solder was characterized, with a comparison to a traditional Sn60Pb40 solder, and the creep fracture mechanisms of different solder joints were analysed. 2 MATERIALS AND EXPERIMENTAL In this research three solders were used for comparative studies, that is, a tin-lead based composite solder reinforced by nano-sized Ag particulates, a lead-free Sn-Ag-Bi alloy solder and an Sn60Pb40 solder close to eutectic composition. Table 1 lists the nominal compositions of the solders. The nano-composite solder was fabricated by mixing nano-sized Ag powders (with a nominal size of 25~35 nm) with Sn60Pb40 powder (with an average size of 43 µm) [Zhang et al., 2004b]. The leadfree Sn-Ag-Bi solder was in continuous foil form manufactured by a rapid quenching technique (with a thickness of 50 µm). Sn60Pb40 solder was commercially available. The melting-points of the solders were measured by a modulated DSC (TA-Instruments) with a heating rate of 20 C/min, as shown in Table 1. Miniature copper dogbone-shaped lap shear joint specimens, with a gauge length of 10 mm, were used for creep testing, as shown in Figure 1. The single overlap soldered joint was in the middle of the specimen s gauge part. This specimen geometry is very close to the geometry of real solder connections in electronic packaging. The creep tests were conducted using a Dynamic Mechanical Analyzer (DMA 2980 model - TA Instruments) under a constant applied stress of 18 MPa at three different test temperatures, that is, 35, 55 and 75 C, respectively. Table 1. Solder alloy systems and their melting-points Solders Melting-point Fabrication method Nano-composite solder: Sn60Pb40-Ag (<3% wt) 183.8 C By mixing alloy powders Lead-free solder: Sn-Ag-Bi (Ag+Bi, <8% wt) 210.6 C By rapid quenching Eutectic Sn60Pb40 solder 183.3 C Commercially available

0.10 Over-lap 1 mm 1 10 20 40 Figure1: The miniature copper dogbone-shaped lap shear joint specimen for creep test 6 3 RESULTS AND DISCUSSION 3.1 Characteristics of creep fracture behaviour of soldered joints The creep behaviours of the soldered joints were characterized by measuring the evolution of strain with elapsed time under a given temperature and a constant stress. Typical creep curves of strain versus time for Sn60Pb40 and nano-composite solder joints subjected to a constant stress of 18 MPa at 35, 55 and 75 C, respectively, are shown in Figure 2. Both solders show the expected creep deformation characteristics, that is, three regimes of primary, secondary and tertiary creep, at all test temperatures. For the secondary steady-state creep regime, the creep rate follows the stressdependent power law given by: dε n ε = = Cσ (1) dt where ε is creep strain, σ applied stress, C a numerical constant, and n a stress-exponent. The total time for creep rupture at the end of the tertiary regime is defined as the creep lifetime of the solder joints, which, for these two kinds of solders, clearly decreases with temperature. It can also be seen that incorporation of less than 3 wt% of nano-sized Ag does not change the melting-point of the nano-composite solder, while has significantly increased the creep lifetimes of the solder joints relative to the Sn60Pb40 solder joints without the nano-fillers at all test temperatures. 3.0 2.5 75 55 35 C 3.0 2.5 55 35 75 C 2.0 2.0 Strain [%] 1.5 1.0 Strain [%] 1.5 1.0 0.5 0.5 0.0 0 50 100 150 200 250 300 Time [min] 0.0 0 50 100 150 200 250 300 350 400 450 Time [min] (a) Sn60Pb40 solder joints (b) Nano-composite solder joints Figure 2: Creep curves of solder joints at three test temperatures.

Figure 3 compares the creep curves of Sn60Pb40, SnAg3.5Bi4 and nano-composite solder joints under a tensile stress of 18 MPa at 75 C. It is clear that lead-free SnAg3.5Bi4 solder has outperformed the Sn60Pb40 solder and the nano-composite solder. At lower test temperatures of 35 and 55 C, SnAg3.5Bi4 solder joints performed even better. For example, at the same applied stress of 18 MPa the solder does not fail after 100 hours (which is near the capacity of the DMA machine used for the creep tests). However, SnAg3.5Bi4 solder has a higher melting-point than other two solders (i.e., about 27 C higher). 4.0 3.5 Sn60Pb40 Sn-Ag-Bi Nan0-comp. 75 C 3.0 2.5 Strain [%] 2.0 1.5 1.0 0.5 0.0 0 50 100 150 200 250 300 350 400 Time [min] Figure 3: Comparison of the creep behaviours of three solder joints at 75 C and 18 MPa. 3.2 Creep failure mechanisms of Sn60Pb40, SnAg3.5Bi4 and nano-composite solder joints The fracture surfaces of the Sn60Pb40, nano-composite and lead-free SnAg3.5Bi4 solder joints after creep rupture are given Figs. 4 and 5. They are apparently different. Sn60Pb40 joints deform dominantly by transgranular sliding along shear stress direction, Figure 4(a), where obvious sliding fracture characteristics exists. However, SnAg3.5Bi4 and nano-composite solder joints are most likely to fail by inter-granular mechanisms, such as grain boundary sliding and void growth particularly at triple points. Thus, SnAg3.5Bi4 solder ruptures by formation of grain boundary wedge cracks as in Figure 5; and the nano-composite solder fails by cavitation due to the nano-sized Ag particles as shown in Figure 6. Creep in metals is a slow-rate plastic deformation process and creep rupture occurs mainly by 3 mechanisms: (a) intergranular failure, which is the most common mechanism for long-term rupturel (b) transgranular failure, which applies to short-term rupture; and (c) point rupture due to dynamic recovery or recrystallization at very high temperatures and low stress levels. As shown in Figs. 4 to 6, SnAg3.5Bi4 and nano-composite solder joints failed by intergranular creep. Note that the leaded solder, Sn60Pb40, fails by transgranular creep. However, addition of nano-ag changes this to intergranular failure with improved creep resistance and ductility, Figure 3. It is suggested that the nano particles uniformly dispersed in the leaded solder matrix provide effective impedance to grain boundary sliding and motions of dislocations. Very importantly, the diffusion of Ag and Cu atoms to Sn-Pb matrix enhances the alloying effect besides the benefit in reducing the surface tension of the solder [Zhang et al., 2004a]. This will increase the solder elasticity modulus which affects the creep performance. This comment of Cu diffusion also applies to the lead-free SnAg3.5Bi4 solder.

Sliding facets load direction load direction Grown voids Boundary sliding (a) Sn60Pb40 solder joint (b) Nano-composite solder joint Figure 4: Fracture morphology of two solder joints after creep rupture at 75 C. load direction Grain boundary wedge microcracks Figure 5: Fracture morphology of lead-free SnAg3.5Bi4 solder joint after creep rupture at 75 C, showing grain boundary wedge cracks. 280 nm Particulate caused cavities Figure 6: Morphology of fractography of the nano-composite solder joint after creep failure

4. CONCLUSIONS (1) The solder joints show similar creep characteristics as bulk materials. (2) Sn60Pb40 solder joints deform dominantly by transgranular sliding, while SnAg3.5Bi4 and nano-composite solder joints rupture by intergranular mechanisms via grain boundary sliding and void growth at triple points. (3) Sn-Pb-Ag nano-composite solder joint has superior creep resistance to Sn60Pb40 solder. This is largely due to the uniformly dispersed nano-sized Ag particles that have provided effective impediment to dislocation movement and grain boundary sliding, in addition to the alloying effect. (4) Lead-free SnAg3.5Bi4 solder has superior creep resistance and creep lifetime than both Sn60Pb40 and Sn-Pb-Ag nano-composite solders. Its joint fails by intergranular creep mainly via formation of grain boundary wedge cracks. ACKNOWLEDGEMENT: This research is performed in collaboration with Prof. L. Dorn and Dr.-Ing. S. Shrestha at Institute of Materials Processing and Surface Engineering, Technical University Berlin, Germany. REFERENCES Bradley, E and Hranisavljevic, J, Characterization of the melting and wetting of Sn-Ag-X solders, IEEE Transactions on Electronic Packaging Manufacturing, 24, 255 (2001). Chen, Z G, Shi, Y W and Xia, Z D, Study on the microstrucutre of a lead-free solder alloy Sn-Ag-Cu-RE and its soldered joints, Journal of Electronic Materials, 31, 1122 (2002). Dorn, L, Herbert, F and Shrestha, S, Pb-free solders under the laser beam, Proc. of System Integration in Micro Electronics, Exhib. & Conf., Nuernberg, Germany, 27-29 July 2000, 349-357. Elger, G, Hutter, M, Oppermann,H, Aschenbrenner, R, Reichl, H, and Jaeger, E, Development of an assembly process and reliability investigations for flip-chip LEDs using the AuSn soldering, Microsystem Technologies, 7, 239 (2002) Hua, F and Glazer, J, Lead-free solders for electronic assembly, Design and Reliability of Solder Interconnections, Mahidhara, R K, Frear, D R, Sastry, S M L et al., Eds., The Minerals, Metals and Materials Society, Pennsylvania, USA, 65-73 (1997). Plumbridge, W J, Solders in electronics, Journal of Materials Science, 31, 2501 (1996). Richards, B P, Levoguer C L, Hunt, C P, Nimmo, K, Peters, S and Cusack, P, Lead-free soldering-an analysis of the current status of lead-free soldering, Rept., Dept. Trade & Industry, 1-80 (1999). Shangguan, D and Gao, G, Lead-free and no-clean soldering for automotive electronics, Soldering and Surface Mount Technology, 26, 5 (1997). Shi, Y W, Creep-fatigue resistant solders for optoelectronic materials joining, China-European Union Workshop on Materials Strategy for New Millenium, Beijing, China, 8 Dec. 2000, 39-43. Tu, K N, Gusak, A M and Li, M, Physics and materials challenges for lead-free solders, Journal of Applied Physics, 93, 1335 (2003). Zhang X P, Wang, H and Shi, Y W, Influence of minute amount of elements Bi, Ag and In on surface tension and soldering process performance of tin-lead based solders, Journal of Materials Science: Materials in Electronics, 15, 511(2004a). Zhang, X P, Shi, Y W, Ye, L and Mai, Y W, A tin-based composite solder reinforced by nano-sized particulates and its soldering ability, Composites Technologies for 2020, Proceedings of the 4th Asian- Australasian Conference on Composite Materials (ACCM-4), July 2004, Sydney, Australia, 645 (2004b)