Influence of Thermal Cycling on the Microstructure and Shear Strength of Sn3.5Ag0.75Cu and Sn63Pb37 Solder Joints on Au/Ni Metallization

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1 68 J. Mater. Sci. Technol., Vol.23 No.1, 2007 Influence of Thermal Cycling on the Microstructure and Shear Strength of Sn3.5Ag0.75Cu and Sn63Pb37 Solder Joints on Au/Ni Metallization Hongtao CHEN 1,2), Chunqing WANG 1), Mingyu LI 3) and Dewen TIAN 1) 1) Microjoining Lab., School of Materials Science and Engineering, Harbin Institute of Technology, Harbin , China 2) Department of Materials Science and Engineering, Jiamusi University, Jiamusi , China 3) Harbin Institute of Technology, Shenzhen Graduate School, Shenzhen , China [Manuscript received November 8, 2005, in revised form April 24, 2006] The influence of thermal cycling on the microstructure and joint strength of Sn3.5Ag0.75Cu (SAC) and Sn63Pb37 (SnPb) solder joints was investigated. SAC and SnPb solder balls were soldered on 0.1 and 0.9 µm Au finished metallization, respectively. After 1000 thermal cycles between 40 C and 125 C, a very thin intermetallic compound (IMC) layer containing Au, Sn, Ni, and Cu formed at the interface between SAC solder joints and underneath metallization with 0.1 µm Au finish, and (Au, Ni, Cu)Sn 4 and a very thin Au- Sn-Ni-Cu IMC layer formed between SAC solder joints and underneath metallization with 0.9 µm Au finish. For SnPb solder joints with 0.1 µm Au finish, a thin (Ni, Cu, Au) 3 Sn 4 IMC layer and a Pb-rich layer formed below and above the (Au, Ni)Sn 4 IMC, respectively. Cu diffused through Ni layer and was involved into the IMC formation process. Similar interfacial microstructure was also found for SnPb solder joints with 0.9 µm Au finish. The results of shear test show that the shear strength of SAC solder joints is consistently higher than that of SnPb eutectic solder joints during thermal cycling. KEY WORDS: Sn3.5Ag0.75Cu; Solder joint; Au finish; Intermetallic compound 1. Introduction Solder joints reliability has drawn tremendous attention because they not only transfer electrical signals and thermal energy from the devices, but also maintain the mechanical integrity. With increasing pressure of legislation and commercial advantages associated with environment-friendly electronics, Pbfree solders were extensively studied in last decades due to the environmental and public concerns for Pbbearing solders [1]. Generally, high Sn alloys are chosen as Pb-free solder, such as Sn-Ag, Sn-Cu, Sn-Ag- Cu, Sn-Ag-Bi, Sn-Ag-In [2]. Most Pb-free solders are based on Sn-3.5Ag solder, and Sn3.5Ag0.75Cu (SAC) solder is one of most promising candidates as replacement for conventional SnPb solder for its mechanical properties and creep resistance [3,4]. On the other hand, Au finish is also extensively used as a protection layer to prevent underlying layer from oxidation and to facilitate solder wetting [5 14]. During the soldering process, the Au finish is dissolved into the solder or reacts with Sn of the solder to form Au-containing intermetallic compounds (IMCs) at the interface or in the solder bulk depending on the Au content in solder and soldering time and temperature [5 14]. It is well known in the electronic packaging industry that if the Au content in a solder exceeds 5 wt pct, it results in a large fraction of Au-Sn IMCs formation, leading to Au-embrittlement or cold joint [15]. This brings us the question for the interconnections of smaller dimensions of future electronic packages since the geometrical structure of Au finish increases more than the solder volume with decreasing solder interconnection size [7,16]. Moreover, Au surface finishes less than Ph.D., to whom correspondence should be addressed, chenht@hit.edu.cn. 0.5 µm in thickness have been considered too porous to provide effective protection because the pinholes in Au layer may cause oxidation of the pad [17]. Thus, Au content in the solder inevitably exceeds its solubility limit for some solder joints with reduced dimensions. Therefore, it is of great importance to study the microstructure of small solder joints with different Au concentration. In this study, the microstructure, IMC morphology evolution and the joint strength of small SAC solder balls with two Au finish thicknesses under thermal cycling were investigated, and SnPb solder was also used for the sake of comparison with Pb-free solder. 2. Experimental A vacuum nozzle with image processing software was used to align SAC or SnPb solder ball (120 µm in diameter) with a rectangular pad with a dimension of 145 µm 138 µm. Subsequently, a Nd:YAG laser with 35 mj pulse energy was adopted for reflow soldering. Au surface finishes with two thicknesses, 0.1 and 0.9 µm, were coated on Cu Pad for Au/Ni metallization. The Ni thickness was 0.2 µm. A thermal shock chamber, TSK-D3L+, was used to perform temperature cycling test. The temperature cycling was performed in a temperature range between 40 C and 125 C. The ramp rate was about 16.5 /min and the dwell times at each extreme temperature were about 20 min. The duration of each cycle was 1 h. The samples were sectioned, ground and polished with 0.1 µm diamond suspension after being mounted in epoxy, and then were slightly etched with 2 vol. pct HCl+98 vol. pct C 2 H 5 OH solution for several seconds to distinguish the different phases. JSM- 6301F scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDX)

2 J. Mater. Sci. Technol., Vol.23 No.1, Fig.1 SEM images of SAC solder joints with 0.1 µm Au finish at different thermal cycles: (a) 0, (b) 100, (c) 500, was used to characterize the microstructure and IMC formed in the solder joints. Backscattered electron (BSE) mode was used for the cross-sectioned samples. The shear strengths of solder joints before and after thermal cycling were measured by PTR-1000 shear tester. The shear test was performed at the rate of 50 µm/s and the shear height above pad is 20 µm. For each condition, 20 measurements were taken to calculate the average value. The fracture surfaces after shear test were characterized by SEM in secondary electron (SE) mode. 3. Results and Discussion Cross-sections for solder joints at different thermal cycles were characterized by BSE mode, which revealed the different phases more clearly than the SE images because of the improved atomic number contrast. SAC solder joints with 0.1 µm Au finish at different thermal cycles are shown in Fig.1, and a little IMC was formed at the interface even after 1000 thermal cycles. The IMC formed at the interface was so thin that the exact atomic ratio cannot be determined by EDX, and the constitutions were identified to be Au, Sn, Ni, and Cu. However, obvious coarsening of Ag 3 Sn particles in the solder bulk took place with increasing the number of thermal cycle. As for SAC solder joints with 0.9 µm Au finish, as shown in Fig.2, needle-type IMC remained at the interface after reaction with Au for the as-soldered sample and its composition was identified as (Au, Ni, Cu)Sn 4 with small amount of Ni and Cu. The concentration of Ni and Cu was less than 3 wt pct even after 1000 thermal cycles. The formed (Au, Ni, Cu)Sn 4 changed gradually from needle-type to layer-type by incorporating with each other. Interface between IMC and solder became smoother and the thickness of IMC increased at the same time. In the wetting reactions, the needle-type IMC is stable in contact with molten solder, but the layer-type IMC is more stable in contact with solid solder. In view of kinetics, needle-type morphology has a larger contacting surface with solder bulk than with a flat surface. Therefore, in the wetting reaction, the rapid gain in compound formation may compensate the surface energy spent in growing the needletype IMC. However, in the solid state reactions, the gain disappears, and the IMC changes to a layer-type with a flat surface because of the high interfacial energy between solid solder and IMC. In addition, a very thin IMC layer containing Au, Sn, Ni, and Cu formed below the (Au, Ni, Cu)Sn 4 IMC layer. As for the eutectic SnPb solder, significant coarsening of the Sn and Pb microstructure after thermal cycles was found, as shown in Fig.3. A thin (Au, Ni)Sn 4 IMC layer with about 10 at. pct Ni formed after 1000 thermal cycles for 0.1 µm Au finish, and Pbrich phases were developed on the top of (Au, Ni)Sn 4 IMC because Sn in solder was involved into the metallurgical reaction with Au, and then Pb was left at the interface to form Pb-rich phases adjacent to the IMC layer. Moreover, a thin dark grey layer, which was denoted as (Ni, Cu, Au) 3 Sn 4 with 11 at. pct Au, 61 at. pct Sn, 16 at. pct Ni, and 12 at. pct Cu, formed below the (Au, Ni)Sn 4 layer. There was no Cu in SnPb solder, so the Cu in the quaternary (Ni, Cu, Au) 3 Sn 4 IMC indicates that Cu diffused through Ni layer and was involved into the IMC formation process. It is assumed that Ni has a columnar structure, which offers the pathway for Cu diffusion [18]. For SnPb solder joint with 0.9 µm Au finish, as shown in

3 70 J. Mater. Sci. Technol., Vol.23 No.1, 2007 Fig.2 SEM images of SAC solder joints with 0.9 µm Au finish at different thermal cycles: (a) 0, (b) 100, (c) 500, Fig.3 SEM images of SnPb solder joints with 0.1 µm Au finish at different thermal cycles: (a) 0, (b) 100, (c) 500, Fig.4, what differentiates with 0.1 µm Au finish is that the needle-type AuSn 4 IMC was formed in the as-soldered state, and enwrapped by Pb-rich phases. It is interesting to note that the needle-type IMCs are much thinner than those formed in Pb-free solder joints. The possible reason is that the limited Sn supply near the interface after excessive reaction with Au and separation of Pb-rich pahses in SnPb solder joints

4 J. Mater. Sci. Technol., Vol.23 No.1, Fig.4 SEM images of SnPb solder joints with 0.9 µm Au finish at different thermal cycles: (a) 0, (b) 100, (c) 500, Fig.5 Shear strength of solder joints with different Au thicknesses at different thermal cycles resulted in the thinner AuSn 4 IMC needle at the interface, while the Sn supply in SAC solder, which is a high-tin based solder alloy, is adequate to support the needle growth at the interface. The needle-type IMC integrated with each other, and formed a continuous (Au, Ni)Sn 4 layer, under which a thin (Ni, Cu, Au) 3 Sn 4 IMC layer formed, similar to those found in Pb-free solder joints with 0.1 µm Au finish. The Pbrich phases were also developed on the top of (Au, Ni)Sn 4 layer after 1000 thermal cycles. The shear strength of solder joints with different solders and Au finish thickness as a function of thermal cycle is shown in Fig.5. The solder joint strength for SAC solder was consistently higher than that of SnPb solder, which proved a good mechanical behavior of SAC solder joints. The shear strengths of SAC solder joint with 0.1 and 0.9 µm Au finish show similar trend, and cannot be distinguished with each other. The SAC solder joint strength decreased rapidly before 200 thermal cycles, and the decrease slowed down with further thermal cycles thereafter. The possible reason is that the significant coarsening of microstructure in SAC solder joints leads to the initial load drop. Opposite to the trend of Pb-free solder, the shear strengths for SnPb solder joints were increased a little or kept unchanged before 200 thermal cycles, and then decreased slowly thereafter. After shear test, fractography of the solder joints after 1000 thermal cycles was observed by SEM. As shown in Fig.6, detailed examination found that fractures occurred mostly through the solder region in the SAC and SnPb solder joints with 0.1 µm Au finish, while fracture occurred partly through (Au, Ni)Sn 4 and (Au, Ni, Cu)Sn 4 IMC for SnPb and SAC solder joints with 0.9 µm Au thickness, respectively. Generally, whether the fracture occurs through interfacial IMC or solder is determined by two factors. One is where the stress is concentrated. The other is the joint characteristic, such as IMC thickness and solder hardness. Solder joints with 0.9 µm Au finish had a thicker IMC than solder joints with 0.1 µm Au finish, and cracks may easily initiate at the IMC layer when stress concentrated at these area. However, the IMC thickness in solder joints does not much affect the solder joint strength. The possible reason is that the IMC formed in the solder joint is thin, and the proportion of IMC exposed on the fractography is not so significant. As a result, the solder hardness played a more important role in determining the shear strength, so the solder joint strength for SAC solder was consistently higher than that for SnPb solder.

5 72 J. Mater. Sci. Technol., Vol.23 No.1, 2007 Fig.6 Shear fractographies of solder joints with different solders and Au thicknesses after 1000 thermal cycles: (a) SnPb solder with 0.1 µm Au finish, (b) SnPb solder with 0.9 µm Au finish, (c) SAC solder with 0.1 µm Au finish, (d) SAC solder with 0.9 µm Au finish 4. Conclusions (1) For the SAC solder joints with 0.1 µm Au finish, very thin IMC was formed at the interface, and constitutions were identified to be Cu, Ni, Au and Sn. Obvious coarsening of Ag 3 Sn particles took place with the increase in the number of thermal cycles. (2) For the SAC solder joint with 0.9 µm Au finish, the morphology of (Au, Ni, Cu)Sn 4 IMC changed gradually from needle-type to layer-type, and very thin IMC layer containing Au, Sn, Ni, and Cu formed below the (Au, Ni, Cu)Sn 4 IMC layer after 1000 thermal cycles. (3) As for SnPb solder joints, significant coarsening of the Sn and Pb microstructure took place during thermal cycling. For SnPb solder joint with 0.1 µm Au finish, a thin (Ni, Cu, Au) 3 Sn 4 IMC layer formed below the (Au, Ni)Sn 4 layer. For SnPb solder joint with 0.9 µm Au finish, the needle-type AuSn 4 IMC formed in the as-soldered state, and enwrapped by the Pb-rich phase. The needle-type IMC integrated with each other and formed similar interfacial microstructure to those in SnPb solder joints with 0.1 µm Au finish after 1000 thermal cycles. (4) The solder joint strength for SAC solder was consistently higher than that for SnPb solder. Fractures occurred mostly through the solder region in the SAC and SnPb solder joints with 0.1µm Au finish after 1000 thermal cycles, while fracture occurred partly through IMC at some locations for both SAC and SnPb solder joints with 0.9 µm Au thickness. However, it does not affect the solder joint strength much. REFERENCES [1 ] K.Zeng and K.N.Tu: Mater. Sci. Eng. R, 2002, 38, 55. [2 ] M.Abtew and G.Selvaduray: Mater. Sci. Eng. R, 2000, R27, 95. [3 ] D.Suraski and K.Seelig: IEEE. T. Electron. Pack., 2001, 24, 244. [4 ] W.K.Choi, J.H.Kim, S.W.Jeong and H.M.Lee: J. Mater. Res., 2002, 17, 43. [5 ] A.M.Minor and J.W.Morris: J. Electron. Mater., 2000, 29, [6 ] C.E.Ho, R.Zheng, G.L.Luo, A.H.Lin and C.R.Kao: J. Electron. Mater., 2000, 29, [7 ] J.H.Lee, J.H.Park, D.H.Shin, Y.H.Lee and Y.S.Kim: J. Electron. Mater., 2000, 30, [8 ] C.E.Ho, Y.M.Chen and C.R.Kao: J. Electron. Mater., 1999, 28, [9 ] F.Zhang, M.Li, C.C.Chum and Z.C.Shao: J. Electron. Mater., 2003, 32, 123. [10] K.Y.Lee and M.Li: J. Electron. Mater., 2003, 32, 906. [11] D.G.Kim, J.W.Kim, J.G.Lee, H.Mori, D.J.Quesnel and S.B.Jung: J. Alloy. Compd., 2005, 395, 80. [12] J.W.Yoon, S.W.Kim and S.B.Jung: J. Alloy. Compd., 2005, 391, 82. [13] M.N.Islam and Y.C.Chan: Mater. Sci. Eng. B, 2005, 117, 246. [14] Y.H.Tian, C.Q.Wang, X.S.Ge, P.Liu and D.M.Liu: Mater. Sci. Eng. B, 2002, 95, 254. [15] K.N.Tu and K.N.Zeng: Mater. Sci. Eng. R, 2001, 34, 43. [16] U.B.Kang and Y.H.Kim: J. Electron. Mater., 2004, 33, 61. [17] K.C.Hung, Y.C.Chan, H.C.Ong, P.L.Tu and C.W.Tang: Mater. Sci. Eng. B, 2000, 76, 87. [18] C.S.Huang, J.G.Duh, Y.M.Chen and J.H.Wang: J. Electron. Mater., 2003, 32, 89.

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