Journal of Alloys and Compounds 391 (2005) 8289

Interfacial reaction and mechanical properties of eutectic Sn0.7Cu/Ni BGA solder joints during isothermal long-term aging
Jeong-Won Yoon, Sang-Won Kim, Seung-Boo Jung
Department of Advanced Materials Engineering, Sungkyunkwan University, 300 Cheoncheon-dong, Jangan-gu, Suwon 440-746, South Korea Received 18 August 2004; accepted 2 September 2004 Available online 12 October 2004

Abstract The interfacial reactions and growth kinetics of intermetallic compound (IMC) layers formed between Sn0.7Cu (wt.%) solder and Au/Ni/Cu substrate were investigated at aging temperatures between 70 and 170 C for up to 100 days. After reow, the IMC formed at the interface was (Cu,Ni)6 Sn5 . In addition, only this (Cu,Ni)6 Sn5 layer was observed in the samples aged at temperatures between 70 and 150 C. On the other hand, after isothermal aging at 170 C for 50 days, the solder/Ni interface exhibited a duplex structure of (Cu,Ni)6 Sn5 and (Ni,Cu)3 Sn4 . The time exponents (n) determined at temperatures below 150 C were about 0.2. The determined n values are presumably related to a grain boundary diffusion-controlled mechanism. In the ball-shear tests, the shear strength signicantly decreased after aging for initial 1 day, after which it remained nearly unchanged through further prolonged aging. In all samples, fracture occurred in the bulk solder. 2004 Elsevier B.V. All rights reserved.
Keywords: Sn0.7Cu solder; Ball-grid-array (BGA); Interfacial reaction; Intermetallic compound (IMC); Ball-shear test

1. Introduction Solder is widely used to connect chips to their packaging substrates in ip-chip technology as well as in ball-grid-array (BGA) technology [1]. In the last 50 years, the electronics industry has relied mainly on one type of solder (SnPb solder) in the manufacturing of computer chips, circuitry, and other electronic equipment [2]. With the discovery of lead (Pb) as a contaminant both to the environment and to human health, new developments have been made to steer away from the use of SnPb solder [3,4]. Among many Pb-free solder alloys, the eutectic SnCu solder (Sn0.7Cu wt.%) is considered the most promising candidate alloy to replace the eutectic SnPb solder for wave soldering [1,5]. In 2000, National Electronics Manufacturing Initiative (NEMI) recommended to replace eutectic SnPb solder by eutectic SnAgCu solder in reow processing and eutectic SnCu solder in wave soldering [1]. In addition, the Sn0.7Cu solder was also identied as a better alloy for ip-chip soldering compared to Sn3.5Ag and Sn3.8Ag0.7Cu [6].

Corresponding author. Tel.: +82 31 290 7359; fax: +82 31 290 7371. E-mail address: sbjung@skku.ac.kr (S.-B. Jung).

Copper is widely used in the under bump metallurgy and substrate metallization for ip-chip and BGA applications. It is known that at the Cu/solder interface, Sn reacts rapidly with Cu to form CuSn intermetallic compounds (IMC), which weakens the solder joints due to the brittle nature of the IMC [7]. Therefore, Ni is used as a diffusion barrier layer to prevent the rapid interfacial reaction between solder and Cu layer in electronic devices. One of the major concerns of BGA technology is the solder joint reliability. Since solder joints are often subjected to mechanical loadings during handling and system use, the mechanical properties of solder joints, such as the fatigue and shear strengths, are the crucial issue for solder joint reliability and the integrity of electronic packaging. High ambient temperatures on the solder joint result in the growth of unwanted IMCs, which weakens the solder joint strength because of their brittleness and weakness [3]. Therefore, it is necessary to understand and control the factors that govern the kinetics of the interfacial reaction. Recently, many studies on the SnCu solder alloy have been reported in the literature [5,6,812]. Nevertheless, the knowledge of solidstate interfacial reaction and shear strength of the solder on Ni metallized Cu substrate remains insufcient. Therefore,

0925-8388/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2004.09.001

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this study focused on the interfacial reaction between eutectic Sn0.7Cu solder and Au/Ni metallized Cu BGA substrate during solid-state aging. In addition, the shear strengths of the solder joints were tested as a function of the time and temperature for isothermal aging. The correlations between the shear strength and their corresponding interfacial reaction on the solder joints are discussed.

2. Experimental procedures BGA solder used in this study was an eutectic Sn0.7Cu (wt.%) solder with a diameter of 500 m. The alloy has an eutectic temperature of 227 C. The substrate was a BT (Bismaleimide Triazine) laminate with subsurface solder bond pads whose nominal size and shape were dened through a circular opening of 460 m diameter. The pad was constructed by electroplated Au/Ni over an underlying Cu pad in thickness of 0.5 and 8.5 m, respectively. The SnCu solder ball was bonded to the BT substrate in a reow process employing rosin mildly activated (RMA) ux in an infrared

four-zone reow machine (RF-430-N2, Japan Pulse Laboratory Ltd. Co.) with a maximum temperature of 250 C for 60 s. Each BGA solder joint was then placed in an oven maintained at a constant aging temperature. The temperature homogeneity for each oven was better than 1 C. Five aging temperatures, 70, 100, 120, 150, and 170 C, were used in this study. The aging times ranged between 1 and 100 days. Upon completion of the aging step, the samples were mounted in epoxy and metallographically polished for micro-structural characterization. The micro-structural and chemical analyses of the samples were obtained by using Philips XL 40 FEG scanning electron microscopy (SEM) equipped with energydispersive X-ray analysis (EDX). The compositions of the phases formed at the interface were determined by a JEOL JXA-8900R electron probe micro analyzer (EPMA, Tokyo, Japan). The layer thickness was evaluated using image analysis software to measure the total area of the inter-metallic layer. The phase areas were divided by the boundary length shown in the cross-section to yield the average layer thickness. In addition, the shear test was performed on reowed and aged samples using a shear tester (Rhesca Co. Ltd., PTR-

Fig. 1. SEM micrographs of the Sn0.7Cu solder/Ni BGA joints aged at 170 C for various times: (a) as-reowed, (b) 6 days, (c) 15 days, (d) 30 days, (e) 50 days, and (f) 100 days.

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Fig. 2. SEM micrographs of the Sn0.7Cu solder/Ni BGA; Joints after aging for 100 days at various temperatures: (a) 70 C, (b) 100 C, (c) 150 C, and (d) 170 C.

1000). The shear tool height of 50 m and shear speed of 200 m/s were used. For every data point, at least 20 measurements were made and the average value was reported. After the ball-shear test, the fracture surfaces were investigated thoroughly by SEM and EDX.

3. Results and discussion Fig. 1 shows the SEM micrographs of the interface between Sn0.7Cu solder and Ni/Cu BGA substrate aged at 170 C for different aging times. Back-scattered electron images of SEM were used to provide more distinguishable boundaries of the interfacial layers. During the reow process, the entire Au layer was dissolved into the molten solder, leaving the Ni layer exposed to the molten solder. The reaction between molten solder and Ni layer formed a (Cu,Ni)6 Sn5 layer at the interface. The Cu in the (Cu,Ni)6 Sn5 layer came from the solder inside because there is no Cu source except the solder. It means that this IMC is Cu6 Sn5 containing some substitutional Ni in its lattice. The CuNi binary system forms a complete solid solution [13]. As the atomic size difference between Cu and Ni is only 2% and both have the same FCC lattice structure, the substitution of Ni into Cu6 Sn5 without causing lattice distortion or new phase formation is reasonable [14]. Therefore, in the Sn0.7Cu solder, the reaction of Cu and Sn is so important that it determines the

formation of (Cu,Ni)6 Sn5 IMC, even though the Cu content in the solder is very low (0.7 wt.%). In the as-reowed joints, the mean thickness of the (Cu,Ni)6 Sn5 layer was approximately 0.8 m. The composition at the center of the relatively big (Cu,Ni)6 Sn5 IMC grains was analyzed and found to be composed of 33.01 at.% Cu, 21.1 at.% Ni, and 45.89 at.% Sn. Fig. 2 shows the SEM micrographs of the interfaces after 100 days of aging at various temperatures. In this study, only the (Cu,Ni)6 Sn5 IMC layer was observed in the samples aged at temperatures between 70 and 150 C. This (Cu,Ni)6 Sn5 IMC was composed of 3335 at.% Cu, 1821 at.% Ni, and 4647 at.% Sn. On the other hand, after isothermal aging at 170 C for 50 days, the solder/Ni interface exhibited a duplex structure of (Cu,Ni)6 Sn5 and (Ni,Cu)3 Sn4 , as shown in Fig. 1(e) and (f). The (Ni,Cu)3 Sn4 IMC layer started to form under the (Cu,Ni)6 Sn5 IMC. The formation of the (Ni,Cu)3 Sn4 IMC must have been caused by the decrease of Cu diffusion into the interface. A similar observation was reported recently in the literature [9]. Jeon et al. investigated the interfacial reactions and reliability of three widely used Pb-free solder bumps (Sn3.5Ag, Sn4.0Ag0.5Cu, and Sn0.7Cu) on the electroless NiP layer. According to the results of their study, in Sn0.7Cu solder bump, only (Cu,Ni)6 Sn5 IMC was observed after aging at 175 C for 500 h, while two IMCs of (Cu,Ni)6 Sn5 and (Ni,Cu)3 Sn4 were observed after aging at 200 C. Unfortunately, in this study, the interface between these two layers

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Fig. 3. EPMA line proles of the Sn0.7Cu solder/Ni interfaces: (a) as-re-owed and (b) aged at 170 C for 100 days.

was not observed in the micrograph. To identify these two phases found in the solder joint, EPMA analyses were performed. According to the EPMA measurements, the compositions for these two layers were (Cu0.65 Ni0.35 )6 Sn5 and (Ni0.86 Cu0.14 )3 Sn4 , respectively. The growth of the IMC layer at temperatures between 70 and 150 C was much slower than that in the case of aging at 170 C, as shown in Fig. 2. In cases of samples aged at

150 and 170 C for 100 days, the thickness of the total IMC layer was about 2.1 and 8.9 m, respectively. As shown in Figs. 1 and 2, as the aging conditions became more severe, the IMC layer grew. As a whole, all IMCs formed at the interface were well attached on the Ni substrate. Fig. 3 (a) and (b) shows the results of EPMA line prole of the Sn0.7Cu/Ni interface reowed and aged at 170 C for 100 days, respectively. This EPMA result clearly conrmed

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J.-W. Yoon et al. / Journal of Alloys and Compounds 391 (2005) 8289 Table 1 Calculated time exponents (n) Temperature ( C) 70 100 120 150 170 n 0.22 0.22 0.18 0.23 0.42

The time exponents were evaluated using the following equation representing the growth kinetics at each aging temperature: Y = At n + B (2)

Fig. 4. Thickness of the total IMC layer with aging temperature and time.

where Y is the layer thickness, t the reaction time, n the time exponent, A a constant, and B the layer thickness at t = 0. This equation was converted into a logarithmic expression: ln (Y B) = n ln t + ln A (3)

the coexistence of (Cu,Ni)6 Sn5 and (Ni,Cu)3 Sn4 layers in the sample aged at 170 C for 100 days. The (Ni,Cu)3 Sn4 layer grew by the reaction of the Ni and (Cu,Ni)6 Sn5 layers. According to EPMA line analysis, the thickness of the (Ni,Cu)3 Sn4 layer was approximately one-third of that of the total IMC layer after aging at 170 C for 100 days (Fig. 3(b)). Fig. 4 shows the thickness of the total IMC layer as a function of aging times for different temperatures. The mean thickness of the interfacial IMC layer was found to increase with aging time and the growth was faster for higher aging temperatures. As mentioned above, the growth of the IMC layer at temperatures between 70 and 150 C was much slower than that at 170 C. After isothermal aging at 170 C for 50 days, two IMC layers of (Cu,Ni)6 Sn5 and (Ni,Cu)3 Sn4 were formed at the interface. As shown in Fig. 4, the growth rate of the total IMC layer after aging at 170 C for 50 days was very fast. This was probably due to the formation of (Ni,Cu)3 Sn4 IMC. The (Ni,Cu)3 Sn4 IMC layer started to form under the (Cu,Ni)6 Sn5 IMC due to the decrease of Cu diffusion into the interface. Compared to the compositions for these two IMC layers, the Cu content of (Ni,Cu)3 Sn4 IMC was much lower than that of (Cu,Ni)6 Sn5 IMC. Therefore, the growth of the (Ni,Cu)3 Sn4 IMC layer on the Ni substrate would have been relatively easy. After further prolonged aging, these two IMC layers grew simultaneously. However, the thickness of these two IMC layers could not be measured because unfortunately the interface between them was not observed. Generally, the thickness of a reaction layer in the solder joints can be expressed by a simple power law equation: W = kt n (1)

where W is the thickness of the reaction layer, k the growth rate constant, t the reaction time, and n the time exponent. If the growth process is controlled by a diffusion mechanism, the increase of the IMC layer after aging should follow the square root time law, W = kt0.5 .

The time exponents (n) were obtained from the slope of the plot of ln (Y B) versus ln t. Table 1 represents the time exponents determined by the linear-regression analysis of each aging temperature using Eq. (3). We calculated up to the value of IMC thickness after aging at 170 C for 30 days. The time exponents determined at aging temperatures below 150 C were approximately 0.2. It is known that the interfacial reaction follows an ideal diffusion-controlled mechanism when n (time exponent) equals 0.5, whereas when n equals 0.33, the reaction follows a grain boundary diffusion-controlled mechanism [9,15]. Many of the experimental IMC growth rate studies for solid-state systems in the literature [1517] show that intermetallic layers exhibit a nearly parabolic dependence of layer thickness (W) versus time (t), i.e., W = kt0.5 . However, most of these papers report deviations from parabolic behavior in the regime where intermetallic layers are relatively thin [15,16]. On the other hand, the results in this study indicated that the growth of the IMC layer does not follow the standard volume diffusion model. As shown in Figs. 2 and 4, the growth of the IMC layer at temperatures between 70 and 150 C was relatively slow and the layer was very thin. Furthermore, the interface between solder and (Cu,Ni)6 Sn5 IMC layer had an irregular and uneven shape. In other words, smaller grains lead to more grain boundaries, which could be the dominant diffusion paths at lowaging temperatures (see Fig. 2(ac)). This is in agreement with previous research results [15,18]. Also, as mentioned above, the role of the Cu atom in the Sn0.7Cu solder is so important that it determines the formation of (Cu,Ni)6 Sn5 IMC even though the Cu content in the solder is very low. In the case of the interfacial reaction between Ni and Cucontaining solders such as SnAgCu and SnCu, Sn, Cu, and Ni atoms must diffuse through the IMC layer to form interfacial reaction products, (Cu,Ni)6 Sn5 . Because the grain boundary of the IMC is the easiest diffusion path, the determined n values (about 0.2) are presumably related to the grain boundary diffusion-controlled mechanism [15]. And, n

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Fig. 5. Variations of the ball shear strength with aging temperature and time.

Fig. 6. Cross-section views (a, c, and e) and top views (b, d, and f) of the fracture surfaces of the samples aged at different conditions.

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Fig. 7. Fracture surfaces of the samples aged at different conditions.

increased to 0.42 at the higher aging temperature of 170 C. As the layer grows thicker and grain coarsening progresses (see Fig. 2(d)), the contribution of grain boundary diffusion will diminish and the volume diffusion will predominate. Ball-shear test was also performed to evaluate the effect of the interfacial reactions on the mechanical reliability of the solder balls as a function of aging conditions. Fig. 5 shows the variation of the shear strength with aging temperature and time. The shear strength signicantly decreased after aging for initial 1 day and then remained nearly unchanged by further prolonged aging. Furthermore, the higher shear strength value of the sample aged at a higher aging temperature is surprising. The average shear strengths of the solder joints after reowing, and after aging at 170 and 70 C for 1 day were about 12.6, 11, and 8.8 N, respectively. To verify this phenomenon, a micro Vickers hardness (Hv) test was performed for the solder region of the cross-sectioned solder joints with a load of 50 g. However, the hardness values had a constant value with aging temperature and time. Although the exact reason for this is not clear at this point, it is presumably due to the discrepancy of Cu solubility in the Sn matrix at different aging temperatures.

We also studied the interfacial reaction and shear strength of Sn3Cu solder/Ni BGA joints [19]. In case of Sn3Cu solder, the tendency of shear strength variation was also similar to that in the case of Sn0.7Cu solder. Further research is required to fully clarify this phenomenon. Compared to the IMC thickness data as a function of aging conditions, the IMC thickness does not have a strong inuence on the solder ball-shear strength. To verify the variation of the shear strength, the cross-sectional and the top views of the fracture surfaces after shear test were examined by SEM (see Fig. 6). Regardless of the aging condition, the fracture always occurred in the bulk solder. Fig. 7 shows the fracture surfaces of the samples aged at different aging temperatures and times. In all samples, the fracture surfaces showed a ductile failure. Generally, in the solder ball-shear test, a fracture occurs at the interface or in the solder region with the lowest strength. Over the years many studies have been published concerning the mechanical properties of solder joints. It was known that excessively thick reaction layers formed between solder and substrate could signicantly degrade the mechanical properties of the solder joints [20,21]. However, in this study, fracture analysis indicated that the shear strength could not be

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related to the thickness of the IMC layer formed at the interface between Sn0.7Cu solder and Ni substrate. The results of interfacial reaction and mechanical tests showed that the Sn0.7Cu/Ni solder joint has the desirable joint reliability.

No. 10012693) of The Korea Ministry of Commerce, Industry and Energy. One of the authors (J.W. Yoon) acknowledges the scholarship of the Seoam Scholarship Foundation.

References 4. Conclusion In this study, the effect of isothermal aging on the interfacial reaction and shear strength of Sn0.7Cu solder/Ni BGA joints was investigated. During reow process, the entire Au layer dissolved into the molten solder, leaving the Ni layer exposed to the molten solder. The reaction between the molten solder and Ni layer resulted in the formation of a (Cu,Ni)6 Sn5 layer at the interface. Furthermore, only (Cu,Ni)6 Sn5 layer was observed in the samples aged at temperatures between 70 and 150 C, over all aging times. On the other hand, after isothermal aging at 170 C for 50 days, the solder/Ni interface exhibited a duplex structure of (Cu,Ni)6 Sn5 and (Ni,Cu)3 Sn4 . The growth of the IMC layer at temperatures between 70 and 150 C was much slower than that of aging at 170 C. The time exponents (n) at aging temperatures below 150 C were approximately 0.2. The determined n values are presumably related to the grain boundary diffusion-controlled mechanism. On the other hand, n increased to 0.42 at a higher aging temperature of 170 C. In the ball-shear tests, the shear strength signicantly decreased after aging for initial 1 day and then remained constant. However, the fracture always occurred in the bulk solder. The shear strength of the sample aged at a higher aging temperature was higher. We consider that the main cause of this phenomenon is the discrepancy of Cu solubility in the Sn matrix at different aging temperatures.
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Acknowledgements The present work was carried out with the support of a Standardization Technology Development Program (Project

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