Interfacial reactions and shear strength on Cu and electrolytic Au/Ni metallization with Sn-Zn solder

Jeong-Won Yoon and Seung-Boo Junga)

School of Advanced Materials Science and Engineering, Sungkyunkwan University, Jangan-gu, Suwon, Gyeonggi-do 440-746, Korea (Received 24 September 2005; accepted 22 March 2006)

The interfacial reaction between eutectic Sn-9 wt% Zn solder and two different kinds of ball-grid-array substrates (Cu and Au/Ni electroplated Cu) during aging at 150 C and the shear strength of the resulting joints were investigated. In the Sn-9Zn/Cu joints, only Cu5Zn8 intermetallic compound (IMC) was observed between the solder and Cu layer during the first 100 h of aging. After aging for 1000 h, the layer-type Cu5Zn8 IMC layer was disrupted at the interface, causing it to act as a channel for the diffusion of Sn. As a result, Cu6Sn5 and Cu3Sn IMCs were formed underneath the Cu5Zn8 IMC layer. This interfacial reaction significantly degraded the joint strength. In the case of the Au/Ni/Cu substrate, an AuZn3 IMC layer formed at the interface because of the fast reaction between Au and Zn. In addition, the AuZn3 IMC layer became detached from the interface during reflow. The detachment of the AuZn3 IMC layer is presumably from the mismatch in the coefficients of thermal expansion and weak adhesion between the AuZn3 IMC layer and Ni layer caused by the depletion of the Au layer. When the aging time was extended to 100 h, Ni5Zn21 IMC was observed on the Ni substrate. The shear strength of the aged Sn-9Zn/Au/Ni/Cu joint was significantly related to the detachment of the AuZn3 IMC layer. After aging at 150 C, fracturing occurred on the detached AuZn3 IMC layer. To ensure the reliability of the Sn-Zn/Au/Ni/Cu joint, the detachment of the AuZn3 IMC needs to be prevented.

I. INTRODUCTION

Conventional lead (Pb)-bearing Sn-Pb solders have been used over the past several decades as a joining material for the interconnection and packaging of modern electronic components and devices.15 However, the use of Pb-containing solder is becoming problematic because of environmental and health concerns.1 The draft European Union Restriction of Hazardous Substances (RoHS) in Electrical and Electronic Equipment Directive will ban Pb from all new electronic consumer products sold in Europe starting in July 2006. Therefore, the pursuit of Pb-free solder has become an important issue in the field of electronic materials, and has led to extensive research and development work.13,513 Many different solder alloys have been proposed as potential Pb-free solders, and the most promising of these falls into the category of the Sn-Ag, Sn-Ag-Cu, and Sn-Cu family of alloys.2,7 However, these alloys have somewhat higher melting temperatures than conventional Sn-Pb alloy, therefore their use may require the modification of the
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Address all correspondence to this author. e-mail: sbjung@skku.ac.kr DOI: 10.1557/JMR.2006.0198

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present manufacturing lines. In addition, the use of a higher soldering temperature may cause damage to electronic components. Recently, compared with Sn-Ag solders, Sn-Zn solders have been highly recommended as a substitute for eutectic Sn-Pb solder because of their low melting point, excellent mechanical properties, and low cost.1418 Eutectic Sn-9 wt% Zn solder has a melting temperature (198 C), which is relatively close to that of eutectic Sn-Pb solder (183 C), and this has enabled industries to use this alloy without having to replace their existing manufacturing lines or electronic components.18 Nevertheless, there are several problems that need to be addressed to facilitate the practical use of this solder alloy, such as its inferior wettability, easy oxidation, micro-void formation, and low reliability.17,18 At present, it is not common to use Zn-containing Pb-free solders because of these drawbacks; however, many studies have been performed to address these issues.1921 One recent study pointed out that Sn-containing organic compound fluxes provided adequate wetting of the Cu substrate with Zn-containing solders.19 Also, Yu et al.21 reported that the mechanical properties of Sn-Zn alloy can be improved by adding Al. These efforts are expected to promote the use of Zn-containing Pb-free solders in the electronics industry.
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J-W. Yoon et al: Interfacial reactions and shear strength on Cu and electrolytic Au/Ni metallization with Sn-Zn solder

Generally, Cu is widely used in the under bump metallurgy and substrate metallization for ball-grid-array (BGA) and flip-chip applications. It is known that at the solder/Cu interface, Sn (Zn for Sn-Zn solders) reacts rapidly with Cu to form Cu-Sn (Cu-Zn for Sn-Zn solders) intermetallic compounds (IMCs), which weaken the solder joints, due to the brittle nature of these IMCs.16,22 Therefore, Ni is used as a diffusion barrier layer to prevent the rapid interfacial reaction between the solder and Cu layer in electronic devices. One of the major concerns of BGA and flip-chip technology is the reliability of the solder joint. Because solder joints are often subjected to mechanical loadings during handling and system use, the mechanical properties of solder joints, such as their fatigue and shear strengths, are the crucial issue in determining the reliability and integrity of electronic packaging. Many studies have been performed on the interfacial reaction between Sn-Zn solders and the various surface finish layers, such as Cu, Au/Ni/Cu and electroless nickel-immersion gold (ENIG), during reflow or aging.1418,23 According to these previous studies,16,23 unlike the general reaction layer formed in the Sn-base solder (solder without Zn), stable binary Cu-Zn, Au-Zn, and Ni-Zn IMCs are formed between the Sn-Zn solder and various substrates. Nevertheless, our knowledge of the mechanical properties and joint reliabilities of Sn-Zn solder joints is still insufficient. This study focused on the interfacial reaction between eutectic Sn-9Zn solder and two different bond-pads (Cu and an Au/Ni metallized Cu BGA substrate) during isothermal aging. In addition, the mechanical reliability of the joints was investigated by means of the ball shear test. The correlations between the shear strength and the interfacial reactions on the solder joints are discussed.
II. EXPERIMENTAL

for observation of the cross-section of the interface. Common metallographic practices were used to prepare the samples. An etchant consisting of 95% C2H5OH-4% HNO3-1% HCl was used to reveal the cross-sectional microstructure. The microstructures and chemical compositions were observed with scanning electron microscopy (SEM; XL 40 FEG, Philips, Mahwah, NJ and/or S-3000H; Hitachi, Tokyo, Japan) equipped with energy dispersive x-ray spectroscopy (EDX). Also, the compositions of the phases formed at the interface were determined by means of a JXA-8900R (JEOL; Tokyo, Japan) electron probe microanalyzer (EPMA) with wavelength dispersive x-ray spectroscopy. Ball shear tests were also performed on the reflowed and aged samples using a shear tester (PTR-1000; Rhesca Co. Ltd.). A shear tool height of 50 m and shear speed of 200 m/s were used. The average peak shear force of 20 solder balls with the minimum and maximum values removed was taken for each condition. The peak shear force was divided by the pad area of the substrate to yield the peak shear stress. After the ball shear testing, the fracture surfaces were investigated thoroughly by SEM as well as by EDX.

III. RESULTS A. Interfacial reaction of Sn-9Zn solder on Cu pad

The BGA solder used in this study was a eutectic Sn-9Zn (wt%) solder with a diameter of 500 m. Also, two kinds of bond-pads (Cu and Au/Ni/Cu) were prepared, and the pad size was set to 460 m by applying solder resist. The Au/Ni/Cu pad was constructed by electroplating Au (0.5 m)/Ni (8.5 m) over an underlying Cu pad. Rosin mildly activated-type flux was applied to the bond pads and the solder balls were placed on the pads. Reflow was then conducted in a reflow machine (SAT-5100 + profile temperature raise heater; Rhesca Co. Ltd., Tokyo, Japan). The peak temperature and dwell time during reflow were 230 C and 60 s, respectively. After the reflow process, the samples were cooled to room temperature. Each BGA solder joint was then cleaned with isopropyl alcohol. Subsequently, the samples were aged at 150 C for up to 1000 h. After the reflow and aging treatment, the samples were prepared

Figure 1 shows the cross-sectional SEM micrographs of the Sn-9Zn/Cu interfaces aged at 150 C for different aging times. As shown in Fig. 1(a), the microstructure of the solder after reflow consisted of a -Sn matrix (gray phase) and fine rod-shaped Zn precipitates (black phase), without any Cu-Zn or Cu-Sn IMCs. The layer-type IMC phase formed at the interface of the as-reflowed sample was confirmed to be Cu5Zn8 by EPMA analysis. The composition of the IMC layer was 34.46 at.% Cu and 65.54 at.% Zn, and its thickness was approximately 1.5 m. Figure 1(b) and (c) show the Sn-9Zn/Cu interfaces after aging at 150 C for 24 and 100 h, respectively. It was found that the thickness of the Cu5Zn8 layer formed at the interface increased as the aging time increased. In addition to the IMC layer formed at the interface, Cu5Zn8 IMC particles were also formed within the solder matrix near the interface, and the fraction of these particles increased with increasing aging time. During aging, the Zn phases adjacent to the joint interface migrated toward the interface, resulting in the growth of the Cu-Zn IMC layer and the extension of the Sn-rich layer above the interfacial IMC layer. The extension of the Sn-rich layer, which corresponds to the Zn-depletion layer, is indicated by the black dashed lines in Fig. 1. When the aging time was extended to 250 h, a new Cu-Sn phase was observed at the interface between the
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FIG. 2. Cross-sectional images of the Sn-9Zn/Cu interface aged at 150 C for 250 h.

FIG. 1. Cross-sectional images of the Sn-9Zn/Cu interfaces aged at 150 C for various times: (a) 0 h, (b) 24 h, (c) 100 h, (d) 250 h, and (e) 1000 h.

interfacial Cu5Zn8 IMC layer and the Cu substrate. Figure 2 shows this phenomenon in more detail. The layer-type Cu5Zn8 IMC layer was disrupted locally at the interface, which caused it to act as a channel for the diffusion of Sn. As a result, Cu6Sn5 IMC formed underneath the Cu5Zn8 IMC layer. Similar results have been reported in the literature.14,1618 In addition, the interfacial Cu5Zn8 IMC layer consisted of individual IMC particles, as shown in Fig. 2(b). After prolonged aging time
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(1000 h), most of the interfacial Cu5Zn8 IMC layer was disrupted and more Cu6Sn5 IMCs formed between the Cu5Zn8 IMC layer and Cu substrate, as shown in Fig. 1(e). Cu3Sn IMC also formed between the Cu6Sn5 IMC and the Cu substrate. In addition, the size of the Zn-depletion area increased with increasing aging time. Especially, in the case of the sample aged at 150 C for 1000 h, the Zn-depletion layer extended to the top of the solder ball. Many voids (and/or holes) formed along the Sn-Zn solder/Cu5Zn8 and Cu5Zn8/Cu6Sn5 interfaces. This interfacial microstructural evolution would be expected to degrade the joint strength. However, we could not measure the thickness of the interfacial IMC layers because of the spalling of the IMCs and the disruption of the Cu5Zn8 IMC layer, as shown in Fig. 1.
B. Interfacial reaction of Sn-9Zn solder on Au/Ni/Cu pad

Figure 3 shows the cross-sectional SEM micrographs of the Sn-9Zn solder/Au/Ni/Cu interfaces aged at 150 C for various times. Generally, an Au/Ni/Cu substrate has been used as the metallization in BGA applications. The Au and Ni layers are used as a wetting layer and diffusion

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the interface. The composition of the IMC formed at the interface after reflow was 19.624.8 at.% Au and 75.2 80.4 at.% Zn. Similar results have been observed in previous studies.17,18 On the other hand, the present result differs from those reported in other studies15,16 in which 13:87) and Au-Zn (Au:Zn 47.4: AuZn8 (Au:Zn 52.6) IMCs formed as a result of the Sn-9Zn/Au/Ni(P) and Sn-7Zn/Au/Ni/Cu reactions, respectively. The discrepancy among these results may be from the differences in the reflow profile, solder alloy, and surface finish used. In addition, the AuZn3 IMC layer was detached from the interface in many parts of the sample after reflow, as shown in Fig. 3(a). Additionally, solder was observed between the detached AuZn3 IMC layer and substrate. It was very interesting that the AuZn3 IMC layer was detached from the interface during reflow in some parts of the interface. In other parts of the sample, the AuZn3 IMC layer was still attached to the interface [see Fig. 3(a)]. Up to an aging time of 24 h at 150 C, only an AuZn3 IMC layer was observed in this study, as shown in Fig. 3(b). Figure 4 shows the EPMA line profile of the Sn-9Zn/Au/Ni/Cu interface aged at 150 C for 24 h. This EPMA result clearly showed the existence of the detached AuZn3 IMC layer. When the aging time was extended to 100 h, a new Ni-Zn phase was observed on the substrate. Figure 3(d) shows the Sn-9Zn/Au/Ni/Cu interface after aging at 150 C for 250 h. The interfacial structure is similar to that of the interface of the sample

FIG. 3. Cross-sectional images of the Sn-9Zn/AuNiCu interfaces aged at 150 C for various times: (a) 0 h, (b) 24 h, (c) 100 h, (d) 250 h, and (e) 1000 h.

barrier layer, respectively. It is known that Au dissolves into the solder matrix quickly, and then Ni3Sn4 IMC is formed at the interface during reflow with Sn-Pb and Sn-Ag solders.3,22 However, the interfacial reaction between the Sn-9Zn solder and Au/Ni/Cu substrate was found to be different from that observed in the case of the Sn-Pb and Sn-Ag solders. As shown in Fig. 3(a), Au did not dissolve into the solder. As a result of the fast reaction between Au and Zn, an AuZn3 IMC layer formed at

FIG. 4. EPMA line profile of the Sn-9Zn/AuNiCu interface aged at 150 C for 24 h.
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aged for 100 h. The thickness of the detached AuZn3 layer did not change with prolonged aging time because the entire Au layer was consumed. The chemical composition of the AuZn3 IMC was 19.429.9 at.% Au and 70.180.6 at.% Zn. On the other hand, the thickness of the Ni-Zn IMC layer formed on the Ni layer increased with increasing aging time. The compound was composed of 18.420.2 at.% Ni and 79.881.6 at.% Zn, corresponding to Ni5Zn21 IMC.24 The thicknesses of the detached AuZn3 and interfacial Ni5Zn21 IMC layers were approximately 4 and 3 m, respectively. When the aging time was extended to 1000 h, the thickness of the Ni5Zn21 IMC layer grew to about 5 m. In addition, the Zn-depletion layer was extended when the aging time was prolonged, as shown in Fig. 3(e). The Zn-depletion layer is also indicated by the black dashed lines in Fig. 3. Figures 5 and 6 show the results of the EPMA line profile and mapping, respectively, for the Sn-9Zn/Au/Ni/Cu interface aged at 150 C for 1000 h. These EPMA analysis results showed the coexistence of the detached AuZn3 and interfacial Ni5Zn21 IMC layers.
C. Shear strength of Sn-9Zn solders on Cu and Au/Ni/Cu pads

FIG. 6. EPMA element mapping of the Sn-9Zn/AuNiCu interface aged at 150 C for 1000 h.

Ball shear tests were performed to evaluate the effect of the interfacial reactions on the mechanical reliability of the Sn-9Zn solder joints as a function of the aging time at 150 C. Generally, shear force has been used as representing unit for the mechanical reliability of solder

joints. However, it is not possible to make a direct comparison of mechanical strengths of solder joints represented by the shear force because in marking solder joints, there are many variables, such as solder chemistry, solder bump size, solder geometry, and metallization scheme. Therefore, we used the peak shear stress for presenting the mechanical property of solder joints. Figure 7 shows the variations of the peak shear stress with the surface finish and aging time. Regardless of the substrate, both of the as-reflowed joints had high shear strengths. In the case of the as-reflowed samples, the values of the peak shear stress were approximately 66.5 and 72.4 N for the Cu and Au/Ni/Cu substrates,

FIG. 5. EPMA line profile of the Sn-9Zn/AuNiCu interface aged at 150 C for 1000 h.
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FIG. 7. Variations of the peak shear stress with aging time at 150 C.

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respectively. For the Au/Ni/Cu substrate, the shear strength decreased during the initial 100 h, and then remained constant with prolonged aging. The average peak shear stresses of the solder joints aged at 150 C for 100 and 1000 h were approximately 59.5 and 56.2 N, respectively. Compared with the stress measured after reflow, the shear stress decreased by 22.4% after 1000 h of aging at 150 C. On the other hand, the shear strength of the Sn-9Zn/Cu joint was significantly degraded during the initial period of aging. After aging for 100 h, the shear strength was reduced to about one-half of its initial value. The average peak shear stresses of the solder joints after aging at 150 C for 100 and 1000 h were approximately 35.4 and 27.6 N, respectively. To verify the variations of the peak shear stress observed in the ball shear test, the fracture surfaces after

ball shear testing were examined using SEM. Figure 8 shows the cross-sectional views and top views of the fracture surfaces of the Sn-9Zn/Cu joints aged at 150 C for various times. The direction of the shear action was from left to right for the cross-sectional views and from top to bottom for the top views. In the case of the asreflowed sample, fracturing occurred in the bulk solder [see Fig. 8(a)]. However, after aging treatment for 24 h at 150 C, the fracture surface showed mainly brittle failure at the interface between the solder and IMC layer [see Fig. 8(b)]. Also, dimples were observed in the fracture surface, and the presence of the Cu5Zn8 IMC is clearly observed in the center of each dimple. The size of the dimples increased with increasing aging time, and the tendency for fracture to occur at the interface was more pronounced [see Fig. 8(d)]. In this study, the results of the fracture analysis show that the shear strength of the Sn-9Zn/Cu joints after aging treatment was significantly related to the IMC layer formed at the interface. Figure 9 shows the cross-sectional views and top views of the fracture surfaces of the Sn-9Zn/Au/Ni/Cu joints aged at 150 C for various times. The shear direction is indicated by the white arrows. In the as-reflowed sample, fracturing occurred in the bulk solder. The presence of AuZn3 IMC layer detached from the interface was clearly observed in the cross-sectional view of Fig. 9(a). However, the shear fracture of the solder joint was not found to be significantly related to the detachment of the AuZn3 IMC layer. On the other hand, after aging at 150 C, fracturing occurred on the detached AuZn3 IMC layer [see Figs. 9(b)9(d)]. The correlation between the interfacial reaction and the shear strength will be discussed later.
IV. DISCUSSION A. Formation of Cu6Sn5 IMC underneath Cu5Zn8 IMC for Sn-9Zn/Cu joint

FIG. 8. Cross-sectional and top views of fracture surfaces of the Sn9Zn/Cu joints aged at 150 C for various times: (a) 0 h, (b) 24 h, (c) 100 h, and (d) 1000 h.

As shown in Fig. 1(e), the interface between the Cu5Zn8 IMC layer and the solder did not remain flat, and the reacted region became much more irregular. The disruption of the Cu5Zn8 IMC layer caused it to act as a channel for the diffusion of Sn. As a result, Cu6Sn5 and Cu3Sn IMCs formed underneath the Cu5Zn8 IMC layer. The Sn transported through the channels reacts with the Cu at the end of the channels to form Cu-Sn IMCs in the Cu so that the penetration of the Cu-Sn IMCs into the Cu is channel like rather than layer like. The penetration of Sn into the Cu5Zn8 IMC layer and the formation of the Cu-Sn IMC are enhanced because of the restriction in the supply of Zn atoms from the solder to the interface. If Zn atoms were continually supplied from the solder to the interface, the layer-type Cu5Zn8 IMC layer would not be expected to be disrupted at the interface. Similar results have been reported in the literature.14,16 Date et al.16
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FIG. 9. Cross-sectional and top views of fracture surfaces of the Sn9Zn/AuNiCu joints aged at 150 C for various times: (a) 0 h, (b) 24 h, (c) 100 h, and (d) 1000 h.

investigated the interfacial reactions of Sn-Zn solder joints on a Cu bond pad. In their study, when the aging time was extended to 1000 h at 150 C, the Cu5Zn8 IMC formed at the interface was no longer of the layer type. Most of the interfacial Cu5Zn8 IMC layer was disrupted and more Cu6Sn5 IMCs were formed on the Cu substrate. Suganuma et al.14 investigated the interfacial reactions between Sn-9Zn solder and a Cu substrate during aging at 125 C and 150 C. They reported that the Cu-Zn reaction layer partly disappeared in those areas where Sn diffused into the Cu side behind the reaction layer to form a Cu-Sn reaction product. In addition, many voids (and/or holes) formed along the Sn-Zn solder/Cu5Zn8 and Cu5Zn8/Cu6Sn5 interfaces, as shown in Fig. 1(e). To investigate this phenomenon in more detail, the nonetched solder joint was analyzed. Figure 10 shows the
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FIG. 10. SEM micrograph and EDX analysis results of phases formed at the Sn-9Zn/Cu interface aged at 150 C for 2400 h.

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SEM micrograph and EDX analysis results of the nonetched sample aged at 150 C for 2400 h. Interestingly, there were no voids or holes at the Sn-Zn solder/Cu5Zn8 and Cu5Zn8/Cu6Sn5 interfaces. Only cracks were found at the interface between the Sn-Zn solder and Cu5Zn8 IMC. Although the exact reason for the formation of these cracks is not clear at this point, it is presumably from the mechanical stress applied during polishing. This result means that the Sn-Zn solder/Cu5Zn8 interface was significantly weakened during isothermal aging. The voids and/or holes shown in Fig. 1(e) were originally trapped Sn shown in Fig. 10. As mentioned above, the Sn transported through the channels reacted with the Cu, and formed Cu-Sn IMCs underneath the Cu5Zn8 IMC. During the preparation of the sample, the Sn trapped in these channels was etched away.
B. Detachment of AuZn3 IMC layer from the interface for Sn-9Zn/Au/Ni/Cu joint

IMC spalling is a reliability concern because it can result in the dewetting of the molten solder during joining and thereby yield weak adhesion of the solder joints during field operation. The most interesting interfacial reaction observed in the Sn-9Zn/Au/Ni/Cu joint is the detachment of the AuZn3 IMC layer from the interface. A similar result was also reported by previous researchers.15,17 Sogo et al.17 investigated the effect of several Cu pad plating materials and reflow peak temperatures on the interfacial reaction and reliability of the chip-scale package joint with Sn-3.0Ag-0.5Cu solder balls using Sn-8Zn-3Bi solder paste. They reported that the Au-Zn IMC layer formed in the solder apart from the interface in the Sn-Ag-Cu ball/Sn-8Zn-3Bi paste/Ni-P (5 m)/Au (0.5 m) joint reflowed at 230 C. They also suggested that the layer was formed by the dissolution and diffusion of the Au-Zn layer into the solder during the reflow process. Kim et al.15 investigated the interfacial reaction and shear strength between Sn-Zn solders (Sn-7Zn and Sn-8Zn-3Bi, where the numbers are in wt%) and an Au/ Ni/Cu substrate during isothermal aging. They reported that no Au layer was found at the interface after reflow. Instead, band-shaped compounds were observed in the solder. However, they did not report the main reason for the detachment of the Au-Zn IMC layer. We think that the AuZn3 IMC layer becomes detached from the interface during the final reflow stage and/or the solidification of the solder alloy because of the depletion of the Au layer at the interface caused by a soldering reaction. As shown in Fig. 3(a), the AuZn3 IMC layer became detached from the interface in many parts of the asreflowed sample. Also, large voids existed onto the detached AuZn3 IMC layer, as shown in Figs. 3(b)3(d). This provides evidence of the detachment of the AuZn3 IMC layer during the reflow stage and/or the solidification of the solder alloy, because the voids cannot become

detached from the interface during isothermal aging. In other words, both of these voids and the AuZn3 IMC layer became detached from the interface while remaining attached to each other. The detachment of the AuZn3 IMC layer is presumably from the mismatch in the coefficients of thermal expansion and weak adhesion between the AuZn3 IMC layer and Ni layer caused by the depletion of the Au layer. As a whole, the shear strength of the aged Sn-9Zn/Au/Ni/Cu joint was found to be related to the detachment of the AuZn3 IMC layer. In this study, when the aging time was extended to 1000 h, the thickness of the interfacial Ni5Zn21 IMC layer was increased to approximately 5 m, which was greater than that of the detached AuZn3 IMC layer in the same sample. In spite of the presence of the thicker interfacial Ni5Zn21 IMC layer, no fracturing occurred at the interface of the Ni5Zn21 IMC layer formed on the Ni substrate. This was probably because of the concentration of shear stress at the detached AuZn3 IMC layer near the shear ram height. The result in this study clearly demonstrates that the detachment of the AuZn3 IMC needs to be prevented to ensure the reliability of the Sn-Zn/Au/ Ni/Cu joint.
C. Effect of substrate metallization on interfacial reactions between Sn-9Zn solder and substrates

It was found that the interfacial reaction between the Sn-9Zn solder and the Au/Ni/Cu substrate was slower than that with the Cu substrate, as shown in Figs. 1 and 3. Recently, we also investigated the interfacial reactions and mechanical properties of Sn-9Zn/ENIG-plated Cu joints during isothermal aging at temperatures between 70 C and 150 C for aging times of up to 2400 h, and the results are reported elsewhere.25 The results are repeated here only to provide a direct comparison between the Sn-9Zn/Cu, Sn-9Zn/Au/Ni/Cu, and Sn-9Zn/ENIG joints. Figure 11 shows the SEM image of the Sn-9Zn/ENIG interface aged at 150 C for 1000 h. In spite of the severe aging conditions, only the AuZn3 IMC layer was observed. In addition, the AuZn3 IMC layer effectively inhibited the interfacial reaction between the Sn-Zn solder and the Ni-P plating layer. No Ni-containing reaction products, such as Ni-Zn, Ni-Sn, and Ni3P, were observed to form at the interface. In that study, the thickness of the AuZn3 IMC layer did not vary significantly with the aging temperature and time because of the limited thickness of the Au layer. The shear strength also remained nearly unchanged, irrespective of the reflow and aging time, and the fractures occurred in the solder matrix. In the case of the Cu substrate in the present study, a Cu5Zn8 IMC layer formed at the interface after reflow. Also, it was found that the thickness of the Cu5Zn8 layer significantly increased with increasing aging time. The layer-type Cu5Zn8 IMC layer was disrupted locally at the
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FIG. 11. SEM micrograph of the Sn-9Zn/ENIG interfaces aged at 150 C for 1000 h.

interface, causing it to act as a channel for Sn diffusion. As a result, a Cu6Sn5 IMC formed underneath the Cu5Zn8 IMC layer. This interfacial microstructural change weakened the interface and caused fracturing to occur at the interface between the solder and IMC layer. In the case of the Sn-9Zn/Au/Ni/Cu joint, the shear strength was related to the detachment of the AuZn3 IMC layer, as mentioned above. In contrast to the interfacial reaction of the two solder joints used in this study, the ENIG plating layer in the Sn-9Zn/ENIG joint protected the interface from undesirable interfacial reactions (see Fig. 11). Although the same AuZn3 IMC layer formed at the Sn-9Zn/Au/Ni/Cu and Sn-9Zn/ENIG interfaces, the detachment of the AuZn3 IMC layer did not occur at the Sn-9Zn/ENIG interface. The exact reason for this phenomenon is not clear at this point. We attributed this to the difference in the adhesion strengths of the AuZn3/Ni in the Sn-9Zn/Au/Ni/Cu joint and the AuZn3/Ni-P in the Sn-9Zn/ENIG joint. Electroless Ni plating contains concentrations of P ranging from several % through 10 wt% because of the use of the hypophosphite as a reducing agent during plating. More studies on the mismatch in the coefficients of thermal expansion and the difference in the adhesion strengths between the AuZn3 IMC and different Ni substrates, and the effect of P in the Ni-P layer, are needed to verify this phenomenon. As a result, the interfacial reaction between the Sn-Zn solder and the Ni-P plating layer is suppressed by the formation of the attached layer-type AuZn3 IMC layer, which acts as a diffusion barrier, thereby promoting desirable interfacial reactions.
V. CONCLUSIONS

1000 h and the shear strength of the resulting joints were investigated. In the Sn-9Zn/Cu joints, only Cu5Zn8 IMC was observed between the solder and Cu layer up to an aging time of 100 h. After aging for 1000 h, the interface between the Cu5Zn8 IMC layer and the solder did not remain flat and the reacted region became much more irregular. The disrupted Cu5Zn8 IMC layer acted as a channel for the diffusion of Sn. As a result, Cu6Sn5 and Cu3Sn IMCs formed underneath the Cu5Zn8 IMC layer. This interfacial microstructural evolution significantly degraded the strength of the solder joint. After aging treatment, fractures occurred at the interface between the solder and IMC layer. In the case of the Au/Ni/Cu substrate, an AuZn3 IMC layer formed at the interface. In addition, the AuZn3 IMC layer became detached from the interface. The detachment of the AuZn3 IMC layer is presumably from the mismatch in the coefficients of thermal expansion and weak adhesion between the AuZn3 IMC layer and Ni layer caused by the depletion of the Au layer. When the aging time was extended to 100 h, Ni5Zn21 IMC was observed on the Ni substrate. The shear strength of the aged Sn-9Zn/Au/Ni/Cu joint was significantly related to the detachment of the AuZn3 IMC layer. In contrast to the two solder joints used in this study, for which unwanted interfacial reactions occurred, the attached AuZn3 IMC layer in the Sn-9Zn/ENIG joint protected the interface from undesirable interfacial reactions. Although the same AuZn3 IMC layer formed at the Sn-9Zn/Au/Ni/Cu and Sn-9Zn/ENIG interfaces, the detachment of the AuZn3 IMC layer did not occur at the Sn-9Zn/ENIG interface. We attributed this to the difference in the adhesion strength of the AuZn3/Ni in the Sn-9Zn/Au/Ni/Cu joint and the AuZn3/Ni-P in the Sn9Zn/ENIG joint. Even though the interfacial reaction between the Sn-9Zn solder and Au/Ni/Cu substrate was slower than that with the Cu substrate, we think that the detachment of the AuZn3 IMC needs to be prevented to ensure the reliability of the Sn-Zn/Au/Ni/Cu joint.
ACKNOWLEDGMENT

This work was supported by Grant No. RTI04-03-04 from the Regional Technology Innovation Program of the Ministry of Commerce, Industry and Energy (MOCIE).
REFERENCES
1. M. Abtew and G. Selvaduray: Lead-free solders in microelectronics. Mater. Sci. Eng. R R27, 95 (2000). 2. K. Zeng and K.N. Tu: Six cases of reliability study of Pb-free solder joints in electronic packaging technology. Mater. Sci. Eng. R 38, 55 (2002). 3. M.N. Islam, Y.C. Chan, and A. Sharif: Interfacial reactions of Sn-Cu and Sn-Pb-Ag solder with Au/Ni during extended time reflow in ball grid array packages. J. Mater. Res. 19, 2897 (2004). 4. Y.H. Liu, C.M. Chuang, and K.L. Lin: Failure behavior upon

The interfacial reaction between eutectic Sn-Zn solder and two different kinds of BGA substrates (Cu and Au/Ni/Cu) during isothermal aging at 150 C for up to
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J. Mater. Res., Vol. 21, No. 6, Jun 2006

J-W. Yoon et al: Interfacial reactions and shear strength on Cu and electrolytic Au/Ni metallization with Sn-Zn solder

5.

6.

7.

8.

9.

10.

11. 12.

13.

14.

shear test of 5Sn-95Pb solder bump after high temperature reliability test. J. Mater. Res. 19, 2471 (2004). M.O. Alam, Y.C. Chan, and K.N. Tu: Effect of reaction time and P content on mechanical strength of the interface formed between eutectic Sn-Ag solder and Au/electroless Ni(P)/Cu bond pad. J. Appl. Phys. 94, 4108 (2003). W.T. Chen, C.E. Ho, and C.R. Kao: Effect of Cu concentration on the interfacial reactions between Ni and Sn-Cu solders. J. Mater. Res. 17, 263 (2002). J.W. Yoon, S.W. Kim, J.M. Koo, D.G. Kim, and S.B. Jung: Reliability investigation and interfacial reaction of ball-grid-array packages using the lead-free Sn-Cu solder. J. Electron Mater. 33, 1190 (2004). C.W. Hwang, K. Suganuma, M. Kiso, and S. Hashimoto: Interface microstructures between Ni-P alloy plating and Sn-Ag-(Cu) leadfree solders. J. Mater. Res. 18, 2540 (2003). Y.C. Sohn, J. Yu, S.K. Kang, D.Y. Shih, and T.Y. Lee: Spalling of intermetallic compounds during the reaction between lead-free solders and electroless Ni-P metallization. J. Mater. Res. 19, 2428 (2004). Z. Chen, M. He, and G. Qi: Morphology and kinetic study of the interfacial reaction between the Sn-3.5Ag solder and electroless Ni-P metallization. J. Electron Mater. 33, 1465 (2004). K.N. Tu, A.M. Gusak, and M. Li: Physics and materials challenges for lead-free solders. J. Appl. Phys. 93, 1335 (2003). J.W. Yoon, C.B. Lee, and S.B. Jung: Growth of an intermetallic compound layer with Sn-3.5Ag-5Bi on Cu and Ni-P/Cu during aging treatment. J. Electron Mater. 32, 1195 (2003). J.W. Jang, D.R. Frear, T.Y. Lee, and K.N. Tu: Morphology of interfacial reaction between lead-free solders and electroless Ni-P under bump metallization. J. Appl. Phys. 88, 6359 (2000). K. Suganuma, T. Murata, H. Noguchi, and Y. Toyoda: Heat resistance of Sn-9Zn solder/Cu interface with or without coating. J. Mater. Res. 15, 884 (2000).

15. K.S. Kim, K.W. Ryu, C.H. Yu, and J.M. Kim: The formation and growth of intermetallic compounds and shear strength at Sn-Zn solder/Au-Ni-Cu interfaces. Microelectron Reliab. 45, 647 (2005). 16. M. Date, K.N. Tu, T. Shoji, M. Fujiyoshi, and K. Sato: Interfacial reactions and impact reliability of Sn-Zn solder joints on Cu or electroless Au/Ni(P) bond-pads. J. Mater. Res. 19, 2887 (2004). 17. Y. Sogo, T. Hojo, H. Iwanishi, A. Hirose, K.F. Kobayashi, A. Yamaguch, A. Furusawa, and K. Nishida: Influence of the interfacial reaction layer on reliability of CSP joints using Sn8Zn-3Bi solder and Ni/Au plating. Mater. Trans. 45, 734 (2004). 18. C.W. Huang and K.L. Lin: Interfacial reactions of lead-free Sn-Zn based solders on Cu and Cu plated electroless Ni-P/Au layer under aging at 150 C. J. Mater. Res. 19, 3560 (2004). 19. S. Vaynman, G. Ghosh, and M.E. Fine: Some fundamental issues in the use of Zn-containing lead-free solders for electronic packaging. Mater. Trans. 45, 630 (2004). 20. A. Hirose, H. Yanagawa, E. Ide, and K.F. Kobayashi: Joint strength and interfacial microstructure between Sn-Ag-Cu and SnZn-Bi solders and Cu substrate. Sci. Technol. Adv. Mater. 5, 267 (2004). 21. S.P. Yu, M.H. Hon, and M.C. Wang: The adhesion strength of a lead-free solder hot-dipped on copper substrate. J. Electron Mater. 29, 237 (2000). 22. C.B. Lee, S.B. Jung, Y.E. Shin, and C.C. Shur: Effect of isothermal aging on ball shear strength in BGA joints with Sn-3.5Ag0.75Cu solder. Mater. Trans. 43, 1858 (2002). 23. C.W. Hwang, K.S. Kim, and K. Suganuma: Interfaces in lead-free soldering. J. Electron Mater. 32, 1249 (2003). 24. T.B. Massalski: Binary Alloy Phase Diagrams, 2nd ed. (ASM, New York, NY, 1987), p. 2887. 25. J.W. Yoon, H.S. Chun, and S.B. Jung: Interfacial reaction and mechanical characterization of eutectic Sn-Zn/ENIG solder joints during reflow and aging. Mater. Trans. 46, 2386 (2005).

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