Research Summary

Lead-Free Solder

The Root Cause of Black Pad Failure of Solder Joints with Electroless Ni/Immersion Gold Plating
Kejun Zeng, Roger Stierman, Don Abbott, and Masood Murtuza
This paper reports on a study of the reaction of solder with the electrolessnickel with immersion gold (ENIG) plating system, and the resulting interfacial structures. A focused-ion beam (FIB) was used to polish the cross sections to reveal details of the microstructure of the ENIGplated pad with and without soldering. High-speed pull testing of solder joints was performed to expose the pad surface. Results of scanning-electron microscopy/ energy-dispersive x-ray analysis of the cross sections and fractured pad surfaces support the suggestion that black pad is the result of galvanic hyper-corrosion of the plated electroless nickel by the gold plating bath. Criteria are proposed for diagnosing black pad of ENIG plating. INTRODUCTION The plating system of electroless nickel with immersion gold (ENIG) has been widely used to nish solder pads of printed circuit boards (PCBs), as well as ball-grid array (BGA) and ip chip substrates. It wets well by solder,13 provides a at and uniform surface, and shows high via strength, an important design consideration for thick PCBs with high aspect ratio vias.4,5 Electroless nickel plating Ni(P) often has a lower total cost of ownership than electrolytic nickel plating. The most attractive advantage of ENIG over electrolytic Ni/Au plating is that it can be applied to ne-pitch BGA substrates without complicating the design layout.6,7 Any electrolytic process requires electric connection to each pad. If the pitch is too small, the electric connection (bussing) is difcult, and processing costs become prohibitive. Therefore, electrolytic Ni/Au is used only for substrates with a sufciently large conductor pitch to permit busses to each pad. Another disadvantage of electrolytic Ni/Au plating is thickness variation. The thickness of electrolytic plating is sensitive to current density, the voltage drop over the conductors, and the geometry of the metal surface. On some designs, thickness variations can be as much as 1 m in the nickel (for a nominal 5 m nickel thickness specication) and 0.2 m in the gold (for nominal 0.7 m gold thickness). The upper end of this gold thickness may cause gold embrittlement in ne-pitch BGA joints.8,9 For ENIG, the thickness of both nickel and gold is much better controlled. Usually, thickness is 50.5 m for electroless Ni(P) and 0.10.02 m or less for immersion gold. However, ENIG nishes have exhibited a black pad defect that can cause brittle fracture at the interface between the solder and metal pad.4,5,1016 The failure typically occurs during mechanical or thermal-mechanical testing. The worst cases are BGA package solder joint failure during a customers surface mount assembly process, or in the products nal use by a consumer. To the unaided eye, a solder joint that fails from black pad shows a at pad where the solder ball separated from the pad. Under an optical microscope, the at pad surface is observed to have little or no solder remaining on it. In a scanningelectron microscope (SEM), some small crystals of tin-bearing intermetallic compounds (IMCs) may be found on the pad surface. However, no evidence for the ductile fracture of the solder can be observed. In cross sections of the failed joint, Ni3Sn4 (for SnPb solder joints) or Cu6Sn5 (for SnAgCu solder joints) is found on the solder side, but a phosphorous content higher than that of the Ni(P) plating is detected on the pad side. Because of this observed high phosphorous content, many in the industry hold that the ENIG black pad defect solder joint failure is caused by the phosphorous

50 m

Figure 1. A 30-degree tilt view of a black pad. The pad surface appeared clean. Only a small amount of ne IMC particles (gray) and little solder residue were present on the pad.

50 m

Figure 2. (a) The top view and (b) side view of mud-cracks in the entire pad surface.

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Figure 3. A cross section through several cracks. Spikes in the cross section are conclusive evidence for black pad. 1 m

5 m

content of the Ni(P) plating. The purpose of this paper is to clear the confusion about the solder joint failure caused by ENIG black pad defect. The authors will demonstrate that a high phosphorous content by itself cannot be taken as evidence for black pad, and the origin of black pad is not in the solder or soldering process. Criteria will be dened for identication of black pad failure. See the sidebar for experimental procedures. RESULTS Figure 1 presents an ENIG-plated pad where the solder ball fell off after thermal cycling. Though there were some bright IMC crystals on the pad, there was virtually no solder residue. In a tilt view, the pad appeared at. At higher magnication, a feature that looked like the boundaries of the plating nodules was observed in a top view (Figure 2a). In the 30-degree tilt view in Figure 2b, the boundary-like features appeared as separations from the plating nodules, hereafter called mud-cracks because of their appearance. The pad surface was rather clean. Energy-dispersive x-ray (EDX) analysis of the area in Figure 2a, which was about 765 m2, found 81.0Ni, 5.2Sn, and 13.8P (wt.%). Assuming that all the signals of tin were from the few bright Ni3Sn4 crystals, and neglecting this solder residue on the pad surface, the atomic ratio of Ni:P in the pad surface was calculated from these data to be 75.1:24.8, very close to the stoichiometry of Ni3P. This indicates that the joint was broken between Ni3P and Ni3Sn4, and the mud-cracks were in the Ni3P layer. In a cross section of the pad, the mud-cracks shown in Figure 2 appeared as spikes in the pad surface (Figure 3). This is the conclusive evidence that the
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ENIG plating had the black pad defect. To nd out whether or not the mudcracks in the pad surface were created by soldering, the cross section of the as-received substrates with ENIG plating from vendors A and B were polished by FIB. It was found that the known-bad substrate from vendor A had spikes in the pad surface. The spikes were clearly observed at 10,000X (Figure 4a). In contrast, no such defects were found in substrate B even at 35,000X. A thin layer of gold plating was seen on the top surface and the boundaries between plating nodules were free of defects (see Figure 4b). The details of the defect region of substrate A are revealed in Figure 5. It can be seen that the featherlike structure around the spike or crack is different from the normal Ni(P) plating. The defect region consists of two different areas: a bright core with dark surrounding material. Elemental mapping by EDX shows that the bright core

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Figure 4.The FIB cutting of the as-received ENIG platings (without soldering). (a) Mudcracks are clearly seen in a black pad at 10,000X. (b) No such defect was found in a known-good ENIG plating at even a much higher magnication.

is rich in gold and the phosphorous content in the defect region is higher than the Ni(P) plating (Figure 5). A typical ENIG-plated substrate from vendor A that has not been subjected to soldering is presented in Figure 6. The pad had severe defect regions at the periphery. In a top view, the boundaries of the plating nodules appeared gray and wide, decorated by a dark material, prob-

EXPERIMENTAL PROCEDURES The test vehicle in this study was a substrate with SnPb solder balls and electroless nickel with immersion gold plated pads. Substrates from two vendors, A and B, were used in the investigation. It was known before the investigation that substrate A exhibited black pad but substrate B did not. Solder balls were attached to the pads by a standard reow process for eutectic SnPb solder. Before thermo-mechanical testing, samples were subjected to a standard preconditioning test that included 20 h of burn-in at 125C and three reows at 235C. The thermo-mechanical test of the samples was standard thermal cycling between 55C and +125C. After mechanical testing, both the fractured pads and cross sections of failed joints were examined by scanning-electron microscopy (SEM) (JEOL 840). A quantitative analysis of the compositions of the phases involved was performed using a silicondrifted lithium energy-dispersive x-ray analyzer (EDX), with the SEM running at 20 kV. The software for quantitative analysis of phase compositions was Iridium by iXRF Systems. Quantitative calibration of the software was carried out using National Institute of Standards and Technology-traceable standards. The interfacial phases were identied by their atomic ratios that were determined by EDX analysis. An FEI-830 dual-beam focused-ion beam (FIB) was used to polish the mechanically polished cross sections so that no details of the microstructure would be hidden by smeared materials on the polished surface. The polished cross sections for microanalysis were not chemically etched. For some samples, no mechanical grinding was carried out, but cross sections were made by FIB cutting.

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ably phosphorous. In the side view, the boundaries looked deep. One boundary in the photo was so deep that it looked like a crack, as indicated by the arrow in Figure 6b. Cross sectioning of this area by FIB found that in addition to the spikes between the plating nodules, the nodules were porous (Figure 7). Figure 8 presents another BGA pad from vendor A. The boundary of the nodule at the edge of the pad has been completely cracked. The neighboring nodule has a large defect region, and gold has penetrated into the crack as indicated by the arrow (Figure 8a). Nodules such as this will likely fall off under low shear stress. Indeed, missing nodules were observed in the substrates from vendor A, as indicated by the arrow in Figure 8b.

DISCUSSION Diagnosis of Black Pad When the black pad defect of ENIG plating causes a solder joint failure, usually a high phosphorous content is detected at the fractured pad surface. Because of this, a high phosphorous content at the pad surface is often cited in failure analysis reports as the evidence for black pad and, accordingly, a lower phosphorous content of the Ni(P) plating is recommended as a x. In fact, a phosphorous content of about 15 wt.% (25 at.%), higher than the original Ni(P) plating deposit, is expected after soldering, no matter whether the ENIG plating suffers from black pad defect or not. To understand this, we need to know the solder reaction with the ENIG plating. When solder melts on ENIG plating, the gold plating quickly dissolves into the molten solder and tin will be in direct contact with the Ni(P) plating. 17,18 Depending on the type of solder, a layer of IMC will form at the interface after cooling. The IMC layer is Ni3Sn4 for the joints of SnPb1,1921 and SnAg,22,23 but (Cu,Ni)6Sn5 for SnAgCu solder joints.24 26 The solder reaction enhances the crystallization of the amorphous Ni(P) plating.19,27,28 For many commercially produced substrates, the phosphorous content in the Ni(P) plating is in the range of 710 wt.%.29 After crystallization, the amorphous Ni(P) plating in this composition range is converted into the mixture of nickel and Ni3P.30,31 The nickel atoms will be taken into the crystals of (Cu,Ni)6Sn5 or react with tin to form Ni3Sn4. Therefore, after reow, the crystallized portion of the Ni(P) plating will become Ni3P that has 15 wt.% (25 at.%) phosphorous.19,32 Between these two compound layers, there is another very thin layer, about 100 nm thick, containing nickel, tin, and phosphorous.20,26,3338 The composition of this layer has not been agreed upon yet in the literature. For convenience, it will be referred to as Ni3SnP according to Reference 36. When the ENIG black pad defect causes solder ball failure, the solder ball is usually separated from the pad between the IMC layer (Ni3Sn4 or (Cu,Ni)6Sn5) and the Ni3P layer. Thus, if the pad surface is analyzed by EDX, the signals detected will be mainly from the Ni3P layer and

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Figure 6. (a) The top view and (b) side view of defected boundaries of the Ni(P) plating nodules from vendor A. The sample was as-received without soldering. A deep and wide groove is indicated by the black arrow. A dark substance is seen on the walls of the deep boundaries.

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c Figure 5. (a) The FIB cutting of a mudcrack in the as-plated substrate (without soldering) from vendor A. Elemental mapping indicates that (b) the corroded area is rich in phosphorous and (c) the gold atoms have penetrated into the core volume of the corroded area.

a phosphorous content of about 15 wt.% or 25 at.% is expected. This high phosphorous content in the fractured pad surface, by itself, is not good evidence for black pad defect. Based on the authors experience and the literature data, the following criteria are proposed for identifying the black pad defect of the ENIG plating. At low magnication, either by optical microscope or SEM, the failed pad appears at. There is very little solder, or no solder, remaining on the pad (Figure 1). At high magnication under SEM, the pad appears dark. Some isolated IMC crystals or solder residues may be visible, but the pad is not covered by solder or IMC layer. Nodule boundaries are clearly seen in a top view of the pad surface (Figure 2a). To verify that the nodule boundaries are separated, approximately 30 degrees of sample tilt of the pad surface should be taken (e.g., Figure 2b) to view the mud-cracks. To obtain conclusive evidence, cross section the pad to reveal spikes in the pad surface (Figure 3). When spikes are observed in the cross section and they can be correlated to the
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1 m Figure 7. An FIB cutting through the defected peripheral area of the pad in Figure 6. Deep corrosion of the Ni(P) plating was revealed.

mud-cracks in the tilted view of the pad surface, then it can be concluded that the ENIG plating has black pad defects. It should be pointed out that while the present work uses cross sections polished by FIB, the spikes can also be revealed by traditional metallographic techniques.39,40 Origin of Black Pad Defect Since the black pad defect is usually found when the BGA package falls off the PCB during assembly, it is logical to suspect that soldering caused the black pad defect. However, this was not found to be true. The as-received (before soldering) substrates from two vendors, A and B, were analyzed. Before analysis, it was known that the ENIG plating by vendor A had black pad defect but that of vendor B did not. Cross sections in Figure 4 show that A had spikes that corresponded to mud-cracks, but even at much higher magnication B did not show any defect and the nodule boundaries were good. The root cause for the black pad defect of the ENIG plating has been discussed in the literature and several models have been proposed. 4,7,13,19,4144 Of these models, Biunnos42 is supported by the results of the present work. His model suggests that black pad defect is the result of galvanic hyper-corrosion of the Ni(P) plating by the immersion gold bath. Earlier experimental results conrmed the validity of this model.7,40,45 The immersion gold process is a controlled corrosion (displacement) process during which nickel atoms on the surface of the Ni(P) plating are replaced by gold atoms.7 In principle, it is a self-limiting process because once the surface of the Ni(P)
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plating is covered by the gold, the displacement reaction stops. However, if the process is out of control, hyperactive corrosion may happen. For instance, the surface of the electroless Ni(P) plating has a nodular structure. There are boundaries and crevices between the nodules.46 If a boundary or crevice is too deep and thus the supply of gold atoms to the crevice is slowed down, the gold concentration in the crevice will be different from that of the plating bath. Consequently, a galvanic cell will be set up between the crevice and the surface, resulting in heavy corrosion in the crevice. Also, reducing agents can be added to immersion gold baths to deposit the gold more quickly. A poor choice of or poor control of these reducing agents may produce the inconsistent nature of the black pad defect (i.e., not every pad on a substrate shows the same degree of defects). Figure 5 provides evidence for this model. The boundary between the two nodules is voided and its opening to the surface is very narrow. The consumed gold of the plating solution in the void cannot be replenished quickly. The concentration difference leads to galvanic corrosion of the Ni(P) plating around the void. The corrosion converts the dense, amorphous Ni(P) into a porous, micro-crystallized structure into which the gold atoms have penetrated, shown by the elemental mapping images in Figure 5. Another fact that should be noted is that, because of the depth of the void and the near-closure of its opening to the surface, after the plating process the plating solution was trapped in it. The rinsing process after plating could not effectively remove the residual plating solution. Therefore, corrosion would continue until the residual solution was exhausted. Failure Mechanism of Solder Joints with Black Pad As mentioned previously, after the molten solder spreads onto the ENIGplated pad, the gold plating dissolves into the solder. The molten solder follows the gold that has penetrated deeply into the corroded area, making the corroded area more porous (see the gold-rich area in Figure 5c). It can be assumed that, even if the corroded area is still solder-

able, the bonding will be very weak due to the porosity of the corroded Ni(P). A low shear stress would be enough to crack the joint. Previous work has found that Kirkendall voids formed between the main IMC (Cu6Sn5 or Ni3Sn4) and the Ni3P layer (i.e., in the thin layer of Ni3SnP).34,35,47 Because of the formation of this voided layer, the interfacial bonding of solder to the ENIG plating is by nature weak even if the Ni(P) plating does not suffer from hyperactive corrosion. Obviously, if the periphery is severely corroded (e.g., Figure 6), cracking is easily initiated and propagates through the voided Ni3SnP layer, leading to fracture of the joints between the main IMC layer and the Ni3P layer. The drawing in Figure 9 schematically shows this fracture process. It can be seen that, after fracture, two different kinds of regions should be observed on the pad side by

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Figure 8. (a) An FIB cutting of the pad periphery without soldering.The Ni(P) layer was cracked and a large area beneath the cracks was defected. (b) The top view of the pad periphery after the solder ball was pulled off. Samples from vendor A.

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Figure 9. A schematic illustration of a solder joint with ENIG that was corroded during the gold plating process. Black pad failure is the result of propagation of the mud-cracks in the Ni(P) plating through a voided thin layer of Ni-Sn-P between IMC and Ni3P layers.

top view. One is the exposed Ni3P and mud-cracks and the other one is the fractured Ni 3SnP layer. Indeed,the authors have seen these two different regions in Figure 2athe dark regions are Ni3P and the gray regions are Ni3SnP. CONCLUSION Since mud-cracks are often observed in the ENIG-plated pads after the solder joints fail, there have been many discussions on whether or not the black pad failure of solder joints was caused by an improper soldering process. In the present work, the authors found that when a BGA substrate has black pad failure of solder joints, it has mud-cracks or spikes in the nickel plating before soldering, and the material around the cracks is corroded. These obervations support the theory that the black pad decit in ENIG plating is the result of hyperactive corrosion of the electroless nickel plating by the immersion gold plating bath. Mud-cracks are created by the soldering process. Interfacial failure of solder joints with the ENIG plating is the combined effect of hyper-galvanic corrosion of the electroless nickel during gold plating and Kirkendall voiding in the Ni3SnP layer after reow. To avoid the black pad failure of solder joints, the key is to avoid hyper-galvanic corrosion of the electroless nickel plaating during the immersion gold plating process.

ACKNOWLEDGEMENT The authors would like to thank B. Holdford for assistance in microanalysis of FIB-polished cross sections. Valuable discussions with Kuldip Johal, Atotech USA, and R.J. Coyle, Lucent Technologies, are gratefully appreciated.
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