Intermetallic phase detection in lead-free solders using synchrotron X-ray diffraction

The high-intensity, high-resolution x-ray source at the European Synchrotron Radiation Facility (ESRF) has been used in x-ray diffraction (XRD) experiments to detect intermetallic compounds (IMCs) in lead-free solder bumps. The IMCs found in 95.5Sn3.8Ag0.7Cu solder bumps on Cu pads with electroplated-nickel immersion-gold (ENIG) surface finish are consistent with results based on traditional destructive methods. Moreover, after positive identification of the IMCs from the diffraction data, spatial distribution plots over the entire bump were obtained. These spatial distributions for selected intermetallic phases display the layer thickness and confirm the locations of the IMCs. For isothermally aged solder samples, results have shown that much thicker layers of IMCs have grown from the pad interface into the bulk of the solder. Additionally, the XRD technique has also been used in a temperature-resolved mode to observe the formation of IMCs, in situ, during the solidification of the solder joint. The results demonstrate that the XRD technique is very attractive as it allows for nondestructive investigations to be performed on expensive state-of-the-art electronic components, thereby allowing new, lead-free materials to be fully characterized.

Effect of adding 0.3wt% Ni into the Sn-0.7wt% Cu solder - Part II: Growth of intermetallic layer with Cu during wetting and aging

The growth behavior of intermetallic layer with or without adding 0.3 wt% Ni into the Sn-0.7Cu solder was studied during the wetting reaction on Cu-substrate and thereafter in solid-state aging condition. The Cu-solder reaction couple was prepared at 255, 275 and 295 °C for 10 s. The samples reacted at 255 °C were then isothermally aged for 2-14 days at 150 °C. The reaction species formed for the Sn-0.7Cu/Cu and Sn-0.7Cu-0.3Ni/Cu soldering systems were Cu6Sn5 and (CuNi)6Sn5, respectively. The thickness of the intermetallic compounds formed at the solder/Cu interfaces and also in the bulk of both solders increased with the increase of reaction temperature. It was found that Ni-containing Sn-0.7Cu solder exhibited lower growth of intermetallic layer during wetting and in the early stage of aging and eventually exceeded the intermetallic layer thickness of Sn-0.7Cu/Cu soldering system after 6 days of aging. As the aging time proceeds, a non-uniform intermetallic layer growth tendency was observed for the case of Sn-0.7Cu-0.3Ni solder. The growth behavior of intermetallic layer during aging for both solders followed the diffusion-controlled mechanism. The intermetallic layer growth rate constants for Sn-0.7Cu and Sn-0.7Cu-0.3Ni solders were calculated as 1.41 × 10-17 and 1.89 × 10-17 m2/s, respectively which indicated that adding 0.3 wt% Ni with Sn-0.7Cu solder contributed to the higher growth of intermetallic layer during aging. © 2006 Elsevier B.V. All rights reserved.

Fracture mechanics analysis of cracks in solder joint intermetallic compounds

The trend towards miniaturization of electronic products leads to the need for very small sized solder joints. Therefore, there is a higher reliability risk that too large a fraction of solder joints will transform into Intermetallic Compounds (IMCs) at the solder interface. In this paper, fracture mechanics study of the IMC layer for SnPb and Pb-free solder joints was carried out using finite element numerical computer modelling method. It is assumed that only one crack is present in the IMC layer. Linear Elastic Fracture Mechanics (LEFM) approach is used for parametric study of the Stress Intensity Factors (SIF, KI and KII), at the predefined crack in the IMC layer of solder butt joint tensile sample. Contrary to intuition, it is revealed that a thicker IMC layer in fact increases the reliability of solder joint for a cracked IMC. Value of KI and KII are found to decrease with the location of the crack further away from the solder interfaces while other parameters are constant. Solder thickness and strain rate were also found to have a significant influence on the SIF values. It has been found that soft solder matrix generates non-uniform plastic deformation across the solder-IMC interface near the crack tip that is responsible to obtain higher KI and KII.

Effect of reflow profile and thermal cycle ageing on the intermetallic formation and growth in lead-free soldering

The formation and growth of intermetallic compound layer thickness is one of the important issues in search for reliable electronic and electrical connections. Intermetallic compounds (IMCs) are an essential part of solder joints. At low levels, they have a strengthening effect on the joint; but at higher levels, they tend to make solder joints more brittle. If the solder joint is subjected to long-standing exposure of high temperature, this could result in continuous growth of intermetallic compound layer. The brittle intermetallic compound layer formed in this way is very much prone to fracture and cold therefore lead to mechanical and electrical failure of the joint. Therefore, the primary aim of this study is to investigate the growth of intermetallic compound layer thickness subjected to five different reflow profiles. The study also looks at the effect of three different temperature cycles (with maximum cycle temperature of 25 0C, 40 0C and 60 0C) on intermetallic compound formation and their growth behaviour.. Two different Sn-Ag-Cu solder pastes (namely paste P1 and paste P2) which were different in flux medium, were used for the study. The result showed that the growth of intermetallic compound layer thickness was a function of ageing temperature. It was found that the rate of growth of intermetallic compound layer thickness of paste P1 was higher than paste P2 at the same temperature condition. This behaviour could be related to the differences in flux mediums of solder paste samples used.

Wetting and Reaction of Sn-2.8Ag-0.5Cu-1.0Bi Solder with Cu and Ni Substrates

The wettability of newly developed Sn-2.8Ag-0.5Cu-1.0Bi lead-free solder on Cu and Ni substrates was assessed through the wetting balance tests. The wettability assessment parameters such as contact angle (ϑc) and maximum wetting force (Fw) were documented for three solder bath temperatures with three commercial fluxes, namely, no-clean (NC), nonactivated (R), and water-soluble organic acid flux (WS). It was found that the lead-free Sn-2.8Ag-0.5Cu-1.0Bi solder exhibited less wetting force, i.e., poorer wettability, than the conventional Sn-37Pb solder for all flux types and solder bath temperatures. The wettability of Sn-2.8Ag-0.5Cu-1.0Bi lead-free solder on Cu substrate was much higher than that on Ni substrate. Nonwetting for Sn-2.8Ag-0.5Cu-1.0Bi and Sn-Pb solders on Ni substrate occurred when R-type flux was used. A model was built and simulations were performed for the wetting balance test. The simulation results were found very close to the experimental results. It was also observed that larger values of immersion depth resulted in a decrease of the wetting force and corresponding meniscus height, whereas the increase in substrate perimeter enhanced the wettability. The wetting reactions between the solder and Cu/Ni substrates were also investigated, and it was found that Cu atoms diffused into the solder through the intermetallic compounds (IMCs) much faster than did the Ni atoms. Rapid formation of IMCs inhibited the wettability of Sn-2.8Ag-0.5Cu-1.0Bi solder compared to the Sn-Pb solder.

High electric current density-induced interfacial reactions in micro ball grid array (μBGA) solder joints

The effect of a high electric current density on the interfacial reactions of micro ball grid array solder joints was studied at room temperature and at 150 °C. Four types of phenomena were reported. Along with electromigration-induced interfacial intermetallic compound (IMC) formation, dissolution at the Cu under bump metallization (UBM)/bond pad was also noticed. With a detailed investigation, it was found that the narrow and thin metallization at the component side produced “Joule heating” due to its higher resistance, which in turn was responsible for the rapid dissolution of the Cu UBM/bond pad near to the Cu trace. During an “electromigration test” of a solder joint, the heat generation due to Joule heating and the heat dissipation from the package should be considered carefully. When the heat dissipation fails to compete with the Joule heating, the solder joint melts and molten solder accelerates the interfacial reactions in the solder joint. The presence of a liquid phase was demonstrated from microstructural evidence of solder joints after different current stressing (ranging from 0.3 to 2 A) as well as an in situ observation. Electromigration-induced liquid state diffusion of Cu was found to be responsible for the higher growth rate of the IMC on the anode side.

Reliability study of the electroless Ni–P layer against solder alloy

Copper (Cu) has been widely used in the under bump metallurgy of chip and substrate metallization for chip packaging. However, due to the rapid formation of Cu–Sn intermetallic compound (IMC) at the tin-based solder/Cu interface during solder reaction, the reliability of this type of solder joint is a serious concern. In this work, electroless nickel–phosphorous (Ni–P) layer was deposited on the Cu pad of the flexible substrate as a diffusion barrier between Cu and the solder materials. The deposition was carried out in a commercial acidic sodium hypophosphite bath at 85 °C for different pH values. It was found that for the same deposition time period, higher pH bath composition (mild acidic) yields thicker Ni–P layer with lower phosphorous content. Solder balls having composition 62%Sn–36%Pb–2%Ag were reflowed at 240 °C for 1 to 180 min on three types of electroless Ni–P layers deposited at the pH value of 4, 4.8 and 6, respectively. Thermal stability of the electroless Ni–P barrier layer against the Sn–36%Pb–2%Ag solder reflowed for different time periods was examined by scanning electron microscopy equipped with energy dispersed X-ray. Solder ball shear test was performed in order to find out the relationship between the mechanical strength of solder joints and the characteristics of the electroless Ni–P layer deposited. The layer deposited in the pH 4 acidic bath showed the weak barrier against reflow soldering whereas layer deposited in pH 6 acidic bath showed better barrier against reflow soldering. Mechanical strength of the joints were deteriorated quickly in the layer deposited at pH 4 acidic bath, which was found to be thin and has a high phosphorous content. From the cross-sectional studies and fracture surface analyses, it was found that the appearance of the dark crystalline phosphorous-rich Ni layer weakened the interface and hence lower solder ball shear strength. Ni–Sn IMC formed at the interfaces was found to be more stable at the low phosphorous content (∼14 at.%) layer. Electroless Ni–P deposited at mild acidic bath resulting phosphorous content of around 14 at.% is suggested as the best barrier layer for Sn–36%Pb–2%Ag solder.

Multiple reflow study of ball grid array (BGA) solder joints on Au/Ni metallization

This paper evaluates the shearing behavior of ball grid array (BGA) solder joints on Au/Ni/Cu pads of FR4 substrates after multiple reflow soldering. A new Pb-free solder, Sn–3Ag–0.5Cu–8In (SACI), has been compared with Sn–3Ag–0.5Cu (SAC) and Sn–37Pb (SP) solders, in terms of fracture surfaces, shearing forces and microstructures. Three failure modes, ball cut, a combination of solder shear and solder/pad bond separation, and pad lift, are assessed for the different solders and reflow cycles. It is found that the shearing forces of the SP and SAC solder joints tend to increase slightly with an increase in the number of reflow cycles due to diffusion-induced solid solution strengthening of the bulk solder and augmentation of the shearing area. However, the shearing forces of the SACI solder joints decrease slightly after four cycles of reflow, which is ascribed to the thermal degradation of both the solder/intermetallic compound (IMC) and IMC/Ni interfaces. The SACI solder joints yield the highest strengths, whereas the SP solder joints give the smallest values, irrespective of the number of reflow cycles. Thickening of the interfacial IMC layer and coarsening of the dispersing IMC particles within the bulk solders were also observed. Nevertheless, the variation of shearing forces and IMC thickness with different numbers of reflow cycles was not so significant since the Ni under layer acted as an effective diffusion barrier. In addition, the initially-formed IMC layer retarded the further extensive dissolution of the pad material and its interaction with the solder

Shear strength analysis of ball grid array (BGA) solder interfaces

Ball shear test is the most common test method used to assess the reliability of bond strength for ball grid array (BGA) packages. In this work, a combined experimental and numerical study was carried out to realize of BGA solder interface strength. Solder mask defined bond pads on the BGA substrate were used for BGA ball bonding. Different bond pad metallizations and solder alloys were used. Solid state aging at 150degC up to 1000 h has been carried out to change the interfacial microstructure. Cross-sectional studies of the solder-to-bond pad interfaces was conducted by scanning electron microscopy (SEM) equipped with an energy dispersive X-ray (EDX) analyzer to investigate the interfacial reaction phenomena. Ball shear tests have been carried out to obtain the mechanical strength of the solder joints and to correlate shear behaviour with the interfacial reaction products. An attempt has been taken to realize experimental findings by Finite Element Analysis (FEA). It was found that intermetallic compound (IMC) formation at the solder interface plays an important role in the BGA solder bond strength. By changing the morphology and the microchemistry of IMCs, the fracture propagation path could be changed and hence, reliability could be improved

High current density induced damage mechanisms in electronic solder joints: a state-of-the-art review

High current density induced damages such as electromigration in the on-chip interconnection /metallization of Al or Cu has been the subject of intense study over the last 40 years. Recently, because of the increasing trend of miniaturization of the electronic packaging that encloses the chip, electromigration as well as other high current density induced damages are becoming a growing concern for off-chip interconnection where low melting point solder joints are commonly used. Before long, a huge number of publications have been explored on the electromigration issue of solder joints. However, a wide spectrum of findings might confuse electronic companies/designers. Thus, a review of the high current induced damages in solder joints is timely right this moment. We have selected 6 major phenomena to review in this paper. They are (i) electromigration (mass transfer due electron bombardment), (ii) thermomigration (mass transfer due to thermal gradient), (iii) enhanced intermetallic compound growth, (iv) enhanced current crowding, (v) enhanced under bump metallisation dissolution and (vi) high Joule heating and (vii) solder melting. the damage mechanisms under high current stressing in the tiny solder joint, mentioned in the review article, are significant roadblocks to further miniaturization of electronics. Without through understanding of these failure mechanisms by experiments coupled with mathematical modeling work, further miniaturization in electronics will be jeopardized

Effect of current stressing on the reliability of 63Sn37Pb solder joints

The effect of current stressing on the reliability of 63Sn37Pb solder joints with Cu pads was investigated at temperatures of −5 °C and 125 °C up to 600 h. The samples were stressed with 3 A current (6.0 × 102 A/cm2 in the solder joint with diameter of 800 μm and 1.7 × 104 A/cm2 in the Cu trace with cross section area of 35 × 500 μm). The temperatures of the samples and interfacial reaction within the solder joints were examined. The microstructural change of the solder joints aged at 125 °C without current flow was also evaluated for comparison. It was confirmed that the current flow could cause the temperature of solder joints to rise rapidly and remarkably due to accumulation of massive Joule heat generated by the Cu trace. The solder joints stressed at 125 °C with 3 A current had an extensive growth of Cu6Sn5 and Cu3Sn intermetallic compounds (IMC) at both top and bottom solder-to-pad interfaces. It was a direct result of accelerated aging rather than an electromigration or thermomigration effect in this experiment. The kinetic is believed to be bulk diffusion controlled solid-state reaction, irrespective of the electron flow direction. When stressed at −5 °C with 3 A current, no significant change in microstructure and composition of the solder joints had occurred due to a very low diffusivity of the atoms as most Joule heat was eliminated at low temperature. The IMC evolution of the solder joints aged at 125 °C exhibited a subparabolic growth behavior, which is presumed to be a combined mechanism of grain boundary diffusion and bulk diffusion. This is mainly ascribed to the retardant effect against the diffusion course by the sufficiently thick IMC layer that was initially formed during the reflow soldering.

Precipitation of heavy metals from wastewater using simulated flue gas: sequent additions of fly ash, lime and carbon dioxide

Lime is a preferred precipitant for the removal of heavy metals from industrial wastewater due to its relatively low cost. To reduce heavy metal concentration to an acceptable level for discharge, in this work, fly ash was added as a seed material to enhance lime precipitation and the suspension was exposed to CO2 gas. The fly ash-lime-carbonation treatment increased the particle size of the precipitate and significantly improved sedimentation of sludge and the efficiency of heavy metal removal. The residual concentrations of chromium, copper, lead and zinc in effluents can be reduced to (mg L-1) 0.08, 0.14, 0.03 and 0.45, respectively. Examination of the precipitates by XRD and thermal analysis techniques showed that calcium-heavy metal double hydroxides and carbonates were present. The precipitate agglomerated and hardened naturally, facilitating disposal without the need for additional solidification/stabilization measures prior to landfill. It is suggested that fly ash, lime and CO2, captured directly from flue gas, may have potential as a method for wastewater treatment. This method could allow the ex-situ sequestration of CO2, particularly where flue-gas derived CO2 is available near wastewater treatment facilities. (C) 2009 Elsevier Ltd. All rights reserved.

Influence of carbonation on the acid neutralization capacity of cements and cement-solidified/stabilized electroplating sludge

Portland cement (PC) and blended cements containing pulverized fuel ash (PFA) or granulated blast-furnace slag (GGBS) were used to solidify/stabilize an electroplating sludge in this work. The acid neutralization capacity (ANC) of the hydrated pastes increased in the order of PC > PC/GGBS > PC/PFA. The GGBS or PFA replacement (80 wt%) reduced the ANC of the hydrated pastes by 30–50%. The ANC of the blended cement-solidified electroplating sludge (cement/sludge 1:2) was 20–30% higher than that of the hydrated blended cement pastes. Upon carbonation, there was little difference in the ANC of the three cement pastes, but the presence of electroplating sludge (cement/sludge 1:2) increased the ANC by 20%. Blended cements were more effective binders for immobilization of Ni, Cr and Cu, compared with PC, whereas Zn was encapsulated more effectively in the latter. Accelerated carbonation improved the immobilization of Cr, Cu and Zn, but not Ni. The geochemical code PHREEQC, with the edited database from EQ3/6 and HATCHES, was used to calculate the saturation index and solubility of likely heavy metal precipitates in cement-based solidification/stabilization systems. The release of heavy metals could be related to the disruption of cement matrices and the remarkable variation of solubility of heavy metal precipitates at different pH values.