Studies of the mechanical and electrical properties of lead-free solder joints

The mechanical and electrical properties of several Pb-free solder joints have been investigated including the interfacial reactions, namely, the thickness and morphology of the intermetallic layers, which are correlated with the shear strength of the solder joint as well as its electrical resistance. A model joint was made by joining two “L-shaped” copper coupons with three Pb-free solders, Sn-3.5Ag (SA), Sn-3.8Ag-0.7Cu (SAC), and Sn-3.5Ag-3Bi (SAB) (all in wt.%), and combined with two surface finishes, Cu and Ni(P)/Au. The thickness and morphology of the intermetallic compounds (IMCs) formed at the interface were affected by solder composition, solder volume, and surface finish. The mechanical and electrical properties of Pb-free solder joints were evaluated and correlated with their interfacial reactions. The microstructure of the solder joints was also investigated to understand the electrical and mechanical characteristics of the Pb-free solder joints.     

Effect of reaction time on mechanical strength of the interface formed between the Sn-Zn(-Bi) solder and the Au/Ni/Cu bond pad

In this work, the shear strengths and the interfacial reactions of Sn-9Zn, Sn-8Zn-1Bi, and Sn-8Zn-3Bi (wt.%) solders with Au/Ni/Cu ball grid array (BGA) pad metallization were systematically investigated after extended reflows. Zn-containing Pb-free solder alloys were kept in molten condition (240°C) on the Au/electrolytic Ni/Cu bond pads for different time periods ranging from 1 min. to 60 min. to render the ultimate interfacial reaction and to observe the consecutive shear strength. After the shear test, fracture surfaces were investigated by scanning electron microscopy equipped with an energy dispersive x-ray spectrometer. Cross-sectional studies of the interfaces were also conducted to correlate with the fracture surfaces. The solder ball shear load for all the solders during extended reflow increased with the increase of reflow time up to a certain stage and then decreased. It was found that the formation of thick Ni-Zn intermetallic compound (IMC) layers at the solder interface of the Au/electrolytic Ni/Cu bond pad with Sn-Zn(-Bi) alloys deteriorated the mechanical strength of the joints. It was also noticed that the Ni-Zn IMC layer was larger in the Sn-Zn solder system than that in the other two Bi-containing solder systems.     

Effects of mechanical deformation and annealing on the microstructure and hardness of Pb-free solders

The microstructure property relations of several Pb-free solders are investigated to understand the microstructural changes during thermal and mechanical processes of Pb-free solders. The Pb-free solder alloys investigated include pure Sn, Sn-0.7% Cu, Sn-3.5% Ag, and Sn-3.8% Ag-0.7% Cu (in weight percent). To reproduce a typical microstructure observed in solder joints, the cooling rate, ingot size, and reflow conditions of cast alloys were carefully controlled. The cast-alloy pellets are subjected to compressive deformation up to 50% and annealing at 150°C for 48 h. The microstructure of Pb-free solders is evaluated as a function of alloy composition, plastic deformation, and annealing. The changes in mechanical property are measured by a microhardness test. The work hardening in Sn-based alloys is found to increase as the amount of alloying elements and/or deformation increases. The changes in microhardness upon deformation and annealing are correlated with the microstructural changes, such as recrystallization or grain growth, in Pb-free solder alloys.     

Reliability issues in Pb-free solder joint miniaturization

As solder joints become increasingly miniaturized to meet the severe demands of future electronic packaging, it is vitally important to consider whether the solder joint size and geometry could become reliability issues and thereby affect implementation of the Pb-free solders. In this study, three bumping techniques, i.e., solder dipping, stencil printing followed by solder reflow, and electroplating of solders with subsequent reflow, were used to investigate the interfacial interactions of molten Sn-3.5Ag, Sn-3.8Ag-0.7Cu, and pure Sn solders on a copper pad at 240°C. The resultant interfacial microstructures, coming from a variety of Cu pads, with sizes ranging from 1 mm to 25 μm, and representing different solder bump geometries, have been investigated. In addition, a two-dimensional thermodynamic/kinetic model has been developed to assist the understanding of the kinetics of interdiffusion and the formation of interfacial intermetallic compounds. Experimental results and theoretical predictions both suggest that the solder bump size and geometry can influence the as-soldered microstructure; therefore, this factor should be taken into consideration for the design of future reliable ultrafine Pb-free solder joints.     

Effect of microelements addition on the interfacial reaction between Sn-Ag-Cu solders and the Cu substrate

Three kinds of Sn-Ag-based lead-free solders, Sn-3.5Ag-0.7Cu, Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge, and Sn-3.5Ag-0.07Ni (in wt.%), were selected to explore the effect of microelements (Ni and Ge) on the interfacial reaction between the solder and the Cu substrate. The thickness of the interfacial intermetallics formed with the Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge and Sn-3.5Ag-0.07Ni solders is several times that of the Sn-3.5Ag-0.7Cu solder. The added microelements converted the feature of interfacial intermetallics from pebble shape to worm shape. However, the results of x-ray diffraction (XRD) analysis suggest that the interfacial intermetallics formed with both solders have the same crystal structure. The results of energy dispersive spectroscopy (EDS) analysis show that the major interfacial intermetallic formed with the Sn-3.5Ag-0.7Cu solder is Cu₆Sn₅, while it is (Cu_x,Ni_1−x)₆Sn₅ with Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge. Ni influences the interfacial intermetallics and plays the influential role on the difference of interfacial reaction rate between liquid solder and solid Cu and the morphology of interfacial intermetallics. Additionally, the growth kinetics of the interfacial intermetallic compounds (IMCs) formed in the systems of Cu/Sn-3.5Ag-0.7Cu and Cu/Sn-3.5Ag-0.07Ni at high-temperature storage was also explored.     

Interfacial microstructure evolution in Pb-free solder systems

The Sn-3.5Ag and Sn-3.0Ag-0.5Cu ball-grid-array solder balls bonded onto Ni/Au metallization exhibited different interfacial morphology after both wetting and solid-state reactions. In contrast to the eutectic-SnPb solder system, both Pb-free systems showed higher solder-ball shear strength after annealing. Reprecipitation of Au as (Au,Ni)Sn₄ at the interface, as shown in the eutectic-SnPb solder system, was not observed in both Pb-free solder systems. Instead, Ni₃Sn₄ and Cu-Sn-Ni-Au intermetallic compounds (IMCs) were found in the SnAg and SnAgCu systems, respectively. In the SnAgCu system, a thick, acicular-Cu-Sn-Ni IMC formed after wetting, but a faceted-Cu-Sn-Ni-Au phase was found with longer annealing. The growth of this interfacial phase in the Sn-3.0Ag-0.5Cu solder system was also slightly inhibited by the addition of Cu, with a formation energy of about 200 kJ/mol.     

Interfacial reactions in the pb-free composite solders with indium layers

A Pb-free composite solder is prepared with a Pb-free solder substrate and a plated-indium layer. The indium layer melts during the soldering process, wets the substrates, and forms a sound solder joint. Since the melting temperature of indium is 156.6°C, lower than that of the eutectic Sn-Pb, which is at 183°C, the soldering process can be carried out at a temperature lower than that of the conventional soldering process. Composite solder joints with three different Pb-free solders, Sn, Sn-3.5 wt.% Ag, and Sn-3.5 wt.% Ag-0.5 wt.% Cu, and two substrates, Ni and Cu, are prepared. The interfaces between the indium layer, Pb-free solder, and Ni and Cu substrate are examined. A good solder joint is formed after a 2-min reflow at 170°C. A very thick reaction zone at the indium/Pb-free solder interface and a thin reaction layer at the indium/substrate interface are observed.     

Mechanical strength of Sn-3.5Ag-based solders and related bondings

The tensile strengths of bulk solders and joint couples of Sn-3.5Ag-0.5Cu, Sn-3.5Ag-0.07Ni, and Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge solders and the shear strengths of ball grid array (BGA) specimens, solder-ball-attached Cu/Ni/Au metallized substrates were investigated. The tensile strength of the bulk is degraded by thermal aging. The Ni-containing solder exhibits lower tensile strength than Sn-3.5Ag-0.5Cu after thermal aging. However, the Ni-containing solder joints show greater tensile strength than the Cu/Sn-3.5Ag-0.5Cu/Cu joint. Fracture of the solder joint occurs between the intermetallic compound (IMC) and the solder. The shear strength and fracture mechanism of BGA specimens are the same regardless of solder composition.     

Interfacial reaction and joint reliability of fine-pitch flip-chip solder bump using stencil printing method

This study was focused on the formation and reliability evaluation of solder joints with different diameters and pitches for flip chip applications. We investigated the interfacial reaction and shear strength between two different solders (Sn-37Pb and Sn-3.0Ag-0.5Cu, in wt.%) and ENIG (Electroless Nickel Immersion Gold) UBM (Under Bump Metallurgy) during multiple reflow. Firstly, we formed the flip chip solder bumps on the Ti/Cu/ENIG metallized Si wafer using a stencil printing method. After reflow, the average solder bump diameters were about 130, 160 and 190 μm, respectively. After multiple reflows, Ni₃Sn₄ intermetallic compound (IMC) layer formed at the Sn-37Pb solder/ENIG UBM interface. On the other hand, in the case of Sn-3.0Ag-0.5Cu solder, (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄ IMCs were formed at the interface. The shear force of the Pb-free Sn-3.0Ag-0.5Cu flip chip solder bump was higher than that of the conventional Sn-37Pb flip chip solder bump.     

Additive Effect of Kirkendall Void Formation in Sn-3.5Ag Solder Joints on Common Substrates

The Sn-3.5Ag and Sn-3.5Ag-0.2Co-0.1Ni lead-free solders were investigated on common electronics substrates, namely, organic solderability preservative (OSP) and electroless Ni/immersion Au (ENIG) surface finishes. The formation of Kirkendall voids at the interfacial region during isothermal solid aging was explored. For the Sn-3.5Ag-0.2Co-0.1Ni/OSP solder joint, the Kirkendall voids were present after isothermal solid-state aging at higher temperature (e.g., 150°C); however, the size of voids did not change remarkably with prolonged aging time due to the depressed Cu₃Sn layer growth. For ENIG surface finishes, the 0.2Co-0.1Ni additions seemed to enhance the longitudinal groove-shaped voids at the Ni₃P layer; however, void formation at the solder/Ni₃Sn₄ interface was effectively reduced. This might be attributed to the reduced Sn activity in the solder matrix and the suppressed Ni-P-Sn layer formation.     

Reactions of lead-free solders with CuNi metallizations

We have done experimental research on the dissolution rate and intermetallic growth on Cu, Ni, and CuNi-alloy substrates as a function of time and Cu/Ni ratio of the substrate. Reactions that occur when CuNi metallizations are soldered with lead-free solders were investigated. The experiments were performed using Sn-3.5Ag and Sn-3.8Ag-0.7Cu solders and different CuNi alloys. To determine the rate of dissolution of the substrate material into the solder, CuNi foils of different concentrations were immersed in Sn-3.5Ag and Sn-3.8Ag-0.7Cu solder baths for soldering times ranging from 15 sec to 5 min at 250°C. In addition, reflows of solder balls were made on top of bulk substrates to study the reaction when there is a practically infinite amount of CuNi available compared to the amount of solder. Thin film experiments were also done, where Ni containing under bump metallizations (UBMs) were fabricated and reflowed with eutectic SnAg solder balls. The nickel slows down the dissolution of the UBM into the solder and the formation of intermetallics during reflow compared to Cu metallizations. The solder/UBM interfaces were analyzed with SEM to find out how Ni concentration affects the reaction, and how much Ni is needed to obtain a sufficiently slow reaction rate.     

Interfacial reaction and solder joint reliability of Pb-free solders in lead frame chip scale packages (LF-CSP)

Chip scale packages (CSP) have essential solder joint quality problems, and a board level reliability is a key issue in design and development of the CSP type packages. There has been an effort to eliminate Pb from solder due to its toxicology. To evaluate the various solder balls in CSP package applications, Pb-free Sn-Ag-X (X=In, Cu, Bi) and Sn-9Zn-1Bi-5In solder balls were characterized by melting behavior, phases, interfacial reaction, and solder joint reliability. For studying joint strength between solders and under bump metallurgy (UBM) systems, various UBMs were prepared by electroplating and electroless plating. After T/C (temperature cycle) test, Sn3.5Ag8.5In solder was partially corroded and its shape was distorted. This phenomenon was observed in a Sn3Ag10In 1Cu solder system, too. Their fractured surface, microstructure of solder joint interface, and of bulk solder ball were examined and analyzed by optical microscopy, SEM and EDX. To simulate the real surface mounting condition and evaluate the solder joint reliability on board level, Daisy chain test samples using LF-CSP packages were prepared with various Pb-free solders, then a temperature cycle test (−65∼ 150°C) was performed. All tested Pb-free solders showed better board level solder joint reliability than Sn-36Pb-2Ag. Sn-3.5Ag-0.7Cu and Sn-9Zn-1Bi-5In solders showed 35%, 100% superior solder joint reliability than Sn-36Pb-2Ag solder ball, respectively.     

Morphology and Growth of Intermetallics at the Interface of Sn-based Solders and Cu with Different Surface Finishes

Several types of surface finishes have been applied on Cu substrates in an effort to facilitate bonding and improve the reliability of lead-free solder joints. In the current research, the effects of printed circuit board surface finishes on the reliability of the solder joints were investigated by examining the morphology and growth behavior of the intermetallic compounds (IMCs) between Sn-based solders and different surface finishes on Cu. Three types of Cu substrates with different surface finishes were fabricated in this study: organic solderability preservative (OSP)/Cu, Ni/Cu, and electroless nickel immersion gold (ENIG)/Cu. Sn-3.5Ag and Sn-3.0Ag-0.5Cu were used as the solders. In the experiment, the solder joint specimens were aged isothermally at 150°C for up to 1000 h. Experimental results revealed that the OSP surface finish promoted the interdiffusion between Cu and Sn during soldering. The composition and morphology of the IMC layer at the solder/Ni/Cu interface were sensitive to the Cu concentration in the solder. Meanwhile, the solder joints with different morphological features of the IMCs exhibited significant differences in shear strengths. The Au-containing ENIG surface finish affected the shear strength of the solder joint significantly at the initial stage of isothermal aging.     

Comparative study of interfacial reactions of Sn-Ag-Cu and Sn-Ag solders on Cu pads during reflow soldering

The interfacial reaction in soldering is a crucial subject for the solder-joint integrity and reliability in electronic packaging technology. However, electronic industries are moving toward lead-free alloys because of environmental concerns. This drive has highlighted the fact that the industry has not yet arrived at a decision for lead-free solders. Among the lead-free alloys, Sn-3.5Ag and Sn-3.5Ag-0.5Cu are the two potential candidates. Here, detailed microstructural studies were carried out to compare the interfacial reaction of Sn-3.5Ag and Sn-3.5Ag-0.5Cu solder with a ball grid array (BGA) Cu substrate for different reflow times. The Cu dissolution from the substrate was observed for different soldering temperatures ranging from 230°C to 250°C, and the dissolution was found to increase with time and temperature. Dissolution of Cu in the Sn-3.5Ag solder is so fast that, at 240°C, 12 μm of the Cu substrate is fully consumed within 5 min. Much less dissolution is observed for the Sn-3.5Ag-0.5Cu solder. In respect to such high dissolution, there is no significant difference observed in the intermetallic compound (IMC) thickness at the interface for both solder alloys. A simplistic theoretical approach is carried out to find out the amount of Cu₆Sn₅ IMCs in the bulk of the solder by the measurement of the Cu consumption from the substrate and the thickness of the IMCs that form on the interface.     

Wetting characteristics of Pb-free solder alloys and PWB finishes

For a successful transition to Pb-free manufacturing in electronics assembly, it is critical to understand the behavior of Pb-free solders (in bulk and paste form) and their interaction with the Pb-free printed wiring board (PWB) finishes. This paper presents the results obtained from solder paste spread tests and wetting balance experiments with several Pb-free solder alloys and Pb-free PWB finishes. The solder alloys studied were Sn3.4Ag4.8Bi, Sn4.0Ag0.5Cu, Sn3.5Ag and Sn0.7Cu. Eutectic Sn37Pb was used as a reference. The PWB surface finishes were Sn, NiAu, Ag and OSP. Wetting balance experiments were conducted in air while the spread tests were performed in air and nitrogen to understand the effect of reflow atmosphere on the spreading. Surface analysis techniques such as Nomarski phase contrast microscopy, Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to characterize the as-received PWB finishes. Sequential electrochemical reduction analysis (SERA) was also performed on the as-received PWB test coupons and on the Sn test coupons after multiple reflow cycles. The effect of multiple reflow cycles on the wetting performance, spreading and the surface composition of the PWB finishes was studied.     

Comparative Study of ENIG and ENEPIG as Surface Finishes for a Sn-Ag-Cu Solder Joint

Interfacial reactions and joint reliability of Sn-3.0Ag-0.5Cu solder with two different surface finishes, electroless nickel-immersion gold (ENIG) and electroless nickel-electroless palladium-immersion gold (ENEPIG), were evaluated during a reflow process. We first compared the interfacial reactions of the two solder joints and also successfully revealed a connection between the interfacial reaction behavior and mechanical reliability. The Sn-Ag-Cu/ENIG joint exhibited a higher intermetallic compound (IMC) growth rate and a higher consumption rate of the Ni(P) layer than the Sn-Ag-Cu/ENEPIG joint. The presence of the Pd layer in the ENEPIG suppressed the growth of the interfacial IMC layer and the consumption of the Ni(P) layer, resulting in the superior interfacial stability of the solder joint. The shear test results show that the ENIG joint fractured along the interface, exhibiting indications of brittle failure possibly due to the brittle IMC layer. In contrast, the failure of the ENEPIG joint only went through the bulk solder, supporting the idea that the interface is mechanically reliable. The results from this study confirm that the Sn-Ag-Cu/ENEPIG solder joint is mechanically robust and, thus, the combination is a viable option for a Pb-free package system.     

Ball Impact Responses of Ni- or Ge-Doped Sn-Ag-Cu Solder Joints

In this work, we present ball impact test (BIT) responses and fractographies obtained at an impact velocity of 500 mm/s on Sn-4Ag-0.5Cu, Sn-1Ag-0.5Cu, Sn-1Ag-0.5Cu-0.05Ni, Sn-1.2Ag-0.5Cu-0.05Ni, and Sn-1Ag-0.5Cu-0.05Ge package-level solder joints. The solder joints are bonded on substrate pads of either immersion tin (IT) or direct solder on pad (DSOP) surface finishes. Differences of BIT results with respect to multi-reflow are also reported. Taking the impact energy as an indication of board-level drop reliability of the solder joints, the BIT results indicate that better reliability can be achieved by adopting Sn-Ag-Cu solder alloys with low Ag weight contents as well as IT substrate pad finish rather than DSOP. Moreover, the addition of Ni or Ge to the solder alloy provides a large improvement; Ni alters the interfacial intermetallic compound (IMC) structure while Ge enhances the mechanical behavior of the bulk solder.     

The Crystal Orientation of β-Sn Grains in Sn-Ag and Sn-Cu Solders Affected by Their Interfacial Reactions with Cu and Ni(P) Under Bump Metallurgy

Recently, it has been reported that the crystal orientation and grain size of the β-Sn phase in Sn-rich solders have profound effects on the reliabilities of Pb-free solder joints, such as thermo-mechanical fatigue and electromigration. Additionally, it is also known that the microstructure of the Sn-rich solders is strongly affected by their alloy composition. In this study the grain size and orientation of the β-Sn phase were investigated in terms of their alloy composition and interfacial reactions with two different under bump metallurgies (UBMs), Cu and Ni(P). Solder balls (380 μm in diameter) of pure Sn, Sn-0.5Cu, Sn-0.5Ag, and Sn-1.8Ag (in weight percent) were reflowed on Cu and Ni(P) UBMs. After the reflow at 250°C for 120 s, the microstructure of the solder joints was analyzed by cross-polarization light microscopy and electron backscatter diffraction. For the compositional analysis of solder joints, electron probe micro-analysis was used and thermodynamics calculations were also performed. During reflow on Cu or Ni(P) UBM, Cu and Ni atoms were dissolved quickly and were saturated to their solubility limits in the solders, causing changes in composition and β-Sn grain orientation.     

Interfacial reaction study on a solder joint with Sn-4Ag-0.5Cu solder ball and Sn-7Zn-Al (30 ppm) solder paste in a lead-free wafer level chip scale package

The interfacial reactions of solder joints between the Sn-4Ag-0.5Cu solder ball and the Sn-7Zn-Al (30 ppm) presoldered paste were investigated in a wafer level chip scale package (WLCSP). After appropriate surface mount technology (SMT) reflow process on the printed circuit board (PCB) with organic solderability preservative (Cu/OSP) and Cu/Ni/Au surface finish, samples were subjected to 150°C high-temperature storage (HTS), 1,000 h aging. Sequentially, the cross-sectional analysis is scrutinized using a scanning electron microscope (SEM)/energy-dispersive spectrometer (EDS) and energy probe microanalysis (EPMA) to observe the metallurgical evolution in the interface and solder buck itself. It was found that Zn-enriched intermetallic compounds (IMCs) without Sn were formed and migrated from the presolder paste region into the solder after reflow and 150°C HTS test.     

Dissolution behavior of Cu and Ag substrates in molten solders

This study investigated the dissolution behavior of Cu and Ag substrates in molten Sn, Sn-3.5Ag, Sn-4.0Ag-0.5Cu, Sn-8.6Zn and Sn-8.55Zn-0.5Ag-0.1Al-0.5Ga lead-free solders as well as in Sn-37Pb solder for comparison at 300, 350, and 400°C. Results show that Sn-Zn alloys have a substantially lower dissolution rate of both Cu and Ag substrates than the other solders. Differences in interfacial intermetallic compounds formed during reaction and the morphology of these compounds strongly affected the substrate dissolution behavior. Soldering temperature and the corresponding solubility limit of the substrate elements in the liquid solder also played important roles in the interfacial morphology and dissolution rate of substrate.