Interfacial reaction studies on lead (Pb)-free solder alloys

Recently, the research and development activities for replacing Pb-containing solders with Pb-free solders have been intensified due to both competitive market pressures and environmental issues. As a result of these activities, a few promising candidate solder alloys have been identified, mainly, Sn-based alloys. A key issue affecting the integrity and reliability of solder joints is the interfacial reactions between a molten solder and surface finishes in the solder joint structures. In this paper, a fundamental study of the interfacial reactions between several Pb-free candidate solders and surface finishes commonly used in printed-circuit cards is reported. The Pb-free solders investigated include Sn-3.5 Ag, Sn-3.8 Ag-0.7 Cu, and Sn-3.5 Ag-3.0 Bi. The surface finishes investigated include Cu, Au/Ni(P), Au/Pd/Ni(P), and Au/Ni (electroplated). The reaction kinetics of the dissolution of surface finishes and intermetallic compound growth have been measured as a function of reflow temperature and time. The intermetallic compounds formed during reflow reactions have been identified by SEM with energy dispersive x-ray spectroscopy.     

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.     

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.     

Interfacial behaviors of Sn-Pb,Sn-Ag-Cu Pb-free and mixed Sn-Ag-Cu/Sn-Pb solder joints during electromigration

SnPb-SnAgCu mixed solder joints with Sn-Pb soldering Sn-Ag-Cu Pb-free components are inevitably occurred in the high reliability applications. In this study, the interfacial behaviors in Sn-37Pb and Sn-3.0Ag-0.5Cu mixed solder joints was addressed and compared with Sn-37Pb solder joints and Sn-3.0Ag-0.5Cu solder joints with the influence from isothermal aging and electromigration. Considering the difference on the melting point between Sn-3.0Ag-0.5Cu and Sn-37Pb solder, two mixed solder joints: partial mixing and full mixing between Sn-Pb and Sn-Ag-Cu solders were reached with the peak reflowing temperature of 190 and 250 °C, respectively. During isothermal aging, the intermetallic compound (IMC) layer increased with aging time and its growth was diffusion controlled. There was also no obvious affect from the solder composition on IMC growth. After electromigration with the current density of 2.0 × 10³ A/cm², Sn-37Pb solder joints showed the shortest lifetime with the cracks observed at the cathode for the stressing time < 250 h. In Sn-3.0Ag-0.5Cu Pb-free solder joints, current stressing promoted the growth of IMC layer at the interfaces, but the growing rate of IMC at the anode interface was far faster than that at the cathode interface. Therefore, there existed an obvious polarity effect on IMC growth in Sn-Ag-Cu Pb-free solder joints. After Sn-37Pb was mixed with Sn-3.0Ag-0.5Cu Pb-free solder, whether the partial mixing or the full mixing between Sn-Pb and Sn-Ag-Cu can obviously depress both the crack formation at the cathode side and the IMC growth at the anode.     

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.     

Joint Strength and Microstructure for Sn-Ag-(Cu) Soldering on an Electroless Ni-Au Surface Finish by Using a Flux Containing a Cu Compound

The effect of a flux containing Cu(II) stearate (barrier flux) on the strength of soldered joints between an electroless Ni-Au surface finish and two Pb-free soldering systems, Sn-3Ag-0.5Cu and Sn-3.5Ag (wt.%), was examined. Pull and shock tests showed that barrier flux gave a higher joint strength for both solder compositions than did a flux containing no Cu compounds. Interface analysis revealed that a thin P-rich layer and refined Cu-Ni-Sn intermetallic compounds were formed at the joint interface when barrier flux was used. It is assumed that the supply of Cu from barrier flux suppresses diffusion of Ni into the solder.     

Influence of Cu addition to interface microstructure between Sn-Ag solder and Au/Ni-6P plating

The formation and growth of intermetallics at the interface between Sn-Ag-(Cu) alloy balls and Au/Ni-6P plating were experimentally examined as a function of soldering period. Joint strengths were also evaluated by a ball pull test. For the joint with Sn-3.5Ag, the primary reaction product of Ni₃Sn₄ exhibits growth and shrinkage in thickness repeatedly with a passage of reaction time up to 30 min, while the Ni₃SnP reaction layer monotonously increases its thickness without fluctuation. In the cases of the joints with Cu bearing solder, Sn-3Ag-0.5Cu and Sn-3.5Ag-0.8Cu, a single η-(Cu,Ni)₆Sn₅ interface layer grows by fast Cu segregation from liquid solder to the interface layer on soldering. For all the soldered joints, a P-rich layer appears at the surface region of a Ni-6P plating layer by Ni depletion to form those intermetallic compounds at interfaces. The growth rate of a P-rich layer for Sn-3.5Ag is faster by about 4–8 times than those of the Sn-Ag-Cu. The presence of Cu in solder enhances the formation of the Cu₆Sn₅ intermetallic layer at the interface resulting in prevention of Ni diffusion to liquid solder. For all the soldered joints, coarsened reaction interfaces decrease the joint strengths.     

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.     

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.     

Influence of Cu content on compound formation near the chip side for the flip-chip Sn-3.0Ag-(0.5 or 1.5)Cu solder bump during aging

Sn-Ag-Cu solder is a promising candidate to replace conventional Sn-Pb solder. Interfacial reactions for the flip-chip Sn-3.0Ag-(0.5 or 1.5)Cu solder joints were investigated after aging at 150°C. The under bump metallization (UBM) for the Sn-3.0Ag-(0.5 or 1.5)Cu solders on the chip side was an Al/Ni(V)/Cu thin film, while the bond pad for the Sn-3.0Ag-0.5Cu solder on the plastic substrate side was Cu/electroless Ni/immersion Au. In the Sn-3.0Ag-0.5Cu joint, the Cu layer at the chip side dissolved completely into the solder, and the Ni(V) layer dissolved and reacted with the solder to form a (Cu_1−y,Ni_y)₆Sn₅ intermetallic compound (IMC). For the Sn-3.0Ag-1.5Cu joint, only a portion of the Cu layer dissolved, and the remaining Cu layer reacted with solder to form Cu₆Sn₅ IMC. The Ni in Ni(V) layer was incorporated into the Cu₆Sn₅ IMC through slow solid-state diffusion, with most of the Ni(V) layer preserved. At the plastic substrate side, three interfacial products, (Cu_1−y,Ni_y)₆Sn₅, (Ni_1−x,Cu_x)₃Sn₄, and a P-rich layer, were observed between the solder and the EN layer in both Sn-Ag-Cu joints. The interfacial reaction near the chip side could be related to the Cu concentration in the solder joint. In addition, evolution of the diffusion path near the chip side in Sn-Ag-Cu joints during aging is also discussed herein.     

Interfacial microstructure and bonding strength of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder BGA packages with immersion Ag surface finish

Although it has been verified that tin whiskers can be prevented by the addition of 0.5 wt.% Zn into a Sn-3Ag-0.5Cu-0.5Ce solder, no detailed studies have been conducted on interfacial reactions and mechanical properties of Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with an immersion Ag surface finish. The intermetallic compounds formed during the reflow and aging of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder ball grid array (BGA) packages were investigated. Because more heterogeneous nucleation sites, provided by CeSn₃ intermetallics and Zn atoms, formed in the Sn-3Ag-0.5Cu-0.5Ce-xZn solder matrix, and Cu and Zn have a stronger affinity than Cu and Sn, the Cu-Sn intermetallics growth in Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with Ag/Cu pads was suppressed. The 0.2% Zn addition for inhibiting rapid whisker growth in RE-doped Sn-Ag-Cu solder joints is more appropriate than 0.5 wt.% additions, as excess Zn addition causes poor oxidation resistance and inferior bonding strength.     

热时效和焊点尺寸对SnAgCu微焊点强度的影响

针对高度为100～300μm的无铅钎料Sn-3.0Ag-0.5Cu微焊点,研究了等温热时效和焊点尺寸对其在100℃下拉伸强度的影响。结果表明,保持焊点直径不变时,高度为100,200和300μm微焊点未经热时效的平均拉伸强度分别为53.75,46.59和44.38MPa;热时效时间延长使微焊点内钎料合金显微组织明显粗化,导致焊点拉伸强度降低,前述三种高度的微焊点96h热时效后平均拉伸强度分别为44.13,38.38和33.48MPa,但96h热时效对IMC厚度无明显影响。     

SnAgCu系钎料的合金组织和力学性能

研究了Cu含量对SnAgCu系钎料合金显微组织及其与化学镀Ni基板钎焊接头力学性能的影响。结果表明:高Cu含量SnAgCu合金会产生较多的(CuxNi1-x)6Sn5金属间化合物,从而减少镀Ni层的消耗,进一步提高钎焊接头的剪切强度。与Sn-3.0Ag-0.3Cu相比,Sn-3.0Ag-1.0Cu钎焊接头剪切强度提高了6.78%。经过150℃时效1000h后,界面Ni3(P,Sn)层的增长率从Sn-3.0Ag-0.3Cu合金的约66%降低到Sn-3.0Ag-1.0Cu合金的约40%。     

Alloying effects in near-eutectic Sn-Ag-Cu solder alloys for improved microstructural stability

This study included a comparison of the baseline Sn-3.5Ag eutectic to one near-eutectic ternary alloy, Sn-3.6 Ag-1.0Cu and two quaternary alloys, Sn-3.6Ag-1.0Cu-0.15Co and Sn-3.6Ag-1.0 Cu-0.45 Co, to increase understanding of the beneficial effects of Co on Sn-Ag-Cu solder joints cooled at 1–3 C/sec, typical of reflow practice. The results indicated that joint microstructure refinement is due to Co-enhanced nucleation of the Cu₆Sn₅ phase in the solder matrix, as suggested by Auger elemental mapping and calorimetric measurements. The Co also reduced intermetallic interface faceting and improved the ability of the solder joint samples to maintain their shear strength after aging for 72 hr at 150 C. The baseline Sn-3.5Ag joints exhibited significantly reduced strength and coarser microstructures.     

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.     

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.     

Intermetallic growth studies on Sn-Ag-Cu lead-free solder joints

Solid-state intermetallic compound (IMC) growth behavior plays an important role in solder joint reliability of electronic packaging assemblies. The morphology and growth of interfacial IMC compounds between 95.5Sn-3.8Ag-0.7Cu Pb-free solders and nickel/gold (Ni/Au) surface finish on BGA solder joint specimen is reported. Digital imaging techniques were employed in the measurement of the average IMC growth thickness. The IMC growth behavior subjected to isothermal aging exposure at 125°C, thermal cycling (TC), and thermal shock (TS) with upper soak temperatures of 125°C are compared. An equivalent isothermal aging time is proposed for comparison of IMC layer growth data. It was noted that IMC layer growth under thermal cycling and thermal shock aging gives an acceleration factor of 1.4 and 2.3 based on the equivalent isothermal aging time.     

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.     

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.