Forming high temperature solder joints through liquid phase sintering of solder paste

Eutectic lead-tin has been the solder of choice throughout the history of the electronics industry. Alternatives to this material are now being considered because of environmental concerns, as well as the strength and temperature limitations of eutectic lead-tin. Identifying and using these alternative materials poses significant challenges, many of which we believe can be addressed if one forms solder joints through liquid phase enhanced sintering. First, most alternative solder materials have significantly higher melting temperatures (than eutectic lead-tin), and their use would require the replacement of much of the manufacturing infrastructure. In this work joints with shear stresses approaching that of eutectic lead-tin solder were formed by sintering a eutectic tin-sliver solder paste (T_m=221°C) doped with 3 v/o eutectic Sn-Bi powder at 210°C for 30 min. Second, to date the industry has limited its consideration to eutectic or near-eutectic alloys because of the concern of forming cold solder joints. In this work joints have been prepared by sintering solder pastes with a wide thermal range at temperatures just above the solidus, where a small amount of liquid will form and therefore enhance the rate of sintering, which have shear strengths of 6 MPa or higher. These findings indicate that it may be worthwhile to investigate developing a sinterable solder paste, which can be used to prepare surface mount assemblies.     

Effects of palladium and solder aging on mechanical and fatigue properties of tin-lead eutectic solder

The effects of (a) 0.5 wt.% of Pd addition, and (b) aging on mechanical and fatigue properties of eutectic solder (63Sn37Pb) were investigated. The creep rate of eutectic solder at room temperature is not affected by Pd addition. However, at 80°C, solder containing Pd creeps slower than Sn-Pb eutectic. Strain rate dramatically affects yield and tensile stress of eutectic solder with Pd as it does for the binary solder. Isothermal fatigue life of solder at 25°C is essentially not changed by Pd addition. The microstructure of Pd-containing solder consisted of polyhedral grains of (Pb), (Sn), and a dispersion of PdSn₄ intermetallic. Significant microstructural changes and interphase interface phenomena take place during creep deformation at 25 and 80°C. Ambient aging for seven years leads to solder softening and to moderate increase in isothermal fatigue life.     

Ethylene glycol ether free solder paste development

There are growing concerns in the electronics industry for not only finding alternatives to lead but also other potentially hazardous materials as well. This paper summarizes the development of ethylene glycol ether (EGE)-free solder flux for the formulation of lead-free solder pastes. Replacing the toxic components in the flux was only the first challenge, the criteria of commercially proven pastes also had to be met. Both commercial and in-house solder paste formulations were evaluated for printability, reflow, wetting, flux residue removal, and solder void characteristics. Two critical issues, solder bump boids and flux residue removal, were identified and associated with the high temperature reflow of Pb-free pastes. These issues were not effectively improved by the existing commercial EGE-free solder pastes. New solder paste formulations were developed utilizing alternative chemistry than those found in traditional solder paste fluxes. These pastes, some, of which are also water soluble, reduced void frequency and size by more than 4x as compared to vendors' pastes. Solder bump height uniformity of 135 4 m within each die was consistently achieved. Thermal-mechanical reliability tests were performed on various lead-free solder alloys using the new flux formulations. The reliability of flip chip assembled DCA on organic boards with both OSP/Cu and Cu/Ni/au pad metallizations were comparable to eutectic Sn63Pb37 bumped assemblies using commerical pastes.     

Creep properties of eutectic Sn-3.5Ag solder joints reinforced with mechanically incorporated Ni particles

The creep deformation behavior of eutectic Sn-3.5Ag based Ni particle rein forced composite solder joints was investigated. The Ni particle reinforced composite solder was prepared by mechanically dispersing 15 vol.% of Ni particles into eutectic Sn-3.5Ag solder paste. Static-loading creep tests were carried out on solder joint specimens at 25 C, 65 C, and 105 C, representing homologous temperatures ranging from 0.6 to 0.78. A novel-design, miniature creep-testing frame was utilized in this study. Various creep parameters such as the global and localized creep strain, steady-state creep rate, onset of tertiary creep and the activation energy for creep were quantified by mapping the distorted laser ablation pattern imprinted on the solder joint prior to testing. The Ni-reinforced composite solder joint showed improved creep resistance compared to the results previously reported for eutectic Sn-3.5Ag solder, Sn-4.0Ag-0.5Cu solder alloys, and for eutectic Sn-3.5Ag solder reinforced with Cu or Ag particle reinforcements. The activation energy for creep was ∼0.52 eV for Sn-3.5Ag and Sn-4Ag-0.5Cu solder alloys. The activation energies ranged from 0.55–0.64 eV for Cu, Ag, and Ni reinforced composite solder joints, respectively. Most often, creep fracture occurred closer to one side of the solder joint within the solder matrix.     

The creep and strain rate sensitivity of a high Pb content solder with comparisons to 60Sn/40Pb solder

Creep plays an important role in the mechanical behavior of solder alloys. This paper presents creep and strain rate sensitivity data for a Pb rich solder (92.5Pb, 2.5Ag, 5Sn-Indalloy 151) and compares it to the behavior of near eutectic 60Sn/40Pb solder. The high Pb alloy is used for exposures to higher temperatures than can be withstood by eutectic Sn/Pb solders. The Pb rich solder tested here is less strain rate sensitive than 60Sn/40Pb. There are also differences in the creep behavior.     

Effects of load and thermal conditions on Pb-free solder joint reliability

Reliability of lead-free solder joints has been a hot topic widely debated in the electronic industry. Most published data indicate that a change to lead-free soldering has the potential benefit of more reliable solder joints than the current Sn-Pb eutectic solder joints. However, in reality many mechanical, metallurgical, thermal, and environmental factors affect the service reliability of solder joints. This paper tries to shed some light on the effects of mechanical loading and thermal conditions on solder joint reliability. These conditions are determined not only by external environments but also by the solder alloy itself and the joint geometry. Analyses with first principles are carried out on solder joints of both areal array and peripheral packages. Effects on fatigue life of solder joint geometry, thermal and mechanical characteristics of components and substrate materials, and application conditions are discussed. The analysis helps explain why lead-free solder joints may not be more reliable in certain application conditions than the current Sn-Pb eutectic solder joints.     

Processing and aging characteristics of eutectic Sn-3.5Ag solder reinforced with mechanically incorporated Ni particles

Composite solders offer improved properties compared to non-composite solders. Ni reinforced composite solder was prepared by mechanically dispersing 15 vol.% of Ni particles into eutectic Sn-3.5Ag solder paste. The average size of the Ni particle reinforcements was approximately 5 microns. The morphology, size and distribution of the reinforcing phase were characterized metallographically. Solid-state isothermal aging study was performed on small realistic size solder joints to study the formation and growth of the intermetallic (IM) layers at Ni reinforcement/solder and Cu substrate/solder interfaces. Effects of reflow on microstructure and solderability, were studied using Cu substrates. Regarding solderability, the wetting angle of multiple reflowed Ni reinforced composite solder was compared to the solder matrix alloy, eutectic Sn-3.5Ag. General findings of this study revealed that Ni particle reinforced composite solder has comparable wetting characteristics to eutectic Sn-3.5Ag solder. Significant IM layers growth was observed in the Ni composite solder joint under isothermal aging at 150 C. Microstructural evolution was insignificant when aging temperature was lower than 100 C. Multiple reflow did not significantly change the microstructure in Ni composite solder joint.     

Pressure-assisted low-temperature sintering of silver paste as an alternative die-attach solution to solder reflow

Pressure-assisted low-temperature sintering of silver paste is shown to be a viable alternative to solder reflow as a die-attachment solution. A quasihydrostatic pressure is used to lower the sintering temperature. The effect of parameters such as temperature and pressure are investigated. Characterization of the silver-attached samples shows a significant improvement in electrical conductivity, thermal conductivity and mechanical strength of the joint. Given that silver deforms with little accumulation of inelastic strains, and given the absence of large voids in the attachment layer, it is also expected that the joint to be more resistant to fatigue failure than a solder attached junction. Due to the high melting temperature of silver, this alternative process is also suitable for high temperature packages.     

A potential drop-in replacement for eutectic Sn-Pb solder—The Sn-Zn-Ag-Al-Ga solder

The Sn-Zn alloy exhibits the closest eutectic temperature to the eutectic Sn-Pb solder, although it suffers an easy oxidation characteristic. A novel alloy based on the Sn-Zn eutectic alloy was developed and found promising as a drop-in replacement for the eutectic Sn-Pb solder. This alloy, consisting of a Sn-Zn-Ag-Al-Ga combination, was developed, showing promising properties. Differential scanning calorimetry (DSC) investigation reveals that the investigated solder exhibits a eutectic temperature of around 199°C. The thermal gravimetric analysis (TGA) study shows it attains much better oxidation resistance than the eutectic Sn-Pb solder does at 250°C. The stress-strain curve indicates that this solder also possesses a higher ultimate tensile strength (UTS) and a better ductility than the eutectic Sn-Pb solder. A wetting time, on Cu, of less than 1 sec was found for this solder with a suitable, organic acid-activated flux. Gallium tended to enhance wetting behavior. The cost of this solder was also estimated and was found to be comparable with the Sn-Pb solder.     

Differential scanning calorimetry studies on eutectic (Sn63/Pb37) solder paste and powder for surface mount technology

The properties of eutectic solder paste (Sn63/Pb37) in an RMA flux and solder powder have been investigated using differential scanning calorimetry. The results show that the melting point for both the paste and powder samples occurs at 182 degrees C and also the effects of supercooling occurs for both the paste and the powder samples. The supercooling results are of vital importance in the modelling of the thermal processes for electronics manufacture using surface mount technology.<>     

Study on Cu particles-enhanced SnPb composite solder

The Sn-Pb solder is widely used in the electronics industry. With the development of surface mount technology and miniaturization of elements, mechanical properties of the solder are critical. Creep resistance and size stability of soldered joints are important for optical electronics. In the present work, Cu particles with a size of about 8 μm were added to the eutectic 63Sn-37Pb solder to improve the creep property of the soldering alloy. The contents of the Cu particles are 5 vol.% and 10 vol.% separately. The solder matrix is 63Sn37Pb particles with a normal size of 43 μm. The composite solder pastes are manufactured from a mixture of these particles with no-clean flux. Under reflow soldering, the metal particles were uniformly dispersed in the Sn-Pb alloy, and very thin intermetallic compounds were formed between the particles and matrix. To simulate practical soldering of printed circuit boards, a specially designed mini specimen with lap joint is used for the creep-rupture test. For the condition of ambient temperature, the creep-rupture lifetime of the soldered joint can be increased by one order quantitatively using the composite solder compared to the 63Sn37Pb eutectic solder. Other mechanical properties are measured also. In addition, the wetting property of the enhanced solder is good through the wettability test.     

A study of large area die bonding materials and their corresponding mechanical and thermal properties

We tested the ability of Au/Sn eutectic, silver paste, and solder paste to bond to a large area as well as the bonding of a high power LED die to a highly conductive submount. The samples ran through several tests including ultrasound image, shear force, and thermal resistance measurement. Finite element analysis (FEA) models were built for comparison and analysis. Au/Sn bonding shows the best thermal and mechanical properties. Silver paste shows lower contact thermal resistance compared with solder paste. Although the thickness of the silver paste bonding layer is greater than the solder paste bonding layer, the average total thermal resistance is noticeably lower than the solder paste bonded samples.     

Microstructure, creep properties, and failure mechanism of SnAgCu solder joints

The effect of microstructure on the creep properties and the failure mechanism of SnAgCu solder joints was studied. Single overlap shear specimens made of FR-4 printed circuit boards (PCBs) with organic solderability preservative (OSP), NiAu, and immersion Sn surface finish were reflow-soldered with hypoeutectic, eutectic, and hypereutectic SnAgCu solder paste. Creep tests of the solder joints were performed at 85°C and 105°C under constant load. The effect of microstructure on the creep behavior of the joints was studied by examining the fracture surfaces and cross-sectional samples of the tested joints. Results show that the intermetallic compound at the interface between the PCB and solder affects the fracture behavior of SnAgCu solder joints, thus creating a significant difference in the creep properties of solder joints on different surface finishes. Composition of SnAgCu solder was also found to affect the creep properties of the joints.     

Effects of Co addition in eutectic Sn-3.5Ag solder on shear strength and microstructural development

In this study, the approach of composite solder using eutectic Sn-3.5Ag solder and Co was tried. Co particles and Sn-3.5Ag solder paste were mechanically mixed at Co weight fractions from 0.1% to 2.0%. For the Co-mixed Sn-3.5Ag solder pastes, their melting temperatures and spreading areas were measured. The solder pastes were stencil printed on test substrates and reflowed to form solder bumps. Ball shear test was performed to examine shear strength of Co-reinforced Sn-3.5Ag solder bumps. As a result, Co addition up to 2 wt.% did not alter the melting temperature under heating but reduced undercooling. The maximum shear strength of Co-reinforced Sn-3.5Ag solder bumps increased by 28% compared to normal ones. The increase in shear strength can be attributed to the (Cu,Co)₃Sn₂ intermetallic compounds.     

低银无铅焊膏板级封装工艺和焊点可靠性试验

针对低Ag无铅焊膏的市场需求,研究开发了一种适用于99.0Sn0.3Ag0.7Cu低Ag无铅焊膏用松香型无卤素助焊剂(WTO—LF3000),配制了相应的无铅焊膏(WTO—LF3000—SAC0307),并对其板级封装工艺适应性及焊点可靠性进行了考察,用测试后样品的电气可靠性作为接头可靠性评价条件。结果表明:所开发的低Ag无铅焊膏熔点和润湿性符合产品实际要求。配制的焊膏印刷质量良好,焊点切片观察其孔隙率<25%,满足行业标准IPC—A—610D之要求。样品分别经跌落、震动和温度循环试验后,无焊点脱落等现象,电气功能正常。     

The effect of soldering process variables on the microstructure and mechanical properties of eutectic Sn-Ag/Cu solder joints

Fundamental understanding of the relationship among process, microstructure, and mechanical properties is essential to solder alloy design, soldering process development, and joint reliability prediction and optimization. This research focused on the process-structure-property relationship in eutectic Sn-Ag/Cu solder joints. As a Pb-free alternative, eutectic Sn-Ag solder offers enhanced mechanical properties, good wettability on Cu and Cu alloys, and the potential for a broader range of application compared to eutectic Sn-Pb solder. The relationship between soldering process parameters (soldering temperature, reflow time, and cooling rate) and joint microstructure was studied systemati-cally. Microhardness, tensile shear strength, and shear creep strength were measured and the relationship between the joint microstructures and mechani-cal properties was determined. Based on these results, low soldering tempera-tures, fast cooling rates, and short reflow times are suggested for producing joints with the best shear strength, ductility, and creep resistance.     

Lead contamination of a transient liquid-phase-processed Sn-Bi lead-free solder paste

The influence of Pb contamination on the solidification behavior of a transient liquid-phase powder-processed Sn-Bi solder paste has been studied using differential scanning calorimetry. The development of low-temperature ternary reactions was found to be very sensitive to both the Pb and Bi content of the solder. Solders with high Bi content favored the formation of the ternary eutectic reaction. Solders with high Pb contents favored the formation of a ternary peritectic reaction. These results agree very well with solidification predictions present in the literature for ternary Sn-Bi-Pb alloys. In particular, the dependence of ternary reactions on composition is due to a change in solidification path. Alloy compositions which mark the transition from one path to the next were identified.     

Interfacial reactions and mechanical properties of ball-grid-array solder joints using Cu-cored solder balls

Interfacial reactions and mechanical properties of the ball-grid-array (BGA) solder joints using monolithic eutectic SnPB and Cu-cored solder balls after reflow and solid-state annealing were investigated. The Cu cores of three different sizes were used in the solder joints. The incorporation of a Cu core into the BGA solder joint effectively inhibits the (Au_1−xNi_x)Sn₄ regrouping and the (Cu_1−x−yAu_xNi_y)₆Sn₅ phase is formed at the joint interface instead. Growth of the intermetallic compounds formed in the monolithic and Cu-cored solder joints approximately obeys the parabolic law. In the Cu-cored solder joints, the larger the Cu core is, the slower the intermetallic compounds grow. The size effect of the Cu core on the intermetallic compound growth results from the inconsistent amount of the outer solder layer. Shear and tensile strengths of the Cu-cored solder joints decrease with increasing solid-state annealing time, and do not have a noticeable relationship with the Cu-core size. Shear and tensile tests also show that the mechanical strength of the Cu-cored solder joint is better than that of the monolithic solder joint.     

Constitutive and damage model for a lead-free solder

A unified creep plasticity theory with damage is presented for a lead-free solder. The damage is caused by microcracking both inside grains and along grain boundaries and increases with cyclic loading and creep. The Mura theory of microcrack nucleation was used to model the microcrack formation, while the percolation theory was used to characterize the damage such microcracking caused to the mechanical performance of the solder. The model is materials science based and is capable of application to solder joints of different sizes. It is also cast within the framework of phenomenological damage mechanics and is therefore convenient for implementation into commercially available computational software package. The theory was used to model isothermal experimental data for a eutectic solder 96.5Sn-3.5Ag, and good agreement was achieved.     

无铅焊膏的设计与展望

分析了无铅焊膏的构成和技术要求。对无铅焊膏用焊粉及助焊剂配方设计的现状进行了讨论,焊粉的成分多为Sn、Ag和Cu,粒度越来越多地采用20μm;助焊剂多为改性松香、有机酸活化剂等。展望了无铅焊膏的研究与发展趋势。