Epitaxial growth of Cu6Sn5 formed at Sn-based lead-free solder/non-textured polycrystalline Cu plate interface

This study examines the epitaxial growth of the intermetallic compound (IMC) of Cu₆Sn₅ (or (Cu,Ni)₆Sn₅) that forms at the interface between molten Sn-based lead-free solders and non-textured polycrystalline Cu substrates. Sn, Sn–Cu, Sn–Cu–Ni and Sn–Ag–Cu solders were investigated. The dominant growing planes in a hexagonal structure of this IMC on Cu substrates are (101) and (102). Addition of trace Ni into Sn–Cu solders leads to an increase in (101) growth and a decrease in (102) growth. The presence of Ag in Sn–Ag–Cu solders facilitates (102) growth and suppresses (101) growth. Such an epitaxial growth should have a large influence on the mechanical and electrical characteristics of the Sn-based solder/Cu joints.     

Wettability of molten Sn-Bi-Cu solder on Cu substrate

The wetting behavior of a new Sn-Bi-Cu Pb-free solder on Cu substrate was investigated by sessile drop method under an Ar-H₂ flow in the temperature range from 493 K to 623 K. The contact angle curves tested at 548 K and 623 K are found to fit exponential rule very well. However, the contact angle curve tested under 493 K is not well consistent with exponential rule, for which the spreading course may be classified into three stages. Equilibrium contact angles between Sn-Bi-Cu solder and Cu substrate decrease monotonously with the increase in temperature, which are 28°, 24° and 18° at 493 K, 548 K and 623 K, respectively. The results show that 69.5Sn-30Bi-0.5Cu exhibits good wettability on Cu substrate. Intermetallics formed at the 69.5Sn-30Bi-0.5Cu/Cu interface are identified as Cu₆Sn₅ adjacent to the solder and Cu₃Sn adjacent to the Cu substrate, respectively. Formation of intermetallic seems to improve strong wetting of the substrate by the solder.     

无铅焊料研究现状与发展展望

随着电子工业飞速发展以及人们环保意识的提高，以“绿色焊接”为主题的电子装配技术对无铅焊料的需求也尤为迫切。本文从焊料可焊性和焊接蛄构的可靠性等方面介绍了近年来国内外无铅焊料研究方面的最新成果；着重概括了为提高焊接性能而在配料组分、金属间化合物析出与组织控制等工作，重点阐明了稀土元素在焊料组织控制中的关键作用；针对我国稀土资源蕴藏丰富的特点，指出了元铅焊料进一步发展的方向。     

Failure mode analysis of lead-free solder joints under high speed impact testing

Using an Instron micro-impact system, this study investigates the failure characteristics of 96.5Sn–3Ag–0.5Cu lead-free solder joints aged at either room temperature or 125 °C, respectively, and then impacted at shear rates of up to 1 m/s. Four types of failure mode are identified, namely M1: interfacial fracture with no residual solder left on the pad; M2: interfacial fracture with residual solder left on the pad; M3: solder ball fracture; and M4: substrate fracture. The experimental results reveal that the solder specimens fail in different failure modes at the same impact speed. The transition from ductile to brittle failure occurs at an impact speed of around 0.5 m/s. At an impact speed of 0.7 (±0.05) m/s or more, over 70% of the specimens fail in the M1 or M2 modes under all of the testing conditions. The isothermal aging process is found to reduce the interfacial strength, and hence the percentage of M3 and M4 mode failures reduces significantly. Overall, the experimental results suggest that the failure mode distribution obtained in high speed impact tests performed at 0.5 m/s provides a feasible component-level quality assurance index.     

Evolution of mechanical and electrical properties of tin-lead and lead free solder to copper joint interface

Cu-(Sn37Pb) and Cu-(Sn3.5Ag0.5Cu) solder joints were prepared at the same reflow temperature of 230 °C. The microstructural observation of the solder assemblies in scanning and transmission electron microscopes confirmed the presence of η-Cu₆Sn₅ in case of the former, and Cu₃Sn + η-Cu₆Sn₅ for the latter in the reaction zone. The findings are correlated with the electrical and mechanical properties of the joints. Lead free solder-Cu joint exhibited lower reaction zone thickness and improved electrical conductivity (0.28 × 10⁶Ω^− 1 cm^− 1) and shear strength ∼ 68MPa compared to conventional lead-tin solder-Cu joint. The latter showed electrical conductivity and shear strength of 0.22 × 10⁶Ω^− 1 cm^− 1 and ∼ 55 MPa, respectively. The difference in reaction zone thickness is explained on the basis of melt superheat, with Sn being the primary diffusing species in the intermetallic layer.     

Fracture load prediction of lead-free solder joints

Continuous and discrete SAC305 solder joints of different lengths were made between copper bars under standard surface mount (SMT) processing conditions, and then fractured under mode-I loading. The load-displacement behavior corresponding to crack initiation and the subsequent toughening before ultimate failure were recorded and used to calculate the critical strain energy release rates. The fracture of the discrete solder joints was then simulated using finite elements with two different failure criteria: one in terms of the critical strain energy release rate at initiation, G_ci, and another based on a cohesive zone model at the crack tip (CZM). Both criteria predicted the fracture loads reasonably well. In addition, the CZM was able to predict accurately the overall load-displacement behavior of the discrete joint specimen. It could also predict the load sharing that occurred between neighboring solder joints as a function of joint pitch and adherend stiffness. This has application in the modeling of the strength of solder joint arrays such as those found in ball grid array packages.     

Nanoindentation characterization of intermetallic compounds formed between Sn–Cu (–Ni) ball grid arrays and Cu substrates

The formation of intermetallic compounds (IMCs) at the solder–substrate interface is essential in the manufacturing of solder joints. In this study, the effect of Ni addition into Sn–Cu lead-free solders on mechanical properties of the IMCs formed at the interface between solder ball grid arrays (BGAs) and Cu substrates, which experienced multiple reflows, were investigated. The results from nanoindentation tests showed that elastic modulus and hardness of (Cu,Ni)₆Sn₅ were higher than those of Cu₆Sn₅. The hardnesses of (Cu,Ni)₆Sn₅ were more scattered compared to those of Cu₆Sn₅, which may be attributed to the crystallographic characteristics such as growth texture of the IMCs.     

Influence of laminate type on tin whisker growth in tin-rich lead-free solder alloys

This paper describes variations in whisker growth on the surface of tin-rich, lead-free alloys soldered on a Cu layer depending on the laminate used for the printed circuit board, which can be either glass-epoxy or paper-phenol. The structure of the glass-epoxy laminate surface is characterized by spatial nonuniformity caused by the regular structure formed by regions of glass fibers and resin in the top layer of the laminate. The higher value of thermal expansion of the resin than of the glass fiber means that the area of the resin expands more than that of the glass fiber. This causes local compressive stress in the solder layer and as a result promotes whisker growth in the area of the alloy soldered on the Cu layer over the glass fiber. This effect does not occur on the surface of an alloy soldered on Cu layer over a paper-phenol laminate.     

Effects of Co and Ni addition on reactive diffusion between Sn–3.5Ag solder and Cu during soldering and annealing

The reactive diffusion between Sn–Ag solders and Cu was experimentally examined during soldering and isothermal annealing. Three sorts of solders with compositions of Sn–3.5Ag, Sn–3.5Ag–0.1Ni and Sn–3.5Ag–0.1Co were used for the experiment. Each solder was soldered on a Cu plate at 523 K (250 °C) for 1–60 s in a pure nitrogen gas, and then the solder/Cu diffusion couple was isothermally annealed at 423 K (150 °C) for 168–1008 h. Due to soldering, only Cu₆Sn₅ is formed at the interface in each diffusion couple. On the other hand, Cu₃Sn is produced between Cu₆Sn₅ and Cu owing to the isothermal annealing. The composition of Cu₆Sn₅ is (Cu_0.8Ni_0.2)₆Sn₅ and (Cu_0.93Ni_0.07)₆Sn₅ on the solder and Cu₃Sn sides, respectively, in the (Sn–3.5Ag–0.1Ni)/Cu diffusion couple, and it is (Cu_0.9Co_0.1)₆Sn₅ and (Cu_0.99Co_0.01)₆Sn₅ on the solder and Cu₃Sn sides, respectively, in the (Sn–3.5Ag–0.1Co)/Cu diffusion couple. Different rate-controlling processes were suggested for the (Sn–3.5Ag)/Cu, (Sn–3.5Ag–0.1Ni)/Cu and (Sn–3.5Ag–0.1Co)/Cu diffusion couples. Finally, thermodynamic models were herein adopted to explore influences of the additives on the thermodynamic interaction of the component elements and the driving force for the growth of intermetallics.     

Characterization of Co-Sn intermetallic compounds in Sn-3.0Ag-0.5Cu-0.5Co lead-free solder alloy

The minor addition of Co into Sn-3.0Ag-0.5Cu lead-free solder alloy triggered the formation of Co-Sn intermetallic compounds. The Sn-3.0Ag-0.5Cu-0.5Co solder alloy was heated up to 300 °C or 400 °C and then cooled down to the room temperature at different rates. A new Co-Sn intermetallic phase, say, CoSn₃ containing small amount of Cu, were detected. Only CoSn₃ phase was formed in the solder alloy from 300 °C regardless of the cooling rate. However, during the solidification from 400 °C, the CoSn₂ + CoSn₃ cascade structures were illustrated after slow furnace cooling due to the peritectical reaction, i.e., CoSn₂ + L(Sn) → CoSn₃, while only CoSn₂ was observed after rapid quench. A novel DSC technique was employed herein to demonstrate the presence of this peritectical reaction. The mechanical properties of the individual phases of Co-Sn intermetallics were measured and compared with other sole phases in the solder alloy.     

High-temperature shear strength of lead-free Sn-Sb-Ag/Al2O3 composite solder

The lead-free Sn-1.7Sb-1.5Ag solder alloy and the same material reinforced with 5 vol.% of 0.3-μm Al₂O₃ particles were synthesized using the powder-metallurgy route of blending, compaction, sintering, and extrusion. The mechanical properties of both monolithic and composite solders were studied by shear punch testing (SPT) at temperatures in the range of 25-130 °C. Depending on the test temperature, the shear yield stress (SYS) increased by 4.8-8.8 MPa, and ultimate shear strength (USS) increased by 6.2-8.8 MPa in the composite material. The strength improvement was mostly due to the CTE mismatch between the matrix and the particles, and to a lesser extent to the Orowan strengthening mechanism of the submicro-sized Al₂O₃ particles in the composite solder. The contribution of each of these mechanisms was used in a modified shear lag model to predict the total composite-strengthening achieved.     

Effect of geometry on the fracture behavior of lead-free solder joints

Copper bars were soldered along their length with a thin layer of lead-free Sn3.0Ag05.Cu alloy under standard surface mount processing conditions to prepare double cantilever beam (DCB) specimens. The geometry of the DCBs was varied by changing the thickness of the solder layer and the copper bars. These specimens were then fractured under mode-I and two mixed-mode loading conditions. The initiation strain energy release rate, G_ci, increased with the relative fraction of mode-II, but was unaffected by the changes in either the substrate stiffness or the solder layer thickness. However, the steady-state strain energy release rate, realized after several millimeters of crack growth, was found to increase with the solder layer thickness at the various mode ratios. The crack path was found to be influenced by mode ratio of loading and followed a path that maximizes the von Mises strain rather than maximum principal stress. Finally, some preliminary results indicated that the loading rate significantly affects the G_ci.     

Intermetallic compounds formed at the interface between Cu substrate and an Sn-9Zn-0.5Ag lead-free solder

The intermetallic compounds (IMCs) formed at the interface between Cu substrate and an Sn-9Zn-0.5Ag lead-free solder alloy have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron diffraction (ED). The XRD patterns show that the main IMCs formed at the interface of Sn-9Zn-0.5Ag/Cu are γ-Cu₅Zn₈ and η′-Cu₆Sn₅. The Ag₃Sn IMC with orthorhombic structure was also observed at the Sn-9Zn-0.5Ag/Cu interface by TEM and ED analyses. The interfacial adhesion strength between the Cu substrate and Sn-9Zn-0.5Ag lead-free solder alloy is higher than that of the Sn-9Zn alloy due to the formation of Ag₃Sn IMC at the interface.     

Effect of a Trace of Bi and Ni on the Microstructure and Wetting Properties of Sn-Zn-Cu Lead-Free Solder

The microstructure and melting behavior of Sn-9Zn-2Cu （SZC） lead-free solder with 3 wt pct Bi and various amount of Ni additions were studied. The wetting properties and the interracial reaction of Sn-Zn-Cu with Cu substrate were also examined. The results indicated that the addition of 3 wt pct Bi could decrease the melting point of the solder and Ni would refine the microstructure and the rod-shape Cu5Zn8 phase changed into square-shape （Cu, Ni）5Zn8 phase. The addition of Bi, Ni greatly improved the wettability of SZC solder. In addition, the interracial phase of the solders/Cu joint was typical planar Cu5Zn8 in SZC-3Bi-INi alloy.     

Shear deformation behavior of a Sn-3Ag-0.5Cu single solder ball at intermediate strain rates

Shear tests were conducted to evaluate the mechanical behavior of miniature single solder ball joints. The tests were carried out at room temperature under displacement control mode and various displacement rates (2.16-0.019 mm/s) using a miniaturized testing machine with an attached piezo-electric actuator. The mean shear stress was estimated on the basis of the mean cross-section area rather than the minimum cross-section area. The shear fracture strength of the present solder ball joints generally increased as the shear strain rate increased due to the sensitivity of the bulk solder strength to the strain rate. The relationship between strain rate and stress of the current shear tests is consistent with findings from other experimental techniques on the same solder alloy. The unloading shear fracture toughness was found to increase as the shear strain rate increased. The unloading shear fracture toughness is generally consistent with the amount of bulk solder on the fractured surface.     

无铅焊接合金的制备及性能研究

制备了Sn-Zn、Sn-Zn-Bi、Sn-Zn-Bi-RE与Sn-Zn-Bi-Ag系无铅焊接合金，研究了合金的熔点、熔化温度区间、对铜板的润湿性、微观结构和电化学性能。实验结果表明：Bi元素的加入能够降低Sn-Zn合金的熔点，但熔化温度区间增大；Bi、Ag、混合RE能够细化晶粒，使组织更均匀；电化学研究表明，加入适量的混合RE和Ag可提高合金的耐腐蚀性。     

The effect of wall-slip formation on the rheological behaviour of lead-free solder pastes

Wall-slip plays an important role in the flow behaviour of solder paste materials. The wall-slip arises due to the various attractive and repulsive forces acting between the solder particles and the walls of the measuring geometry. These interactions could lead to the presence of a thin liquid layer adjacent to the wall, which causes slippage. The aim of this study is to investigate the influence of the solder paste formulation on wall-slip formation and its effect on the printability of these pastes material. A wall-slip model is utilised to calculate the true viscosity and slip velocity for the lead-free solder pastes samples used in this study. The difference in the measured viscosity and the true viscosity could indicate wall-slip formation between the solder pastes and the parallel plate. Sample P1 showed a higher slip velocity compared to sample P2. The slip velocity calculated for the solder pastes could be used as a performance indicator to understand the paste release characteristics in the stencil printing process.     

Electrochemical behavior of a lead-free SnAg solder alloy affected by the microstructure array

The aim of this study is to evaluate the electrochemical corrosion behavior of a Sn–Ag solder alloy in a 0.5 M NaCl solution at 25 °C as a function of microstructural characteristics. Different microstructure morphologies, which can be found in Sn–Ag solder joints and that are imposed by the local solidification cooling rate, are evaluated and correlated to the resulting scale of the dendritic matrix and the morphology of the Ag₃Sn intermetallic compound. Cylindrical metallic molds at two different initial temperatures were employed permitting the effect of 0.15 °C/s and 0.02 °C/s cooling rates on the microstructure pattern to be experimentally examined. Electrochemical impedance spectroscopy (EIS) diagrams, potentiodynamic polarization curves and an equivalent circuit analysis were used to evaluate the electrochemical parameters. It was found that higher cooling rates during solidification are associated with fine dendritic arrays and a mixture of spheroids and fiber-like Ag₃Sn particles which result in better corrosion resistance than coarse dendrite arrays associated with a mixture of fibers and plate-like Ag₃Sn morphologies which result from very slow cooling rates.     

添加微量元素的Sn-Ag-Sb-Zn系无铅焊料性能研究

在Sn-Ag-Sb-Zn焊料合金中添加微量元素P、Bi、In和Ga,进行了力学性能和物理性能试验.结果表明:试验合金的密度比Sn-37Pb合金降低9.26%-10.55%;剪切强度比Sn-37Pb合金增加6%-51.3%;但熔点有所提高,结晶温度在6.32-7.88℃之间.微量元素的加入对合金的润湿性能有所改善;并能明显提高接头剪切强度.新开发的焊料合金的综合性能已经超过了Sn-37Pb焊料.     

高性能梯度复合管制备及界面接合机理研究

本文研究了AlCrFe—FeCr—FeAl高性能梯度复合管中金属过渡层与金属基体接合界面组织结构，及其对力学性能的影响。结果表明：利用金属间化合物作为梯度过渡层，使得基体与内衬层形成牢固的冶金结合。使复合管的力学性能显著提高；同时，高硬度的金属过渡层与陶瓷层组成的双层复合结构，使得复合管的使用寿命显著延长。