Effect of cooling rate on microstructure and shear strength of pure Sn,Sn-0.7Cu,Sn-3.5Ag,and Sn-37Pb solders

The microstructure and shear strength characteristics of pure Sn and the eutectic compositions of Sn-37Pb, Sn-0.7Cu, and Sn-3.5Ag prepared under identical reflow conditions but subjected to two different cooling conditions were evaluated at room temperature. For the four solders, the ultimate shear strength increased with increasing strain rate from 10⁻⁵ s⁻¹ to 10⁻¹ s⁻¹. Decreasing the cooling rate tended to decrease the ultimate shear strength for both the Sn-0.7Cu and Sn-3.5Ag solders. The effects of work hardening resulting from increased strain rate were more prevalent in quench-cooled (QC) samples.     

Effect of cooling rate on growth of the intermetallic compound and fracture mode of near-eutectic Sn-Ag-Cu/Cu pad: Before and after aging

Several near-eutectic solders of (1) Sn-3.5Ag, (2) Sn-3.0Ag-0.7Cu, (3) Sn-3.0Ag-1.5Cu, (4) Sn-3.7Ag-0.9Cu, and (5) Sn-6.0Ag-0.5Cu (in wt.% unless specified otherwise) were cooled at different rates after reflow soldering on the Cu pad above 250°C for 60 sec. Three different media of cooling were used to control cooling rates: fast water quenching, medium cooling on an aluminum block, and slow cooling in furnace. Both the solder composition and cooling rate after reflow have a significant effect on the intermetallic compound (IMC) thickness (mainly Cu₆Sn₅). Under fixed cooling condition, alloys (1), (3), and (5) revealed larger IMC thicknesses than that of alloys (2) and (4). Slow cooling produced an IMC buildup of thicker than 10 μm, while medium and fast cooling produced a thickness of thinner than 5 μm. The inverse relationship between IMC thickness and shear strength was confirmed. All the fast- and medium-cooled joints revealed a ductile mode (fracture surface was composed of the β-Sn phase), while the slow-cooled joints were fractured in a brittle mode (fracture surface was composed of Cu₆Sn₅ and Cu₃Sn phases). The effect of isothermal aging at 130°C on the growth of the IMC, shear strength, and fracture mode is also reported.     

Constitutive relations on creep for SnAgCuRE lead-free solder joints

Taking the most promising substitute of the Sn-3.8Ag-0.7Cu solder as the research base, investigations were made to explore the effect of rare earths (REs) on the creep performance of the Sn-3.8Ag-0.7Cu solder joints. The SnAgCu-0.1RE solder with the longest creep-rupture life was selected for subsequent research. Creep strain tests were conducted on Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints in the intermediate temperature range from 298 K to 398 K, corresponding to the homologous temperatures η=0.606, 0.687, 0.748, and 0.809 and η = 0.602, 0.683, 0.743, and 0.804, respectively, to acquire the relevant creep parameters, such as stress exponent and activation energy, which characterize the creep mechanisms. The final creep constitutive equations for Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints were established, demonstrating the dependence of steady-state creep rate on stress and temperature. By correcting the apparent creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints from the experiments, the true creep-activation energy is obtained. Results indicated that at low stress, the true creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints is close to the lattice self-diffusion activation energy, so the steady-state creep rates of these two solder joints are both dominated by the rate of lattice self-diffusion. While at high stress, the true creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints is close to the dislocation-pipe diffusion activation energy, so the steady-state creep rates are dominated by the rate of dislocation-pipe diffusion. At low stress, the best-fit stress exponents n of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints are 6.9 and 8.2, respectively, and the true creep-activation energy of them both is close to that of lattice self-diffusion. At high stress, it equals 11.6 and 14.6 for Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints, respectively, and the true creep-activation energy for both is close to that of the dislocation-pipe diffusion. Thus, under the condition of the experimental temperatures and stresses, the dislocation climbing mechanism serves as the controlling mechanism for creep deformation of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints. The creep values of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints are both controlled by dislocation climbing. Dislocation glide and climb both contribute to creep deformation, but the controlling mechanism is dislocation climb. At low stress, dislocation climbing is dominated by the lattice self-diffusion process in the Sn matrix and dominated by the dislocation-pipe diffusion process at high stress.     

Growth of Sn and intermetallic compounds in Sn-Ag-Cu solder

The microstructure of the Sn-Ag-Cu solder is examined by optical microscopy and scanning electron microscopy (SEM) for various compositions near the ternary eutectic for different cooling rates from the solder melt. Focus is on the size and orientation of Sn grains as indicated by cross-polarized, light optical microscopy, and pole figures from x-ray diffraction. We find that both composition and cooling rate have strong influences on Sn grain size, with Sn grain size increasing an order of magnitude as Cu concentration increases from 0% to 1.1%. Cyclic growth twinning, with twinning angles near 60°, is observed in Sn-Ag-Cu alloys near the composition Sn-3.9Ag-0.6Cu.     

无铅电子钎料合金蠕变性能研究

设计制作了一种简单可靠的弯折蠕变测量装置,比较了两种无铅电子钎料合金Sn-9Zn和Sn-3.5Cu-0.7Ag与传统电子钎料合金Sn-40Pb的常温蠕变性能,以及冷却条件对其蠕变强度的影响。结果表明:两种无铅钎料的抗蠕变性能大大优于传统锡铅钎料;Sn-3.5Ag-0.7Cu合金的抗蠕变性能优于Sn-9Zn合金;冷却速率对Sn-9Zn合金和Sn-3.5Ag-0.7Cu合金组织的影响类似,然而对蠕变强度的影响却相反:水冷使两种合金的组织相对于空冷都明显细化,Sn-9Zn合金的蠕变强度因之降低,而Sn-3.5Ag-0.7Cu合金的蠕变强度却因之提高。对可能产生的原因进行了讨论。     

Effect of Thermal Aging on Impact Absorbed Energies of Solder Joints Under High-Strain-Rate Conditions

This study was concerned with the effect of thermal aging on the impact properties of solder joints. Three kinds of solders, conventional Sn-37Pb solder, Sn-3.8Ag-0.7Cu solder, and Sn-3.8Ag-0.7Cu doped with rare-earth (RE) elements, were selected to manufacture joint specimens for the Charpy impact test. U-notch specimens were adopted and isothermally aged at 150°C for 100 h and 1000 h, and then impacted by using a pendulum-type impact tester at room temperature. The Sn-37Pb solder joints exhibited higher performance in terms of impact absorbed energy in the as-soldered and 100 h thermally aged conditions. Interestingly, the Sn-3.8Ag-0.7Cu solder joints exhibited improved performance for the impact value after 1000 h of thermal aging. For the Sn-37Pb and Sn-3.8Ag-0.7Cu solder joints, the impact absorbed energies initially increased when the storage duration was limited to 100 h, and then gradually decreased with its further increase. For the Sn-3.8Ag-0.7Cu-RE specimens, impact performance decreased directly with increasing thermal aging. Furthermore, scanning electron microscopy (SEM) observation showed that the fracture paths were focused on the interface zone for the three kinds of joints in the aged conditions. For the Sn-37Pb joints, the fracture surfaces mainly presented a ductile fracture mode. For the Sn-3.8Ag-0.7Cu joints, with microstructure coarsening, crack propagation partly shifted towards the Sn/Cu₆Sn₅ interface. Compared with the 100 h aged joints, the area fraction of intergranular fracture of Sn grains on the Sn-3.8Ag-0.7Cu fracture surfaces was increased when the aging time was 1000 h. On the contrary, the fracture morphologies of Sn-3.8Ag-0.7Cu-RE were mainly brittle as thermal aging increased. Thus, an interrelationship between impact energy value and fracture morphology was observed.     

Stress–Strain Characteristics of Tin-Based Solder Alloys for Drop-Impact Modeling

The stress–strain properties of eutectic Sn-Pb and lead-free solders at strain rates between 0.1 s⁻¹ and 300 s⁻¹ are required to support finite-element modeling of the solder joints during board-level mechanical shock and product-level drop-impact testing. However, there is very limited data in this range because this is beyond the limit of conventional mechanical testing and below the limit of the split Hopkinson pressure bar test method. In this paper, a specialized drop-weight test was developed and, together with a conventional mechanical tester, the true stress–strain properties of four solder alloys (63Sn-37Pb, Sn-1.0Ag-0.1Cu, Sn-3.5Ag, and Sn-3.0Ag-0.5Cu) were generated for strain rates in the range from 0.005 s⁻¹ to 300 s⁻¹. The sensitivity of the solders was found to be independent of strain level but to increase with increased strain rate. The Sn-3.5Ag and the Sn-3.0Ag-0.5Cu solders exhibited not only higher flow stress at relatively low strain rate but, compared to Sn-37Pb, both also exhibited higher rate sensitivity that contributes to the weakness of these two lead-free solder joints when subjected to drop impact loading.     

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.     

Microstructure, solderability, and growth of intermetallic compounds of Sn-Ag-Cu-RE lead-free solder alloys

The near-eutectic Sn-3.5 wt.% Ag-0.7 wt.% Cu (Sn-3.5Ag-0.7Cu) alloy was doped with rare earth (RE) elements of primarily Ce and La of 0.05–0.25 wt.% to form Sn-3.5Ag-0.7Cu-xRE solder alloys. The aim of this research was to investigate the effect of the addition of RE elements on the microstructure and solderability of this alloy. Sn-3.5Ag-0.7Cu-xRE solders were soldered on copper coupons. The thickness of the intermetallic layer (IML) formed between the solder and Cu substrate just after soldering, as well as after thermal aging at 170°C up to 1000 h, was investigated. It was found that, due to the addition of the RE elements, the size of the Sn grains was reduced. In particular, the addition of 0.1wt.%RE to the Sn-3.5Ag-0.7Cu solder improved the wetting behavior. Besides, the IML growth during thermal aging was inhibited.     

Study of the Impact Performance of Solder Joints by High-Velocity Impact Tests

The impact behavior of solder joints was studied using three different high-velocity impact tests: the U-notch Charpy impact test, the no-notch Charpy impact test, and a laboratory-designed drop test. The solder joints were made of five solder alloys, Sn-37Pb, Sn-3.8Ag-0.7Cu, Sn-2.0Ag-0.7Cu, Sn-1.0Ag-0.7Cu, and Sn-0.7Ag-0.7Cu (in wt.%), in which the traditional Cu/solder/Cu butt joint was used. All three impact tests gave the same trend of the impact behavior of the solder joints, with the Sn-37Pb joints having the highest impact resistance and the Sn-3.8Ag-0.7Cu joints having the lowest impact resistance. For the lead-free joints, the Sn-1.0Ag-0.7Cu joints had better impact resistance than the Sn-2.0Ag-0.7Cu joints, and the Sn-2.0Ag-0.7Cu joints better than the Sn-0.7Ag-0.7Cu joints. The impact behavior was correlated well to the fracture morphologies observed by scanning electron microscopy (SEM). Comparison of the three tests showed that the no-notch Charpy impact test is a promising method for evaluating the drop performance of solder joints.     

微量Ce对SnAgCu焊料与铜基界面IMC的影响

配制了w(Ce)为0.1%和不加Ce的两种Sn-3.5Ag-0.7Cu焊料。在443K恒温时效,研究Ce对焊料与铜基板界面金属间化合物(IMC)的形成与生长行为的影响。结果发现,焊点最初形成的界面IMC为Cu6Sn5,时效5d后,两种焊料界面均发现有Cu3Sn形成。随着时效时间的增加,界面化合物的厚度也不断增加。焊料中添加w为0.1%的Ce后,能抑制等温时效过程中界面IMC的形成与生长,生长速率降低近1/2。并且,界面IMC的形成与生长均由扩散机制控制。     

Effect of Strain Rate and Temperature on the Tensile Properties of Tin-Based Lead-Free Solder Alloys

The tensile properties of Sn-3Ag-0.5Cu, Sn-3.5Ag, and Sn-0.7Cu lead-free solders were investigated on small-scale specimens and compared with those of Sn-37Pb eutectic solder at various strain rates from 1 × 10⁻⁴ s⁻¹ to 1 × 10⁻² s⁻¹ and over a wide temperature range from 25°C to 150°C. The tests were under true strain-rate-controlled conditions. The ductility of each lead-free solder is relatively constant while that for Sn-Pb eutectic solder strongly depends on strain rate and temperature. The strain rate sensitivity index m for lead-free solders is relatively stable and showed little dependence on temperature, whereas the values of m for Sn-37Pb increased linearly with increasing temperature.     

Intermetallic growth kinetics for Sn-Ag, Sn-Cu, and Sn-Ag-Cu lead-free solders on Cu, Ni, and Fe-42Ni substrates

Soldering with the lead-free tin-base alloys requires substantially higher temperatures (∼235–250°C) than those (213–223°C) required for the current tin-lead solders, and the rates for intermetallic compound (IMC) growth and substrate dissolution are known to be significantly greater for these alloys. In this study, the IMC growth kinetics for Sn-3.7Ag, Sn-0.7Cu, and Sn-3.8Ag-0.7Cu solders on Cu substrates and for Sn-3.8Ag-0.7Cu solder with three different substrates (Cu, Ni, and Fe-42Ni) are investigated. For all three solders on Cu, a thick scalloped layer of η phase (Cu₆Sn₅) and a thin layer of ε phase (Cu₃Sn) were observed to form, with the growth of the layers being fastest for the Sn-3.8Ag-0.7Cu alloy and slowest for the Sn-3.7Ag alloy. For the Sn-3.8Ag-0.7Cu solder on Ni, only a relatively uniform thick layer of η phase (Cu,Ni)₆Sn₅ growing faster than that on the Cu substrate was found to form. IMC growth in both cases appears to be controlled by grain-boundary diffusion through the IMC layer. For the Fe-42Ni substrate with the Sn-3.8Ag-0.7Cu, only a very thin layer of (Fe,Ni)Sn₂ was observed to develop.     

Creep resistance of tin-based lead-free solder alloys

This paper reports on the microstructure-creep property relationship of three precipitation-strengthened tin (Sn)-based lead (Pb)-free solder alloys (Sn-0.7Cu, Sn-3.5Ag, and Sn-3.8Ag-0.7Cu) in bulk samples, together with Sn-37Pb as the alloy for comparison at temperatures of 303 K, 348 K, and 393 K. The creep resistance of these three Sn-based Pb-free solders increases, i.e., the steady-state creep rates decrease, with increasing volume fraction of precipitate phases for the Pb-free solder alloys. Their apparent stress exponents (n_a ∼ 7.3-17), which are all higher than that of pure Sn, attain higher values with increasing volume fraction of precipitate phases at constant temperature, and with decreasing temperature for the same solder alloy.     

波峰焊及再流焊无铅焊点组织演变规律的研究

以电子封装线上的波峰焊无铅焊点Sn-0.7Cu/Cu、回流焊无铅焊点Sn-3Ag-0.5Cu/Cu为对象,研究了150 ℃时效过程中无铅焊点处金属间化合物(IMC)、焊料合金组织的演化规律及界面处金属间化合物生长的动力学.试验结果表明:两种无铅焊点处IMC层的厚度随着时效时间的延长而增加,IMC层的生长基本上符合抛物线规律,因此IMC层的长大受元素扩散控制;且两种无铅焊点处IMC层的生长速率常数相近,但Sn-0.7Cu焊料中Sn的晶粒尺寸较Sn-3Ag-0.5Cu中的大;长期时效后,在试样的IMC层内发现有孔洞产生.     

Phase equilibria studies of Sn-Ag-Cu eutectic solder using differential cooling of Sn-3.8Ag-0.7Cu alloys

This paper is a study of the phase equilibria of the Sn-3.8Ag-0.7Cu alloy investigated by a differential cooling method. The difficulty in assessing phase equilibria of the Sn-Ag-Cu (SAC) system because of the insufficient resolution of conventional characterization techniques is solved by inducing preferential growth of a solid phase in a melt by holding the alloy at the solid-liquid phase-equilibrium field. Application of the technique to Sn-3.8Ag-0.7Cu with varying holding temperatures yielded results that the alloy is slightly off eutectic composition. The phase-formation sequence of the alloy during solidification was found to be Ag₃Sn, β-Sn, and finally the ternary eutectic microstructure.     

Morphology and growth kinetics of intermetallic compounds in solid-state interfacial reaction of electroless Ni-P with Sn-based lead-free solders

A comparative study of solid/solid interfacial reactions of electroless Ni-P (15 at.% P) with lead-free solders, Sn-0.7Cu, Sn-3.5Ag, Sn-3.8Ag-0.7Cu, and pure Sn, was carried out by performing thermal aging at 150°C up to 1000 h. For pure Sn and Sn-3.5Ag solder, three distinctive layers, Ni₃Sn₄, SnNiP, and Ni₃P, were observed in between the solder and electroless Ni-P; while for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders, two distinctive layers, (CuNi)₆Sn₅ and Ni₃P, were observed. The differences in morphology and growth kinetics of the intermetallic compounds (IMCs) at the interfaces between electroless Ni-P and lead-free solders were investigated, as well as the growth kinetics of the P-enriched layers underneath the interfacial IMC layers. With increasing aging time, the coarsening of interfacial Ni₃Sn₄ IMC grains for pure Sn and Sn-3.5Ag solder was significantly greater than that of the interfacial (CuNi)₆Sn₅ IMC grains for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders. Furthermore, the Ni content in interfacial (CuNi)₆Sn₅ phase slightly increased during aging. A small addition of Cu (0.7 wt.%) resulted in differences in the type, morphology, and growth kinetics of interfacial IMCs. By comparing the metallurgical aspects and growth kinetics of the interfacial IMCs and the underneath P-enriched layers, the role of initial Cu and Ag in lead-free solders is better understood.     

Sn-Cu、Sn-Ag-Cu系无铅钎料的钎焊特性研究

制备了Sn-0.7Cu、Sn-3.5Ag-0.6Cu钎料,用润湿平衡法测量了钎料对铜的润湿曲线,研究了温度、钎剂活性、钎焊时间对润湿行为的影响,并与Sn-37Pb钎料进行了比较。结果表明:升高温度能显著改善无铅钎料对铜的钎焊性。当温度<270℃时,Sn-0.7Cu的钎焊性明显低于Sn-3.5Ag-0.6Cu钎料;而当温度≥270℃时,两种钎料对铜都会显示较好的润湿性,而Sn-0.7Cu略优于Sn-3.5Ag-0.6Cu钎料。提高钎剂活性能显著增强钎料对铜的润湿性,其卤素离子的最佳质量分数均为0.4%左右。随着浸渍时间的延长,熔融钎料与铜的界面间产生失润现象。无铅钎料的熔点和表面张力较高,是钎焊性较差的根本原因。     

Contact angle measurements of Sn-Ag and Sn-Cu lead-free solders on copper substrates

In this study, the contact angles of four lead-free solders, namely, Sn-3.5Ag, Sn-3.5Ag-4.8Bi, Sn-3.8Ag-0.7Cu, and Sn-0.7Cu (wt.%), were measured on copper substrates at different temperatures. Measurements were performed using the sessile-drop method. Contact angles ranging from 30° to 40° after wetting under vacuum with no fluxes and between 10° and 30° with rosin mildly activated (RMA) and rosin activated (RA) fluxes were obtained. The Sn-3.5Ag-4.8Bi exhibited the lowest contact angles, indicating improved wettability with the addition of bismuth. For all soldering alloys, lower contact angles were observed using RMA flux. Intermetallics formed at the solder/Cu interface were identified as Cu₆Sn₅ adjacent to the solder and Cu₃Sn adjacent to the copper substrate. The Cu₃Sn intermetallic phase was generally not observed when RMA flux was used. The effect of temperature on contact angle was dependent on the type of flux used.     

The influence of solder composition on the impact strength of lead-free solder ball grid array joints

This study aims to investigate the shear and tensile impact strength of solder ball attachments. Tests were conducted on Ni-doped and non-Ni-doped Sn-0.7wt.% Cu, Sn-37wt.% Pb and Sn-3.0wt.% Ag-0.7wt.% Cu solder ball grid arrays (BGAs) placed on Cu substrates, which were as-reflowed and aged, over a wide range of displacement rates from 10 to 4000 mm/s in shear and from 1 to 400 mm/s in tensile tests. Ni additions to the Sn-0.7wt.% Cu solders has slowed the growth of the interface intermetallic compounds (IMCs) and made the IMC layer morphology smooth. As-reflowed Ni-doped Sn-0.7wt.% Cu BGA joints show superior properties at high speed shear and tensile impacts compared to the non-Ni-doped Sn-0.7wt.% Cu and Sn-3.0wt.% Ag-0.7wt.% Cu BGAs. Sn-3.0wt.% Ag-0.7wt.% Cu BGAs exhibit the least resistance in both shear and tensile tests among the four compositions of solders, which may result from the cracks in the IMC layers introduced during the reflow processes.