Interfacial reactions between Sn–8Zn–3Bi–xAg lead-free solders and Cu substrate

The formation and the growth of the intermetallic compounds (IMCs) at the interface between the Sn–8Zn–3Bi–xAg (x = 0, 0.5, and 1 wt.%) lead-free solder alloys and Cu substrate soldered at 250 °C for different durations from 5 to 60 min were investigated. It was found that Cu₅Zn₈ and CuZn₅ formed at Sn–8Zn–3Bi/Cu interface, and Cu₅Zn₈ and AgZn₃ formed at the solder/Cu interface when the solder was added with Ag. The thickness of IMC layers in different solder/Cu systems increased with increasing the soldering time. And the growth of the IMCs was found to be mainly controlled by a diffusion mechanism. Additionally, the growth of the IMC layers decreased with increasing content of Ag in the soldering process.     

Phase transformation and morphology of the intermetallic compounds formed at the Sn–9Zn–3.5Ag/Cu interface in aging

The morphology and phase transformation of the intermetallic compounds (IMCs) formed at the Sn–9Zn–3.5Ag/Cu interface in a solid-state reaction have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). The monoclinic η′-Cu₆Sn₅ transforms to the hexagonal η-Cu₆Sn₅ and the orthorhombic Cu₅Zn₈ transforms to the body-centered cubic (bcc) γ-Cu₅Zn₈ as aged at 180 °C. The scallop-shaped Cu₆Sn₅ layer is retained after aging at 180 °C for 1000 h. In the solid-state reaction, Ag is repelled from η′-Cu₆Sn₅ and reacts with Sn to form Ag₃Sn, and the Cu₅Zn₈ layer decomposes. Kirkendall voids are not observed at the Sn–9Zn–3.5Ag/Cu interface even after aging at 180 °C for 1000 h.     

High temperature reliability of lead-free solder joints in a flip chip assembly

The visco-plastic behaviour of solder joints of two models of a flip chip FC48D6.3C457DC mounted on a printed circuit board (PCB) via SnAgCu solder is investigated using Anand's model. While the bumps of one of the models are realistic with 6 μm thickness of intermetallic compound (IMC) at interconnects of solder and bond pads, the other are made up of conventional bumps without IMC at these interconnects. The solder bump profiles were created using a combination of analytical method and construction geometry. The assembled package on PCB was accelerated thermally cycled (ATC) using IEC standard 60749-25. It was found in the result of the simulation that IMC does not only impact solder joint reliability but also is a key factor of fatigue failure of solder joints. The IMC sandwiched between bond pad at chip side and solder bulk is the most critical and its interface with solder bulk is the most vulnerable site of damage. With reference to our results, it is proposed that non inclusion of IMC in solder joint models composed of Sn-based solder and metalized copper substrate is one of the major causes of the discrepancy on solder joint fatigue life predicted using finite element modelling and the one obtained through experimental investigation.     

Study on the properties of Sn–9Zn–xCr lead-free solder

The influences of different Cr content to lead (Sn)–Zn solder were investigated. Sn–9Zn–xCr shows finer and more uniform microstructure than Sn–9Zn. Thermal gravimetric analysis (TGA) and Auger electron spectroscopy (AES) results show that adding Cr significantly improves the oxidation resistance of Sn–9Zn solder, and reduces the thickness of oxidation film of Sn–9Zn–xCr solder. When Cr content is 0.1%, the Sn–9Zn–0.1Cr solder have the best oxidation resistance. In addition, the effect of Cr addition on the wettability, melting point and mechanical properties of Sn–9Zn solder was discussed.     

Thermoelectric characteristics and tensile properties of Sn–9Zn–xAg lead-free solders

This study investigates the structural characteristics and tensile properties of the Sn–9Zn–xAg alloy under an electrical current test and oil bath treatment. Experimental results indicate that alternating current (ac) and direct current (dc) led to different values for the fusing electrical current value. Electromigration of direct current (dc) reduced the fusing electrical resistance. In addition, the electrical conductivity of the Sn–9Zn–xAg alloys deteriorated significantly by adding more 2 wt.% Ag. The Sn–9Zn–1Ag specimen underwent no transformation during oil–silicon heat-treatment, however its structure experienced electromigration under electrical current testing. After electrical current testing, the needle-like Zn-rich phases had decomposed, the Ag–Zn compounds had grown, the amount of Sn–Zn eutectic phases had increased, and the content of Sn-rich phase had decreased. Also, prolonging the duration of thermoelectric testing led to a deterioration in the tensile mechanical properties of the specimens. Raising the heat-treatment temperature enhanced the solid solution effect and raised the tensile strength of the as-cast specimens.     

Investigations of interfacial reactions of Sn–Zn based and Sn–Ag–Cu lead-free solder alloys as replacement for Sn–Pb solder

The interfacial reactions of Sn–Zn based solders and a Sn–Ag–Cu solder have been compared with a eutectic Sn–Pb solder. During reflow soldering different types of intermetallic compounds (IMCs) are found at the interface. The morphologies of these IMCs are quite different for different solder compositions. As-reflowed, the growth rates of IMCs in the Sn–Zn based solder are higher than in the Sn–Ag–Cu and Sn–Pb solders. Different types of IMCs such as γ-Cu₅Zn₈, β-CuZn and a thin unknown Cu–Zn layer are formed in the Sn–Zn based solder but in the cases of Cu/Sn–Pb and Cu/Sn–Ag–Cu solder systems Cu₆Sn₅ IMC layers are formed at the interface. Cu₆Sn₅ and Cu₃Sn interfacial IMCs are formed in the early stages of 10 min reflow due to the limited supply of Sn from the Sn–Pb solder. The spalling of Cu–Sn IMCs is observed only in the Sn–Ag–Cu solder. The size of Zn platelets is increased with an increase of reflow time for the Cu/Sn–Zn solder system. In the case of the Sn–Zn–Bi solder, there is no significant increase in the Zn-rich phases with extended reflow time. Also, Bi offers significant effects on the wetting, the growth rate of IMCs as well as on the size and distribution of Zn-rich phases in the β-Sn matrix. No Cu–Sn IMCs are found in the Sn–Zn based solder during 20 min reflow. The consumption of Cu by the solders are ranked as Sn–Zn–Bi > Sn–Ag–Cu > Sn–Zn > Sn–Pb. Despite the higher Cu-consumption rate, Bi-containing solder may be a promising candidate for a lead-free solder in modern electronic packaging taking into account its lower soldering temperature and material costs.     

Mechanical and electrical properties of In-Bi solder at Bi2212 superconductor interface with annealed Ag spray layers and Ag precoating layers

The electrical properties of solder contact layers between Cu-Ni shunt metal and tube type Bi₂₂₁₂ superconductor that is applied in superconducting fault current limiter were studied. The contact properties of the solders are improved not only by Ag precoating layers, but also by the pre-sprayed Ag layer and subsequent Ag precoating layers. The annealed Ag sprayed layers onto Bi₂₂₁₂ superconductor prior to Ag electroplating work as protecting layers for the superconductor from plating solutions. The contact angle of the electroplated Ag layer is 42.91° and decreases to 15.25° and 5.88° with Ag sprayed layer and additional Ag electroplated layers. The Ag sprayed layer with suitable annealing prior to Ag electroplating improves contact strength of the Ag electroplated layer by about 12% due to denser microstructure of the Ag electroplated layers.     

Effect of immersion Ag surface finish on interfacial reaction and mechanical reliability of Sn–3.5Ag–0.7Cu solder joint

A comparative study on the preparation of specific titanium silicides (including Ti₃Si, Ti₅Si₃, Ti₅Si₄, TiSi, and TiSi₂) in the Ti–Si system was experimentally conducted by self-propagating high-temperature synthesis (SHS) from elemental powder compacts of their corresponding stoichiometries. The effect of initial sample stoichiometry was investigated on combustion characteristics and product composition. Experimental evidence shows a distinct combustion front traversing the entire reactant compact in a self-sustaining manner for all of the samples adopted in this study. However, as a result of the eutectic reaction, test samples composed of Ti:Si = 3:1 and 1:1 experienced excessive melting during the propagation of the reaction front. Moreover, the flame-front propagation rate and combustion temperature were found to vary significantly with starting stoichiometry of the powder compact. The flame-front velocity up to 50 mm/s was observed in the samples of Ti:Si = 5:4 and 5:3, in contrast to the values in the range of 2.6–3.5 mm/s for the compact of Ti:Si = 1:2. Reaction front temperatures between 1380 and 1460 °C were achieved by the powder compacts with Ti:Si = 5:4 and 5:3. For the samples of Ti:Si = 3:1 and 1:1, their flame-front temperatures were comparable and about 1330 °C. Consistent with its slow reaction front, the Ti + 2Si sample had the lowest combustion temperature close to 1150 °C. The XRD analysis confirms complete conversion from the reactant with Ti:Si = 5:3 to a single-phase silicide Ti₅Si₃. Powder compacts of Ti:Si = 5:4 and 1:1 yielded two silicide phases, Ti₅Si₄ and TiSi, in their end products. In spite of formation of a minor amount of TiSi, the disilicide TiSi₂ was identified as the dominant composition in the product obtained from the Ti + 2Si sample. Combustion products containing Ti₅Si₃ and a large amount of unreacted Ti were synthesized from the powder compacts of Ti:Si = 3:1, implying a poor degree of phase conversion.     

加载速率和钎料厚度对SnAgCu/Cu焊点剪切行为影响

采用四种加载速率(1,0.1,0.01,0.001 mm/s),对四种钎料厚度(0.1,0.2,0.3,0.6 mm)的SnAgCu/Cu搭接焊点进行了剪切破坏试验,分析了不同加载速率以及钎料尺寸对焊点抗剪切性能的影响,并通过扫描电镜(SEM)和能谱仪(EDS)分析了剪切试样断口形貌、裂纹的萌生位置及扩展路径,阐释了SnAgCu/Cu焊点断裂失效机理. 结果表明,加载速率在0.001~1 mm/s范围内,焊点抗剪切强度随加载速率的增加而增大,不同加载速率条件下焊点的断裂模式都为韧性断裂. 不同钎料厚度的SnAgCu/Cu焊点随着焊点厚度的减小,其抗剪切性能提高,表现出明显的体积效应,其裂纹萌生位置逐渐由焊点内部向IMC层转移. 焊点断口形貌为拉伸撕裂型伸长韧窝和剪切平面,断裂机理为微孔聚集型-纯剪切复合断裂.     

纳米颗粒增强SAC0307锡膏焊点的分析

研究了纳米颗粒添加对低银SAC0307锡膏焊点显微组织和力学性能的影响.结果表明,添加纳米铜颗粒的焊点钎料共晶区中岛状Cu₆Sn₅相尺寸大、且难于弥散分布,添加量超过0.3%时,Cu₆Sn₅相极易在液/气界面聚集、合并和长大,导致钎料流动性变差、锡膏中助焊剂气体难于逸出而形成气孔.而添加0.1~5.0%纳米银颗粒的焊点均无气孔产生,其焊点钎料中的Ag₃Sn相尺寸小易于弥散分布,且β-Sn初晶相细化明显.随纳米银添加量的增加,焊点抗剪强度先增加后降低,0.5%添加量时抗剪强度最大、较相同条件下的SAC0307焊点提高了30.8%.     

Effect of surface finish on the fracture behavior of Sn–Ag–Cu solder joints during high-strain rate loading

This study assesses the reliability of eutectic Sn–Pb, Sn–1.0Ag–0.5Cu, Sn–3.0Ag–0.5Cu and Sn–4.0Ag–0.5Cu solder bumps on three different pad surface finishes (ENIG, electrolytic Ni/Au and Cu-OSP) with and without an aging treatment at 150 °C for 100 h. This study focused primarily on how the pad surface finish and solder alloy composition affects the reliability of solder joints using a high-speed ball pull test method. The fracture forces and failure mechanisms were also examined. The results showed that the electrolytic Ni/Au surface finish had the highest fracture forces for all four different solder alloys with and without the aging process.     

The 260 °C phase equilibria of the Sn–Sb–Ag ternary system and interfacial reactions at the Sn–Sb/Ag joints

The isothermal section of the Sn–Sb–Ag ternary system at 260 °C has been determined in this study by experimental examination. Experimental results show no existence of ternary compounds in the Sn–Sb–Ag system. Two extensive regions of mutual solubility have been determined. The one located between the two binary isomorphous phases, Ag₃Sn and Ag₃Sb, is labeled as and the other one located between the two binary isomorphous phases, Ag₄Sn and Ag₄Sb, is labeled as ξ. The phase is a very stable phase and is in equilibrium with ξ, Sb, SbSn, Sb₂Sn₃, and liquid Sn phases. Each of the Sb and SbSn phases has a limited solubility of Ag. Only one stoichiometric compound, Sb₂Sn₃, exists. Besides phase equilibria determination, the interfacial reactions between the Sn–Sb alloys and the Ag substrate were investigated at 260 °C. It was found that the phase formations in the Sn–Sb/Ag couples are very similar to those in the Sn/Ag couples.     

The growth and roughness evolution of intermetallic compounds of Sn–Ag–Cu/Cu interface during soldering reaction

The growth behavior and roughness evolution of intermetallic compounds (IMCs) layer between Sn–3.5Ag, Sn–3.5Ag–0.7Cu, Sn–3.5Ag–1.7Cu and Sn–0.5Ag–4Cu lead-free solder alloys and Cu substrate are investigated during soldering under 250 °C. With the increase of Cu content in Sn–3.5Ag, Sn–3.5Ag–0.7Cu and Sn–3.5Ag–1.7Cu solders, the IMC thickness increases due to the decrease of the dissolution rate of the IMCs. The IMC thickness of Sn–0.5Ag–4Cu is quite thinner in a short soldering time. However, with the increase of soldering time, the IMCs layer grows quickly due to the precipitation effect of the Cu₆Sn₅ in the liquid solder. With the increase of soldering time, the roughness of all the IMC layers increases. The roughness of Sn–3.5Ag–0.7Cu and Sn–3.5Ag–1.7Cu interfaces is larger than that of Sn–3.5Ag while Sn–0.5Ag–4Cu/Cu interface has the smallest roughness value. It is believed that the small IMC roughness of Sn–3.5Ag/Cu interface is caused by the IMCs dissolution, and the large IMC/liquid solder interfacial energy maybe the reason for Sn–0.5Ag–4Cu/Cu interface obtaining the smallest IMC roughness.     

微量锌对Sn-3.5Ag无铅钎料/铜界面金属间化合物生长的抑制

在钎焊和时效条件下,研究了Sn-3.5Ag无铅钎料中添加0.2%的Zn元素后对钎料/铜界面组织形貌的影响.结果表明,钎焊条件下,将0.2%的Zn元素加入到Sn-3.5Ag钎料中对Cu-Sn间的金属间化合物及其扇贝形形状不产生影响.时效处理后,0.2%Zn元素的加入对界面IMC层的厚度、组成及形态都有影响.在Sn-3.5...     

电迁移极性效应及其对Sn-3.0Ag-0.5Cu无铅焊点拉伸性能的影响

采用扫描电子显微镜(SEM)、能谱仪(EDS)和微拉伸实验,研究Cu/Sn-3.0Ag-0.5Cu/Cu对接焊点在不同电迁移时间下阳极、阴极界面金属间化合物(IMC)的生长演变规律及焊点抗拉强度的变化,同时对互连焊点的断口形貌及断裂模式进行分析.结果表明:在电流密度(J)为1.78×104 A/cm2、温度为373 K的加载条件下,随着加载时间的延长,焊点界面IMC的生长呈现明显的极性效应,阳极界面IMC增厚,阴极界面IMC减薄,且阳极界面IMC的生长符合抛物线规律;同时,互连焊点的抗拉强度不断下降,焊点的断裂模式由塑性断裂逐渐向脆性断裂转变,断裂位置由焊点中心向阴极界面处转移.     

时效时间对Cu/In-Sn-2.5Ag/Cu焊点组织形貌及剪切性能的影响

研究了Cu/In-Sn-2.5Ag/Cu复合钎料焊点在125℃时效不同时间后的微观组织和剪切性能.结果表明:随着时效时间的延长,Cu/In-Sn-2.5Ag/Cu焊点界面金属间化合物(IMCs)层厚度呈现增加的趋势,焊点界面IMCs层组织先生成Cu6(In,Sn)5相,同时焊点中生成少量的Ag9In4相,随着时效时间的...     

The difference in the types of intermetallic compound formed between the cathode and anode of an Sn–Ag–Cu solder joint under current stressing

An investigation of microstructural evolution with various current densities in a lead-free Cu/SnAgCu/Au/Cu solder system was conducted in this study. Current stressing induced migration of Cu toward the anode and resulted in the formation of Cu₆Sn₅ at the interface. The consumption rates of Cu were calculated to be 2.24 × 10⁻⁷ μm/s and 5.17 × 10⁻⁷ μm/s at 1.0 × 10³ A/cm² and 2.0 × 10³ A/cm², respectively, while the growth rates of Cu₆Sn₅ were 6.33 × 10⁻⁷ μm/s and 7.72 × 10⁻⁷ μm/s. The atomic fluxes of Cu were found to be 2.50 × 10¹² atom/cm² s and 5.88 × 10¹² atom/cm² s at the above-mentioned current densities. The diffusivities of Cu in Cu₆Sn₅ were 2.02 × 10⁻¹¹ cm²/s and 2.38 × 10⁻¹¹ cm²/s under 1.0 × 10³ A/cm² and 2.0 × 10³ A/cm² of current stressing. Current stressing effectively enhances the migration of Cu in Cu₆Sn₅ and results in a 1000-fold increase of magnitude in diffusivity compared to thermal aging. (Cu_1−x,Au_x)₆Sn₅ compound was formed near the anode after a long period of current stressing.     

Kinetics of intermetallic phase formation at the interface of Sn-Ag-Cu-X (X = Bi, In) solders with Cu substrate

The effects of Bi and In additions on intermetallic phase formation in lead-free solder joints of Sn-3.7Ag-0.7Cu; Sn-1.0Ag-0.5Cu-1.0Bi and Sn-1.5Ag-0.7Cu-9.5In (composition given in weight %) with copper substrate are studied. Soldering of copper plate was conducted at 250 °C for 5 s. The joints were subsequently aged at temperatures of 130-170 °C for 2-16 days in a convection oven. The aged interfaces were analyzed by optical microscopy and energy dispersive X-ray spectroscopy (EDX) microanalysis. Two intermetallic layers are observed at the interface - Cu₃Sn and Cu₆Sn₅. Cu₆Sn₅ is formed during soldering. Cu₃Sn is formed during solid state ageing. Bi and In decrease the growth rate of Cu₃Sn since they appear to inhibit tin diffusion through the grain boundaries. Furthermore, indium was found to produce a new phase - Cu₆(Sn,In)₅ instead of Cu₆Sn₅, with a higher rate constant. The mechanism of the Cu₆(Sn,In)₅ layer growth is discussed and the conclusions for the optimal solder chemical composition are presented.     

基于纳米压痕法Sn3.0Ag0.5Cu焊点金属间化合物力学性能及其应变率效应的研究

采用纳米压入测试系统对无铅焊点Sn3.0Ag0.5Cu内金属间化合物(IMCs)Cu3Sn、Cu6Sn5的力学性能进行测试,应变率分别为0.01 s-1,0.05s-1,0.25s-1,0.5s-1,分析IMCs力学性能的应变率效应。研究发现金属间化合物具有应变率强化效应;Cu3Sn和Cu6Sn5的变形机制不同,前者加载曲线呈现锯齿流变,后者曲线光滑;Cu3Sn和Cu6Sn5的接触刚度在不同应变率时均与压痕深度成线性正比例关系;Cu3Sn的弹性模量和硬度明显高于Cu6Sn5;Cu3Sn和Cu6Sn5的硬度值均随着应变率的增大而增大,而对弹性模量没有明显影响。保载阶段,蠕变位移具有应变率强化效应,加载应变率为0.05s-1时做对比实验,Cu焊盘、Cu3Sn、Cu6Sn5和焊点的蠕变应变率敏感指数m分别为0.01627、0.0117、0.0184和0.0661。