服役条件对内生颗粒增强复合钎料性能的影响

内生法制备复合钎料被认为是提高无铅钎料性能的有效途径.为了提高基体钎料的综合性能,试验采用内生均匀分布的Cu6Sn5颗粒作为增强相,以Sn-3.5Ag共晶钎料作为基体,制成内生Cu6Sn5颗粒增强的SnAg基复合钎料.研究了服役条件下内生Cu6Sn5颗粒增强复合钎料的显微组织和抗剪强度,对复合钎料钎焊接头的断裂方式及增强相的作用进行了分析.结果表明,随着再流及时效的进行,复合钎料内部Cu6Sn5颗粒的形貌及尺寸发生变化,进而影响复合钎料钎焊接头的抗剪强度.复合钎料钎焊接头的变形方式主要受滑移带控制,内生Cu6Sn5颗粒增强相可以起到阻碍滑移带扩展的作用.     

热循环对Sn58Bi(纳米Ti)/Cu焊点界面与性能影响

为了改善Sn-58Bi低温钎料的性能,通过在Sn-58Bi低温钎料中添加质量分数为0.1%的纳米Ti颗粒制备了Sn-58Bi-0.1Ti纳米增强复合钎料。在本文中,研究了纳米Ti颗粒的添加对-55～125 _^oC热循环过程中Sn-58Bi/Cu焊点的界面金属间化合物(IMC)生长行为的影响。研究结果表明：回流焊后,在Sn-58Bi/Cu焊点和Sn-58Bi-0.1Ti/Cu焊点的界面处都形成一层扇贝状的Cu₆Sn₅ IMC层。在热循环300次后,在Cu₆Sn₅/Cu界面处形成了一层Cu₃Sn IMC。Sn-58Bi/Cu焊点和Sn-58Bi-0.1Ti/Cu焊点的IMC层厚度均和热循环时间的平方根呈线性关系。但是,Sn-58Bi-0.1Ti/Cu焊点的IMC层厚度明显低于Sn-58B/Cu焊点,这表明纳米Ti颗粒的添加能有效抑制热循环过程中界面IMC的过度生长。另外计算了这两种焊点的IMC层扩散系数,结果发现Sn-58Bi-0.1Ti/Cu焊点的IMC层扩散系数(整体IMC、Cu₆Sn₅和Cu₃Sn IMC)明显比Sn-58Bi/Cu焊点小,这在一定程度上解释了Ti纳米颗粒对界面IMC层的抑制作用。     

Microstructure and Electro-Physical Properties of Sn-3.0Ag-0.5Cu Nanocomposite Solder Reinforced with Ni Nanoparticles in the Melting-Solidification Temperature Range

The electrical conductivity of nanocomposite Sn-3.0Ag-0.5Cu alloys with two different weight percentages of Ni nanoparticles (1.0 and 2.0 wt.%) was measured over a wide temperature range. The samples were produced using a cold pressing method: Sn-3.0Ag-0.5Cu powder and Ni nanopowder were mechanically mixed and pressed into 8 mm diameter rods. Ni nanoparticles were synthesized via a chemical reduction method and characterized by a core/shell structure. Temperature dependencies of the electrical conductivity revealed a hysteresis between the heating and cooling curves in a wide temperature range above the melting temperature. This fact is connected with structure transformations accompanied by a dissolution of Ni nanoparticles, which should be retarded due to an oxide/hydroxide shell on the surface of the nanoparticles. A microstructure analysis of the samples in the solid state showed a fine distribution of intermetallic compounds in the Sn-based matrix. The Ni atoms substituted for Cu atoms in the Cu₆Sn₅ compound forming a (Cu,Ni)₆Sn₅ phase.     

Sn-Ag-Cu solders and solder joints: Alloy development, microstructure, and properties

Slow cooling of Sn-Ag-Cu and Sn-Ag-Cu-X (X = Fe, Co) solder-joint specimens made by hand soldering simulated reflow in surface-mount assembly to achieve similar as-solidified joint microstructures for realistic shearstrength testing, using Sn-3.5Ag (wt.%) as a baseline. Minor substitutions of either cobalt or iron for copper in Sn-3.7Ag-0.9Cu refined the joint matrix microstructure, modified the Cu₆Sn₅ intermetallic phase at the copper substrate/solder interface, and increased the shear strength. At elevated (150°C) temperature, no significant difference in shear strength was found in all of the alloys studied. Ambient temperature shear strength was reduced by largescale tin dendrites in the joint microstructure, especially by the coarse dendrites in solute poor Sn-Ag-Cu.     

Observations of nucleation catalysis effects during solidification of SnAgCuX solder joints

While modification of a strong (high Cu) Sn-Ag-Cu (SAC) solder alloy with a substitutional alloy addition (X=Co, Fe, Zn, and Ni) for Cu has been demonstrated to enhance solder joint strength and ductility after aging at 150°C for 1,000 h, control of the as-solidified SAC+X solder joint microstructure is also needed to inhibit under cooling and nucleation of brittle pro-eutectic phases (e.g., Ag₃Sn). Bulk undercooling measurements of SAC+X alloys and microstructural analysis of SAC+X solder joints were used to rank the effectiveness and consistency of low-level (X < 0.15 wt.%) substitutional additions to a base SAC composition, Sn-3.5Ag-0.95Cu (wt.%). This SAC composition was selected to favor thermodynamically the nucleation of pro-eutectic Cu₆Sn₅ over that of Ag₃Sn and the formation of an enhanced ternary eutectic fraction in the joint microstructure, while retaining a pasty range that is only 3°C. Using differential scanning calorimetry with sample pans that serve as either inert (aluminum) or actively wetting (copper) substrates, reflow cycles were studied that simulated surface mount (1.5°C/s) and ball-grid array (0.17°C/s) cooling rates. Of the SAC+X solders tested with copper pans, X = Zn appeared to be most effective and consistent, providing catalytic enhancement of the nucleation temperature for even the minimum concentration (0.05 wt.%) and lowest cooling rate.     

Pb-free solders for flip-chip interconnects

A variety of lead-free solder alloys were studied for use as flip-chip interconnects including Sn-3.5Ag, Sn-0.7Cu, Sn-3.8Ag-0.7Cu, and eutectic Sn-37Pb as a baseline. The reaction behavior and reliability of these solders were determined in a flip-chip configuration using a variety of under-bump metallurgies (TiW/Cu, electrolytic nickel, and electroless Ni-P/Au). The solder micro-structure and intermetallic reaction products and kinetics were determined. The Sn-0.7Cu solder has a large grain structure and the Sn-3.5Ag and Sn-3.8Ag-0.7Cu have a fine lamellar two-phase structure of tin and Ag₃Sn. The intermetallic compounds were similar for all the lead-free alloys. On Ni, Ni₃Sn₄ formed and on copper, Cu₆Sn₅Cu₃Sn formed. During reflow, the intermetallic growth rate was faster for the lead-free alloys, compared to eutectic tin-lead. In solidstate aging, however, the interfacial intermetallic compounds grew faster with the tinlead solder than for the lead-free alloys. The reliability tests performed included shear strength and thermomechanical fatigue. The lower strength Sn-0.7Cu alloy also had the best thermomechanical fatigue behavior. Failures occurred near the solder/intermetallic interface for all the alloys except Sn-0.7Cu, which deformed by grain sliding and failed in the center of the joint. Based on this study, the optimal solder alloy for flip-chip applications is identified as eutectic Sn-0.7Cu. Editor’s Note: A hypertext-enhanced version of this article can be found at www.tms.org/pubs/journals/JOM/0106/Frear-0106.html For more information, contact D.R. Frear, Interconnect Systems Laboratories, Motorola, Tempe, AZ 85284; (480) 413-6655; fax (480) 413-4511; e-mail darrel.frear@motorola.com.     

Effect of bismuth on the growth kinetics of intermetallic compounds in Sn-3.5Ag solder joints: A growth kinetic model

The effect on the growth kinetics of the intermetallic compounds (IMCs) in solder/Cu joints, caused by adding Bi to eutectic Sn-3.5Ag solder alloy, was examined at the aging temperatures of 150°C and 180°C. The Cu₆Sn₅ layer growth was significantly enhanced, but the Cu₃Sn layer growth was slightly retarded by the addition of Bi, resulting in significant growth enhancement of the total (Cu₆Sn₅+Cu₃Sn) IMC layer with increasing Bi addition. The IMC layer growth in the Bi-containing solder joints was accompanied by the accumulation of Bi ahead of the Cu₆Sn₅ layer that resulted in the formation of a liquid layer at the Cu₆Sn₅/solder interface. A kinetic model was developed for the planar growth of the Cu₆Sn₅ and Cu₃Sn layers in the solder joints, accounting for the existence of interfacial reaction barriers. Predictions from the kinetic model showed that the experimental results could be well explained by the hypothesis that the formation of a Bi-rich liquid layer at the Cu₆Sn₅/solder interface reduces the interfacial reaction barrier at the interface.     

Reaction diffusions of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> and Cu<Subscript>3</Subscript>Sn intermetallic compound in the couple of Sn-3.5Ag eutectic solder and copper substrate

The growth kinetics of intermetallic compound layers formed between Sn-3.5Ag solder and Cu substrate were investigated as a consequence of solid-state isothermal aging. Isothermal aging was carried out in a temperature range between 70°C and 200°C for 0 to 60 days. A quantitative analysis of the intermetallic compound layer thickness as a function of time and temperature was performed. The diffusion couples showed a composite intermetallic layer comprised of Cu₆Sn₅ and Cu₃Sn. The growth of intermetallic compounds followed diffusion-controlled kinetics and the layer thickness reached only 9 μm after 60 day of aging at 150°C. The apparent activation energies were calculated for the growth of the total intermetallic compound (Cu₆Sn₅+Cu₃Sn); Cu₆Sn₅ and Cu₃Sn intermetallic are 65.4, 55.4 and 75.7 kJ/mol, respectively.     

Effects of in situ nickel particle addition on the microstructure and microhardness of Sn–Ag solder

Abstract

In this study, various amounts of Ni particles were added in situ to Sn–3·5 wt-%Ag lead free solder to form new composite solders. Copper substrates were then dipped into these solders and aged at 150°C for 0, 25, 225, or 1000 h. The microstructure and microhardness of the as solidified solder and the aged solder/copper couples were investigated. Experimental results revealed that the addition of Ni particles increased the microhardness of the composite solder. Ni additions of less than 3 wt-% yielded a microstructure of β-Sn grains surrounded by a eutectic mixture of Ag₃Sn and a Sn rich matrix. An intermetallic compound of Ni₃Sn₄ particles was dispersed throughout the eutectic. For 5 wt-%Ni addition, the Ni₃Sn₄ phase and the remaining Ni particles were agglomerated. In the case of copper substrate dipped with a thick layer of composite solder, water quenched and then aged at 150°C, the induced (Ni, Cu)₃Sn₄ particles coarsened and agglomerated. Additionally, the intermetallic (Cu, Ni)₆Sn₅ compound layer formed at the solder/Cu interface thickened with increasing Ni content.     

The Inhibition of Tin Whiskers on the Surface of Sn-8Zn-3Bi-0.5Ce Solders

Through the refinement of the (Ce, Zn)Sn₃ intermetallic phase, the formation of tin whiskers, previously observed on the surface of a Sn-3Ag-0.5Cu-0.5Ce solder, was prevented in a Sn-9Zn-0.5Ce alloy. However, whisker growth can still occur on the surface of Sn-8Zn-3Bi-0.5Ce solder after air storage at room temperature and at 150 °C due to the formation of large (Ce, Zn)Sn₃ intermetallic clusters. Further experiments showed that decreasing the Bi-content in this Sn-8Zn-0.5Ce alloy to 1 and 2 wt.% can recover the beneficial effects of Zn additions on the refinement of the (Ce, Zn)Sn₃ phase and obviously reduce the appearance of tin whiskers. In addition, alloying the Sn-8Zn-3Bi-0.5Ce solder with 0.5 wt.% Ge, which increases the oxidation resistance of the (Ce, Zn)Sn₃ intermetallic clusters, can also effectively inhibit tin whisker growth.     

Suppressing effect of 0.5 wt.% nano-TiO2 addition into Sn-3.5Ag-0.5Cu solder alloy on the intermetallic growth with Cu substrate during isothermal aging

This study investigated the effects of adding 0.5 wt.% nano-TiO₂ particles into Sn3.5Ag0.5Cu (SAC) lead-free solder alloys on the growth of intermetallic compounds (IMC) with Cu substrates during solid-state isothermal aging at temperatures of 100, 125, 150, and 175 °C for up to 7 days. The results indicate that the morphology of the Cu₆Sn₅ phase transformed from scallop-type to layer-type in both SAC solder/Cu joints and Sn3.5Ag0.5Cu-0.5 wt.% TiO₂ (SAC) composite solder/Cu joints. In the SAC solder/Cu joints, a few coarse Ag₃Sn particles were embedded in the Cu₆Sn₅ surface and grew with prolonged aging time. However, in the SAC composite solder/Cu aging, a great number of nano-Ag₃Sn particles were absorbed in the Cu₆Sn₅ surface. The morphology of adsorption of nano-Ag₃Sn particles changed dramatically from adsorption-type to moss-type, and the size of the particles increased.The apparent activation energies for the growth of overall IMC layers were calculated as 42.48 kJ/mol for SAC solder and 60.31 kJ/mol for SAC composite solder. The reduced diffusion coefficient was confirmed for the SAC composite solder/Cu joints.     

Sn-Ag-Cu and Sn-Cu solders: Interfacial reactions with platinum

The interfacial reaction and intermetallic formation at the interface between tin solders containing a small amount of copper with platinum were investigated in this study. Sn-0.7Cu and Sn-1.7Cu solders were reacted with platinum by dipping Pt/Ti/Si specimens into the molten solder at 260°C. Sn-3.8Ag-0.7Cu solder was reacted with platinum by reflowing solder paste on a Pt/Ti/Si substrate at 250°C. PtSn₄ intermetallic formed in all specimens while Cu₆Sn₅ interfacial intermetallic was not observed at the solder/platinum interfaces in any specimens. A parabolic relationship existed between the thickness of the Pt-Sn intermetallic and reaction time, which indicates the intermetallic formation in the solder/platinum interface is diffusion controlled. For more information, contact Young-Ho Kim, Hanyang University, Department of Materials Engineering, Seoul, 133-791, Korea; e-mail kimyh@hanyang.ac.kr.     

相图计算在电子材料焊接中的应用

焊料与基体的界面反应对高性能电子材料焊接接头的力学性能和可靠性都有着很重要的影响。把焊接过程分为界面反应和剩余焊料凝固两个过程进行讨论，在相图热力学的基础上，通过计算亚稳相图、比较界面处局部平衡时各相形成驱动力大小，预测了Sn-3．5％Ag／Cu、Sn-25％Ag／Cu和Sn-3．5％Ag／Ni扩散偶界面反应过程中的中间相形成序列；同时利用Scheil—Gulliver凝固模型模拟了Sn-25％Ag／Cu体系中过剩焊料的非平衡凝固过程，预测了焊料在随后冷却过程中的相演变信息。计算预测的结果与前人的实验结果吻合很好。     

Effects of Co nanoparticle addition to Sn–3.8Ag–0.7Cu solder on interfacial structure after reflow and ageing

Effects of Co nanoparticle additions to Sn–3.8Ag–0.7Cu on the structure of solder/copper interface have been studied after reflow and high temperature ageing (150 °C, up to 1008 h). Results show that the Co nanoparticles substantially suppress the growth of Cu₃Sn but enhance Cu₆Sn₅ growth. Cobalt nanoparticles reduce interdiffusion coefficient in Cu₃Sn. It is suggested that the Co nanoparticles undergo surface dissolution during reflow and exert their influence, at least partially, through alloying effect.     

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.     

Effect of rare earth metal Ce addition to Sn-Ag solder on interfacial reactions with Cu substrate

The effect of adding a small amount of rare earth cerium (Ce) element to low Ag containing Sn-1wt%Ag Pb-free solder on its interfacial reactions with Cu substrate was investigated. The growth of intermetallic compounds (IMCs) between three Sn-1Ag-xCe solders with different Ce contents and a Cu substrate was studied and the results were compared to those obtained for the Ce-free Sn-1Ag/Cu systems. In the solid-state reactions of the Sn-1Ag(-xCe)/Cu solder joints, the two IMC layers, Cu₆Sn₅ and Cu₃Sn, grew as aging time increased. Compared to the Sn-1Ag/Cu joint, the growth of the Cu₆Sn₅ and Cu₃Sn layers was depressed for the Ce-containing Sn-1Ag-xCe/Cu joint. The addition of Ce to the Sn-Ag solder reduced the growth of the interfacial Cu-Sn IMCs and prevented the IMCs from spalling from the interface. The evenly-distributed Ce elements in the solder region blocked the diffusion of Sn atoms to the interface and retarded the growth of the interfacial IMC layer.     

Electrochemical corrosion behaviour of Sn–Ag–Cu (SAC) eutectic alloy in a chloride containing environment

The corrosion behaviour of the Sn_94.5Ag_3.8Cu_1.5 (SAC) eutectic alloy was investigated in 0.1 M NaCl solution by potentiodynamic polarization and impedance spectroscopy measurements and compared with that of the conventional Sn_73.9Pb_23.1 eutectic solder employed for a long time in the packaging of microelectronic components and devices. Scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) were used to characterize the SAC eutectic alloy prior to and after the electrochemical tests. The electrochemical results indicated that the Sn–Ag–Cu eutectic alloy exhibits better corrosion behaviour than the Sn–Pb eutectic solder in NaCl solution. The presence of a corrosion products layer constituted by tin oxy‐chloride was detected at the surface of both alloys investigated after the electrochemical tests. The better corrosion behaviour of SAC eutectic alloy compared to Sn–Pb eutectic solder is ascribed to the formation of a more compact surface film of corrosion products with improved protective properties owing to the presence of copper and silver, as revealed by EPMA.     

Solderability and intermetallic compounds formation of Sn-9Zn-xAg lead-free solders wetted on Cu substrate

The eutectic Sn-9Zn alloy was doped with Ag (0 wt.%-1 wt.%) to form Sn-9Zn-xAg lead-free solder alloys. The effect of the addition of Ag on the microstructure and solderability of this alloy was investigated and intermetallic compounds (IMCs) formed at the solder/Cu interface were also examined in this study. The results show that, due to the addition of Ag, the microstructure of the solder changes. When the quantity of Ag is lower than 0.3 wt.%, the needle-like Zn-rich phase decreases gradually. However, when the quantity of Ag is 0.5 wt.%-1 wt.%, Ag-Zn intermetallic compounds appear in the solder. In particular, adding 0.3 wt.% Ag improves the wetting behavior due to the better oxidation resistance of the Sn-9Zn solder. The addition of an excessive amount of Ag will deteriorate the wetting property because the glutinosity and fluidity of Sn-9Zn-(0.5, 1)Ag solder decrease. The results also indicate that the addition of Ag to the Sn-Zn solder leads to the precipitation of ε-AgZn₃ from the liquid solder on preformed interfacial intermetallics (Cu₅Zn₈). The peripheral AgZn₃, nodular on the Cu₅Zn₈ IMCs layer, is likely to be generated by a peritectic reaction L + γ-Ag₅Zn₈ → ɛ-AgZn₃ and the following crystallization of AgZn₃.     

Creep properties of Sn-Ag solder joints containing intermetallic particles

The creep behavior of the eutectic tin-silver joints and tin-silver composite solder joints containing 20 vol.% of Cu₆Sn₅, Ni₃Sn₄, and FeSn₂ intermetallic reinforcements introduced by in-situ methods was investigated. These creep tests were carried out using single shear lap solder joints at room temperature, 85°C, and 125°C. The creep resistance was similar in magnitude for all alloys, and with increasing temperature, the stressexponents decreased in a manner consistent with power-law breakdown behavior. The FeSn₂ intermetallic reinforced composite solder was found to be the most creep-resistant alloy at room temperature. Creep failure was observed to occur within the solder matrix in all these solder joints. Although a detailed analysis of the processes involved was difficult because of smearing of the features in the fracture surface, there were indications of grain-boundary separation, ductile fracture, and interfacial separation. For more information, contact K.N. Subramanian, Michigan State University, Department of Materials Science and Mechanics, 3536 Engineering Building, East Lansing, Michigan 48824-1226; (517) 353-5397; fax (517) 353-9842; e-mail subraman@egr.msu.edu.     

Progress in the design of new lead-free solder alloys

Various alloy design approaches have been employed to develop new lead-free solder alloys that can not only substitute for the lead-tin solders, but also offer significantly improved mechanical properties. Three new alloys are described in this article. In Sn-3.5Ag-1Zn (melting point ~217°C), the solidification structure and the eutectic precipitate morphology are6 refined by the addition of zinc. As a result, a high-strength, high-ductility solder with significantly improved creep resistance is obtained. In Bi-43Sn+2.5Fe, a eutectic alloy (melting point ~137°C), dispersion hardening by magnetically distributed iron particles retards both high-temperature deformation and microstructural coarsening, thus widening the useful service range of Bi-Sn eutectic alloys to much higher homologous temperatures than are typical for the Sn-Pb eutectic alloy. Lastly, Sn-Zn-In based alloys (melting point ~185°C) have been developed for consideration as a drop-in replacement for the neareutectic Sn-Pb alloy(melting point ~183°C).