Sn基无铅钎料与Cu基板间化合物Cu_6Sn_5的研究进展

主要介绍了Sn基无铅钎料和Cu基板在界面处反应生成的金属间化合物Cu6Sn5与焊接点可靠性的关系。综述了近年来Cu6Sn5的研究进展,内容包括:Sn基无铅钎料在Cu基板上形成的Cu6Sn5的生长形态、晶体取向、生长动力学以及纳米颗粒对界面Cu6Sn5尺寸及形貌的影响。     

Ti对Sn0.7Cu无铅钎料润湿性和界面的影响

研究了Ti的加入对Sn0.7Cu无铅钎料润湿性能以及钎料/Cu界面微观组织的影响.结果表明:在Sn0.7Cu中添加微量Ti,提高了钎料的润湿性能,可使铺展面积提高5％左右,当钎焊时间为3s时,界面金属间化合物(IMC)形貌由原来的扇贝状变为锯齿状;随着钎焊时间延长,Sn0.7Cu/Cu和Sn0.7Cu0.008Ti/C...     

热循环条件下Sn基钎料接头电迁移行为研究

通过电迁移和热疲劳循环实验,研究了热循环和高电流密度耦合作用下Sn58Bi和Sn3.0Ag0.5Cu钎料焊接接头的失效形式。实验结果表明,在通电和高低温冲击的耦合作用下,两种钎料接头的失效都发生在升温阶段。热循环导致接头内部裂纹的萌生和扩展,导致局部电流密度持续增大,加速了电迁移的发生,最终导致焊点失效。在热电耦合作用下,Sn58Bi钎料接头的使用寿命要长于Sn3.0Ag0.5Cu钎料接头的使用寿命。     

镧对Sn3.5Ag0.5Cu钎料组织性能影响

运用莱卡显微镜、扫描电镜和能谱分析等手段,研究了稀土元素La的添加量对Sn3.5Ag0.5Cu钎料及其与Cu基体焊接后微观组织及性能的影响。结果表明:添加不同含量的稀土La均能使钎料及其与Cu基体焊接后组织与性能得到改善,其中以w(La)达到0.05%时为最优,显微硬度及剪切强度分别提高14%和10.7%。键参数函数计算结果表明La具有"亲Sn"倾向,可细化钎料组织,降低IMC(界面金属间化合物)的长大驱动力。     

BiSbCuSn高温无铅软钎料物理性能及润湿性能研究

研制开发熔点在250～450℃之间的高温无铅软钎料一直是钎焊领域一大难题。熔点为300℃左右的Bi5Sb2Cu钎料因润湿性能和导电性能不良而受到限制。本文通过在Bi5Sb2Cu中添加不同含量Sn形成新型BiSbCuSn四元合金,来改善Bi5Sb2Cu合金的润湿性能和物理性能。结果表明：在Bi5Sb2Cu钎料合金中添加2-↑10wt．％Sn,BiSbCu钎料合金熔点呈下降趋势且幅度较大,但仍在250～450℃之间,润湿性能和导电性能明显改善。当Sn含量为10wt．％时,（Bi5Sb2Cu）10Sn钎料合金润湿性能和导电性能最好。     

Sn58Bi-xW复合钎料焊点微观组织及性能的研究

采用SEM、EDX等手段,研究了Sn58Bi-x W钎料润湿性能、组织形貌及焊点接头力学性能。结果表明:适量W颗粒可以提高Sn58Bi润湿性,随着W颗粒含量的增加,钎料的润湿性呈现先上升后下降的趋势,W质量分数为0.05%时润湿性最好,其铺展面积为132.73 mm~2。W颗粒可以有效细化Sn58Bi钎料合金的微观组织,减小焊点界面IMC厚度,当W添加量为质量分数0.1%,Sn-58B钎料的微观组织最为细小,界面IMC的厚度为0.71μm,焊点的抗拉强度最高,达101.6 MPa。     

La对Sn3.5Ag0.5Cu钎料界面组织和性能的影响

通过SEM和EDAX等,研究了La添加量对Sn3.5Ag0.5Cu钎料与Cu基体焊合界面IMC微观组织及性能的影响。结果表明:添加不同量的La均对Sn3.5Ag0.5Cu与Cu基体焊合后的组织有细化作用并增强其力学性能。其中以w(La)达到0.05%时最优,剪切强度可提高10.7%。材料热力学理论计算结果表明,La具有"亲Sn"倾向,添加少量La到Sn3.5Ag0.5Cu钎料中,可减小Cu6Sn5/Cu界面Sn的活度,降低IMC的长大驱动力。     

低银Sn—Ag—Cu无铅钎料的性能研究

使用银含量较低的Sn-Ag-Cu无铅钎料是降低焊料成本最直接有效的手段之一,但银含量降低后对钎料性能的影响尚缺乏系统报导。通过向Sn-Cu二元体系中加入不同比例的纯银,制备了一系列低银合金。研究了银含量对钎料的熔点、可焊性及溶铜性能的影响。通过拉伸试验研究了合金的强度及杨氏模量。综合考虑上述各项性能指标,Sn-0.5Ag-0.7Cu是具有最佳性价比的合金成分。     

Sn对BiSbCu钎料钎焊工艺性能的影响

在BiSbCu钎料中添加Sn,分析Sn对BiSbCu钎料合金钎焊工艺性能的主要指标——钎料熔点和铺展面积的影响.结果表明:在Bi5Sb2Cu钎料合金中加入Sn可以显著降低钎料的熔点和显著增强钎料合金的铺展性能.当Sn的质量分数为10％时,Bi5Sb2Cu钎料的铺展面积为26.22 mm2,钎焊工艺性能最好.     

三种高Sn无铅钎料的表面张力和润湿性能研究

采用悬滴法测量了3种无铅钎料合金(Sn-3.0Ag-0.5Cu、Sn-0.7Cu与Sn-9.0Zn)在260℃时的表面张力,分别为525.5,534.8和595.4 mN/m;同时采用座滴法测量了其在260℃熔融状态下与Cu基板的接触角,分别为24.5°、28.0°和102.5°,并且与传统Sn-37.0Pb钎料进行了比较研究。结果表明,无铅钎料合金的表面张力与接触角均大于Sn-37.0Pb钎料。结合Young-Dupre公式讨论了钎料合金表面张力与其润湿性能的相关性,认为Sn基钎料合金在Cu基板上的润湿性能主要取决于其表面张力。     

Role of tin content in the wetting of cu and au by tin-bismuth solders

This study describes tests in which solder composition, substrate metallization, temperature, and dwell time were combined in a factorially designed experiment to determine the effect of those factors on solder spread area. Measure of spread area, reflowed solder shape, solder microstructure, and solder and interface chemistry were taken in order to provide insight about the wetting mechanism(s). The reactivity of Au vs Cu metallization with solder was found to be a major factor in increasing spread area. The role of increasing tin content is to increase spread and spread rate. A similar effect is seen by increasing temperature. Time allowed for spread is a minor contributor to the spread area. Segregation of the tin and bismuth solder components during the wetting process was observed which indicated the role of bismuth as a carrier species. Analysis of variance methods based on the statistically designed experiments^1a’lb were used to show how to generate a model which estimates the spread area as a function of the tested factors.     

Effect of flux on the wetting characteristics of SnAg, SnCu, SnAgBi, and SnAgCu lead-free solders on copper substrates

The effect of flux on the wetting characteristics of four lead-free solders, Sn-3.5Ag, Sn-0.7Cu, Sn-3.5Ag-4.8Bi, and Sn-3.8Ag-0.7Cu (wt.%), on copper substrates have been studied at 240, 260, and 280°C. The fluxes investigated were rosin (R), mildly activated rosin (RMA), and activated rosin (RA). The wetting tests were conducted using the sessile-drop method. Results showed that fluxes significantly affect the wetting properties of the solders. Contact angles ranging from 10° to 30° for RMA, 20° to 30° for RA, and 35° to 60° for R were obtained. The effect of temperature on contact angle depended on the type of flux used. The contact angle decreased with increasing temperature; however, in some cases the contact angle was independent of temperature. The Sn-3.5Ag-4.8Bi exhibited the lowest contact angles indicating improved wettability with addition of bismuth. The microstructure of the solder/copper interface was analyzed by scanning electron microscopy.     

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.     

Solderability testing of Sn-Ag-XCu Pb-free solders on copper and Au-Ni-plated kovar substrates

Solderability was evaluated for four Pb-free alloys: 95.5Sn-4.3Ag-0.2Cu (wt.%), 95.5Sn-4.0Ag-0.5Cu, 95.5Sn-3.9Ag-0.6Cu, and 95.5Sn-3.8Ag-0.7Cu on oxygen-free electronic grade (OFE) Cu and Au-Ni plated Kovar substrates. The solderability metric was the contact angle, θ_c, as determined by the meniscometer/wetting balance technique. Tests were performed at 230°C, 245°C, and 260°C using rosin-based, mildly activated (RMA) flux, a rosin-based (R) flux, and a low-solids (LS) flux. The Pb-free solders exhibited acceptable to poor solderability (35°<θ_c<60°) on Cu with the RMA flux. Nonwetting occurred in most tests using the R flux. Wetting was observed with the LS flux, but only at 245°C and 260°C and with high contact angles. The solderability of the Pb-free solders improved at all test temperatures on the Au-Ni plated Kovar substrate when using the RMA flux (30°<θ_c<50°). Wetting was observed with the R flux (35°<θ_c<60°) and LS flux (50°<θ_c<85°) for all temperatures. The Pb-free solders had generally lower wetting rates and longer wetting times on Cu than the 63Sn-37Pb solder. The wetting rate and wetting time data were superior on the Au-Ni plated Kovar substrates. In general, solderability, as measured by θ_c along with the wetting rate and wetting time, did not exhibit a consistent dependence on the composition of the Sn-Ag-XCu (X=0.2, 0.5, 0.6, and 0.7) alloys. The better performers were 95.5Sn-3.9Ag-0.6Cu alloy with the RMA flux (both Cu and Au-Ni plated Kovar) and 95.5Sn-3.8Ag-0.7Cu with the R and LS fluxes (Au-Ni-Kovar, only). The solder-flux interfacial tension, γ_LF, had a significant impact on the θ_c values. The magnitudes of the contact angle θ_c suggested that the four Pb-free solders would experience higher solderability defect counts at the printed wiring assembly level.     

Effect of alloying elements on properties and microstructures of SnAgCu solders

Recent years, the SnAgCu family of alloys has been found a widely application as a replacement for the conventional SnPb solders in electronic industry. In order to further enhance the properties of SnAgCu solder alloys, alloying elements such as rare earth, Bi, Sb, Fe, Co, Mn, Ti, In, Ni, Ge and nano-particles were selected by lots of researchers as alloys addition into these alloys. Rare earth (RE) elements have been called the ‘‘vitamin” of metals, which means that a small amount of RE elements can greatly enhance the properties of metals, such as microstructure refinement, alloying and purification of materials and metamorphosis of inclusions. In addition, a small amount of Zn addition has the ability to reduce undercooling efficiently and suppress the formation of massive primary Ag₃Sn plates, and Bi/Ga has the ability to enhance the wettability of SnAgCu alloys as well as Ni. Moreover, adding Co/Fe/Ge can effectively refine microstructure, modify interfacial Cu-Sn compounds and increase the shear strength of joints with Cu. This paper summarizes the effects of alloying elements on the wettability, mechanical properties, creep behavior and microstructures of SnAgCu lead-free solder alloys.     

Comparative study of interfacial reactions of Sn-Ag-Cu and Sn-Ag solders on Cu pads during reflow soldering

The interfacial reaction in soldering is a crucial subject for the solder-joint integrity and reliability in electronic packaging technology. However, electronic industries are moving toward lead-free alloys because of environmental concerns. This drive has highlighted the fact that the industry has not yet arrived at a decision for lead-free solders. Among the lead-free alloys, Sn-3.5Ag and Sn-3.5Ag-0.5Cu are the two potential candidates. Here, detailed microstructural studies were carried out to compare the interfacial reaction of Sn-3.5Ag and Sn-3.5Ag-0.5Cu solder with a ball grid array (BGA) Cu substrate for different reflow times. The Cu dissolution from the substrate was observed for different soldering temperatures ranging from 230°C to 250°C, and the dissolution was found to increase with time and temperature. Dissolution of Cu in the Sn-3.5Ag solder is so fast that, at 240°C, 12 μm of the Cu substrate is fully consumed within 5 min. Much less dissolution is observed for the Sn-3.5Ag-0.5Cu solder. In respect to such high dissolution, there is no significant difference observed in the intermetallic compound (IMC) thickness at the interface for both solder alloys. A simplistic theoretical approach is carried out to find out the amount of Cu₆Sn₅ IMCs in the bulk of the solder by the measurement of the Cu consumption from the substrate and the thickness of the IMCs that form on the interface.     

Effect of Zn content on the vibration fracture behavior of Sn-Zn and Sn-Zn-Bi solders

This study investigated the microstructure and vibration properties of Sn-Zn and Sn-Zn-Bi alloys with different Zn contents. Experimental results show that the hypoeutectic Sn-Zn-Bi alloy (with a Zn content of 5 wt.%) has the poorest damping capacity and the lowest critical vibration cycles to failure due to a hardening effect by Bi and intergranular fracturing. On the other hand, since the Zn/Sn interfaces at which internal friction may occur during vibration contribute to the dissipation of vibration energy, the hypereutectic Sn-13Zn samples with numerous massive primary Zn needles possess superior damping capacity and vibration life under constant vibration force conditions.     

Effects of solid-state annealing on the interfacial intermetallics between tin-lead solders and copper

The interfacial intermetallics between Cu and solder were studied for four Sn-Pb compositions at the annealing temperatures of 125°C, 150°C, and 175°C for up to 30 days. The η-phase (Cu₆Sn₅) layer formed during reflow continues to grow during annealing. An additional layer of ɛ-phase (Cu₃Sn) forms at the η/Cu interface after an incubation annealing time. The thickness results fit a power-law relationship against time with average exponents 0.69 and 0.44 for the η phase and the ɛ phase, respectively. On prolonged annealing, the proportions of the individual phases in the total layer reach a steady state.     

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.