SnAgCuRE系钎料的钎焊接头组织与力学性能

以Sn2.5Ag0.7Cu为基础,添加微量的稀土(RE)r(Ce︰La)为4︰1,研究了钎焊接头的显微组织与力学性能。结果表明:添加微量的RE后,钎料与Cu试样间的界面层厚度明显减小,且界面处的组织更加平滑,相应地其剪切强度随微量RE的添加而增大,并在RE含量(质量分数)为0.1%时达到最大值36MPa。     

Sn-3.0Ag-0.5Cu/Cu焊点可靠性研究

采用铺展面积法研究了Sn-3.0Ag-0.5Cu无铅钎料在不同温度下的润湿性能,同时探讨了150℃等温时效对Sn-3.0Ag-0.5Cu/Cu焊点界面组织及力学性能的影响。结果表明,随着钎焊温度的升高,Sn-3.0Ag-0.5Cu钎料的润湿性能明显增加。焊后钎料/Cu界面处对应的金属间化合物为Cu6Sn5相,经150℃时效,界面层的形貌由原来的齿状逐渐转化为层状,且厚度随着时效时间的增加而增加。发现界面层金属间化合物厚度与时效时间的二次方根成线性关系。对焊点在时效过程中的力学性能进行分析,发现Sn3.0Ag0.5Cu/Cu焊点的力学性能随着时效时间的增加逐渐降低,时效初期,焊点的力学性能下降较快,后期趋于平缓。     

BiAgSbCu系高温无铅钎料制备及焊接性能研究

研制开发熔点在260 ℃以上的高温无铅钎料来代替传统的高铅钎料运用于电子封装一直是钎焊领域的一大难题。熔点约为272 ℃的Bi-2.6 Ag-5 Sb钎料合金因润湿性和焊接可靠性不良在运用上受到限制。文中通过在Bi-2.6 Ag-5 Sb钎料合金中添加微量元素Cu来改善B-i2.6 Ag-5 Sb合金的润湿性及焊接可靠性。研究结果表明,Cu含量对BiAgSbCu系钎料合金熔点影响较小,当Cu含量为2 %时,润湿性及焊接可靠性最佳。     

Sn-0.3Ag-0.7Cu-xBi低银无铅钎料的润湿性

以Bi为添加剂对低银型Sn-0.3Ag-0.7Cu无铅钎料进行改性,应用SAT—5100型润湿平衡仪对Sn-0.3Ag-0.7Cu-xBi(x=0,1,3和4.5)钎料的润湿性能作了对比分析。结果表明:适量Bi元素的加入可以改善Sn-0.3Ag-0.7Cu钎料合金的润湿性能,且在240℃下Sn-0.3Ag-0.7Cu-3.0Bi无铅钎料具有最佳的润湿性能,在250℃其润湿力达到最大值3.2×10–3N/cm。     

Ga元素含量对305钎料组织及性能的影响

通过在Sn-3Ag-0.5Cu钎料中添加不同含量的Ga，并采用差示扫描量热法（DSC）、万能试验机测试方法配制合金材料的熔化特性曲线、力学性能、金相结构、焊接润湿扩展率等性质，研究Ga含量对Sn-3Ag-0.5Cu钎料的熔化过程、焊接润湿扩展性以及组织和力学性能方面的影响。结果表明，Sn-3Ag-0.5Cu钎料中加入Ga元素以后，随着Ga增加，钎料的熔点显著降低，熔程也逐渐增大；适量的Ga元素可以改善Sn-3Ag-0.5Cu钎料的润湿性能；当Ga元素的添加量质量分数达到0.5%时，Sn-3Ag-0.5Cu钎料的组织均匀，晶粒明显细化，钎料的力学性能最佳，但Ga元素含量进一步增加时，在晶界处析出黑色富Ga相，对钎料力学性能产生了不利影响。     

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。     

SnAgCu系钎料合金对表面贴装元件润湿特性研究

采用润湿平衡法,研究了水溶性钎剂条件下SnAgCu系钎料合金对表面贴装元件的润湿特性.试验结果表明,钎焊温度对润湿力作用显著.Sn2.5Ag0.7Cu钎料合金的最大润湿力为1.265 mN,其最佳工艺参数分别为:预热时间15 s,钎焊温度255℃和钎焊时间5 s.该润湿力高于目前商用的Sn3.0Ag0.5Cu钎料,与Sn3.8Ag0.7Cu钎料润湿力相当,完全能够满足表面组装行业对无铅钎料润湿性能的要求.     

回流焊对SnAgCu焊点IMC及剪切强度的影响

研究了回流焊次数对Sn-0.3Ag-0.7Cu-xNi/Cu(x=0,0.05)焊点的界面反应及其剪切强度的影响。结果表明:随着回流焊次数的增加,界面金属间化合物(IMC)Cu6Sn5和(Cu1-xNix)6Sn5的厚度均增加。在钎料中添加w(Ni)为0.05%,可有效抑制IMC的生长,与回流焊次数无关。回流焊次数对Sn-0.3Ag-0.7Cu/Cu和Sn-0.3Ag-0.7Cu-0.05Ni/Cu的剪切强度影响都不大,五次回流焊后剪切强度略有下降,剪切强度分别为21MPa和25MPa。发现断裂面部分在钎料中,部分在钎料和IMC之间。     

微量Sn添加对BiAgSb系高温无铅钎料焊接性能的影响

通过在Bi-2.6Ag-5Sb钎料合金中添加微量元素Sn来改善Bi-2.6Ag-5Sb合金的润湿性和焊接可靠性。研究结果表明:Bi-2.6Ag-5Sb钎料合金中添加质量分数0.5%~3.0%的Sn,随着Sn含量的增加,钎料的熔点呈下降趋势,熔点仍然在260~280℃,能明显改善其润湿性和焊接可靠性。     

颗粒增强Sn-Ag基无铅复合钎料显微组织与性能

通过外加法向Sn-3.5Ag焊料中加入体积分数为10%的微米级Cu、Ni颗粒制备了无铅复合钎料,对钎料的显微组织、拉剪及润湿性能进行了研究。结果表明,颗粒周围以及基板界面处的显微组织中生成了金属间化合物,其形态及大小因加入颗粒而不同。颗粒的加入提高了钎料钎焊接头的剪切强度,其中Cu颗粒增强的接头的剪切强度提高了33%,Ni颗粒的提高了20%。两种复合钎料的铺展面积均下降了约15%,其中Cu颗粒增强复合钎料润湿角由11°增加到18°。     

Interfacial reaction between multicomponent lead-free solders and Ag,Cu, Ni,and Pd substrates

The interfacial reaction between two prototype multicomponent lead-free solders, Sn-3.4Ag-1Bi-0.7Cu-4In and Sn-3.4Ag-3Bi-0.7Cu-4In (mass%), and Ag, Cu, Ni, and Pd substrates are studied at 250°C and 150°C. The microstructural characterization of the solder bumps is carried out by scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis. Ambient temperature, isotropic elastic properties (bulk, shear, and Young’s moduli and Poisson’s ratio) of these solders along with eutectic Sn-Ag, Sn-Bi, and Sn-Zn solders are measured. The isotropic elastic moduli of multicomponent solders are very similar to the eutectic Sn-Ag solder. The measured solubility of the base metal in liquid solders at 250°C agrees very well with the solubility limits reported in assessed Sn-X (X=Ag, Cu, Ni, Pd) phase diagrams. The measured contact angles were generally less than 15° on Cu and Pd substrates, while they were between 25° and 30° on Ag and Ni substrates. The observed intermediate phases in Ag/solder couples were Ag₃Sn after reflow at 250°C and Ag₃Sn and ζ (Ag-Sn) after solid-state aging at 150°C. In Cu/solder and Ni/solder couples, the interfacial phases were Cu₆Sn₅ and (Cu,Ni)₆Sn₅, respectively. In Pd/solder couples, only PdSn₄ after 60-sec reflow, while both PdSn₄ and PdSn₃ after 300-sec reflow, were observed.     

Interfacial reaction and solder joint reliability of Pb-free solders in lead frame chip scale packages (LF-CSP)

Chip scale packages (CSP) have essential solder joint quality problems, and a board level reliability is a key issue in design and development of the CSP type packages. There has been an effort to eliminate Pb from solder due to its toxicology. To evaluate the various solder balls in CSP package applications, Pb-free Sn-Ag-X (X=In, Cu, Bi) and Sn-9Zn-1Bi-5In solder balls were characterized by melting behavior, phases, interfacial reaction, and solder joint reliability. For studying joint strength between solders and under bump metallurgy (UBM) systems, various UBMs were prepared by electroplating and electroless plating. After T/C (temperature cycle) test, Sn3.5Ag8.5In solder was partially corroded and its shape was distorted. This phenomenon was observed in a Sn3Ag10In 1Cu solder system, too. Their fractured surface, microstructure of solder joint interface, and of bulk solder ball were examined and analyzed by optical microscopy, SEM and EDX. To simulate the real surface mounting condition and evaluate the solder joint reliability on board level, Daisy chain test samples using LF-CSP packages were prepared with various Pb-free solders, then a temperature cycle test (−65∼ 150°C) was performed. All tested Pb-free solders showed better board level solder joint reliability than Sn-36Pb-2Ag. Sn-3.5Ag-0.7Cu and Sn-9Zn-1Bi-5In solders showed 35%, 100% superior solder joint reliability than Sn-36Pb-2Ag solder ball, respectively.     

Effect of Ag on the Microstructure of Sn-8.5Zn-xAg-0.01Al-0.1Ga Solders Under High-Temperature and High-Humidity Conditions

The effect of Ag on the microstructure and thermal behavior of Sn-Zn and Sn-8.5Zn-xAg-0.01Al-0.1Ga solders (x from 0.1 wt.% to 1 wt.%) under high-temperature/relative humidity conditions (85°C/85% RH) for various exposure times was investigated. Scanning electron microscopy (SEM) studies revealed that, in all the investigated solders, the primary α-Zn phases were surrounded by eutectic β-Sn/α-Zn phases, in which fine Zn platelets were dispersed in the β-Sn matrix. SEM micrographs revealed that increase of the Ag content to 1 wt.% resulted in coarsening of the dendritic plates and diminished the Sn-9Zn eutectic phase in the microstructure. Differential scanning calorimetry (DSC) studies revealed that the melting temperature of Sn-8.5Zn-xAg-0.01Al-0.1Ga solder decreased from 199.6°C to 199.2°C with increase of the Ag content in the solder alloy. Both ZnO and SnO₂ along with Ag-Zn intermetallic compound (IMC) were formed on the surface when Sn-8.5Zn-0.5Ag-0.01Al-0.1Ga solder was exposed to high-temperature/high-humidity conditions (85°C/85% RH) for 100 h. The thickness of the ZnO phase increased as the Ag content and exposure time were increased. Sn whiskers of various shapes and lengths varying from 2 μm to 5 μm were extruded from the surface when the investigated five-element solder with Ag content varying from 0.5 wt.% to 1 wt.% was exposed to similar temperature/humidity conditions for 250 h. The length and density of the whiskers increased with further increase of the exposure time to 500 h and the Ag content in the solder to 1 wt.%. The Sn whisker growth was driven by the compressive stress in the solder, which was generated due to the volume expansion caused by ZnO and Ag-Zn intermetallic compound formation at the grain boundaries of Sn.     

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.     

Low-cycle fatigue behavior of Sn-Ag, Sn-Ag-Cu, and Sn-Ag-Cu-Bi lead-free solders

Low-cycle fatigue (LCF) tests on as-cast Sn-3.5Ag, Sn-3Ag-0.5Cu, Sn-3Ag-0.5Cu-1Bi, and Sn-3Ag-0.5Cu-3Bi solders was carried out using a noncontact strain-controlled system at 20°C with a constant frequency of 0.1 Hz. The addition of Cu does not significantly affect the fatigue life of eutectic Sn-Ag solder. However, the fatigue life was significantly reduced with the addition of Bi. The LCF behavior of all solders followed the Coffin-Manson relationship. The fatigue life of the present solders is dominated by the fracture ductility and can be described by the ductility-modified Coffin-Manson’s relationship. Steps at the boundaries of dendrite phases were the initiation sites for microcracks for Sn-3.5Ag, Sn-3Ag-0.5Cu, and Sn-3Ag-0.5Cu-1Bi solders, while for Sn-3Ag-0.5Cu-3Bi solder, cracks initiated along both the dendrite boundaries and subgrain boundaries in the dendrite phases. The linking of these cracks and the propagation of cracks inside the specimen occurred both transgranularly through eutectic phases and intergranularly along dendrite boundaries or subgrain boundaries.     

Effects of Trace Amounts of Rare Earth Additions on Microstructure and Properties of Sn-Bi-Based Solder Alloy

The effect of trace amounts of rare earth additions on the microstructure and properties were studied for the Sn-58Bi and Sn-58Bi-Ag solder alloys. At the same time, the intermetallic compounds (IMCs) in the solder alloys and intermetallic layer (IML) thickness at the solder/Cu substrate interface were investigated, both as-reflowed and after high-temperature aging. The results indicate that adding trace amounts of rare earth (RE) elements has little influence on the melting temperature and microhardness of the solders investigated, but adding RE elements improves the wettability and shear strength of the Sn-58Bi and Sn-58Bi-Ag solder alloys. In addition, it was found that the addition of RE elements not only refines the microstructure and size of the IMC particles, but also decreases the IML thickness and shear strength of the Sn-58Bi solder joint after high-temperature aging. Adding trace amounts of RE elements is superior to adding trace amounts of Ag for improving the properties of the Sn-58Bi solder. The reason may be related to the modification of the microstructure of the solder alloys due to the addition of trace amounts of RE elements.     

Dissolution behavior of Cu and Ag substrates in molten solders

This study investigated the dissolution behavior of Cu and Ag substrates in molten Sn, Sn-3.5Ag, Sn-4.0Ag-0.5Cu, Sn-8.6Zn and Sn-8.55Zn-0.5Ag-0.1Al-0.5Ga lead-free solders as well as in Sn-37Pb solder for comparison at 300, 350, and 400°C. Results show that Sn-Zn alloys have a substantially lower dissolution rate of both Cu and Ag substrates than the other solders. Differences in interfacial intermetallic compounds formed during reaction and the morphology of these compounds strongly affected the substrate dissolution behavior. Soldering temperature and the corresponding solubility limit of the substrate elements in the liquid solder also played important roles in the interfacial morphology and dissolution rate of substrate.     

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.     

Effect of reflow and thermal aging on the microstructure and microhardness of Sn-3.7Ag-xBi solder alloys

This work investigates the effect of reflow and the thermal aging process on the microstructural evolution and microhardness of five types of Sn-Ag based lead-free solder alloys: Sn-3.7Ag, Sn-3.7Ag-1Bi, Sn-3.7Ag-2Bi, Sn-3.7Ag-3Bi, and Sn-3.7Ag-4Bi. The microhardness and microstructure of the solders for different cooling rates after reflow at 250°C and different thermal aging durations at 150°C for air-cooled samples have been studied. The effect of Bi is discussed based on the experimental results. It was found that the microhardness increases with increasing Bi addition to Sn-3.7Ag solder regardless of reflow or thermal aging process. Scanning electron microscopy images show the formation of Ag₃Sn particles, Sn-rich phases, and precipitation of Bi-rich phases in different solders. The increase of microhardness with Bi addition is due to the solution strengthening and precipitation strengthening provided by Bi in the solder. The trend of decrease in microhardness with increasing duration of thermal aging was observed.     

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.