Sn-Zn-Bi-X(Ag,Cu)系钎料的断裂韧性研究

通过对两种具有代表性的无铅软钎料断口的分析,介绍了Sn-Zn-Bi-X(Ag,Cu)系钎料合金的断裂韧性的初步研究结果,发现Bi固溶于钎料基体导致了钎料合金脆性的增加,随着Bi含量的增加,脆性随之增大。同时发现,钎料的冷却方式对钎料的脆性倾向有较大的影响。     

Sn-8Zn无铅钎料性能的研究

研究了不同微量合金元素(Bi、Ag)对Sn-8Zn无铅钎料高温抗氧化性能及接头剪切强度的影响,采用氧化质量增加△m值的方法,在高温下观察钎料表面氧化膜形状和颜色的变化并对氧化膜进行X射线衍射分析,探讨了钎料的高温抗氧化性能的机理,通过对钎料的金相显微组织观察和对热处理后钎焊接头的剪切强度试验,分析了提高接头剪切强度的原因.试验结果表明:在Sn-8Zn钎料中加入适量的合金元素(Bi、Ag)均可以改善和提高钎料的高温抗氧化性能和接头的剪切强度.     

Sn-Zn系无铅钎料最新进展

Sn-Zn系钎料熔点与传统Sn-37Pb钎料十分接近,成本低廉,被研究者所推崇。由于Zn的存在导致Sn-Zn钎料润湿性差及抗氧化性不足,阻碍了该钎料的发展。添加合金元素和纳米颗粒是改善Sn-Zn钎料组织和性能行之有效的方法之一,为国内外研究者所推崇。结合国内外Sn-Zn系无铅钎料最新研究成果,探讨添加微量的合金元素In、Ni、Cr、Ga、Bi、Cu、Al、Ag、稀土元素及纳米颗粒对钎料润湿性、抗氧化性、力学性能、显微组织和界面组织的影响,同时简述有关钎剂对Sn-Zn的影响,并对Sn-Zn系钎料的发展趋势进行分析与展望。     

稀土对Zn20Sn高温无铅钎料组织与性能的影响

向Zn20Sn高温无铅钎料中添加微量铈镧混合稀土（RE）,研究了RE的添加量对该钎料合金显微组织及性能的影响。结果表明,添加微量RE的合金显微组织中出现含RE的金属间化合物（IMC）。随着RE的添加,形状各异的IMC的数量显著增加。RE质量分数为0.5%~1.0%的合金的固相线温度不变,而液相线温度略有降低。当RE质量分数为0.5%时,钎料在Cu基板上的铺展面积最大,比Zn20Sn钎料提高了57.6%。但随着RE的继续添加,钎料的润湿性降低。当RE质量分数超过0.1%时,钎料的显微硬度和电阻率随着RE含量的增加而增大。综合考虑,合适的RE添加量为质量分数0.5%。     

Ag对Sn-9Zn合金钎料组织及性能的影响

用莱卡显微镜、XRD研究添加元素Ag对Sn-9Zn钎料组织及性能的影响。结果表明:Ag与Zn形成AgZn3化合物,能抑制粗大针状富Zn相的形成,可使Sn-9Zn钎料合金的润湿性提高20%,并明显改善Sn-9Zn的耐蚀性。     

Sn-Zn系钎料研究及应用现状

随着钎料无铅化的发展,Sn-Zn钎料以其低廉的成本,与SnPb钎料相近的熔点成为无铅钎料研究的重点.但是Sn-Zn钎料存在易氧化,抗腐蚀性差,润湿性差的问题,通常在SnZn钎料中加入不同元素,改善其性能.主要阐述不同添加元素Bi、Al、In、Re(稀土元素)、Ag、Cu、P和多元合金对SnZn钎料自身性能和钎料与Cu结合性能的影响,概述SnZn系钎料的工业应用现状.     

基于纳米压痕法的SnBi-xNi钎料的塑性比较

借助纳米压痕的方法,采用压痕形成过程中塑性应变与总应变的比值来表征钎料塑性。对Sn Bi-x Ni(x=0,0.05,0.1,0.15和0.2)成分钎料的硬度、弹性模量及塑性进行了对比。结果表明:Sn58Bi钎料合金加入Ni元素后,钎料硬度和弹性模量升高。当Sn58Bi-x Ni钎料中Ni含量的质量分数为0.1%时,其硬度及弹性模量最大。当Ni质量分数超过0.1%时,钎料的硬度与弹性模量有所下降。当添加Ni元素质量分数为0.05%~0.1%时,钎料合金的组织得到了细化,钎料合金的塑性提高;当Ni质量分数大于0.15%时,钎料的塑性降低。     

无铅制程导入面临的问题及解决方案(续)

(上接2006年第5期第55页)3.4.6杂质元素控制表8为无铅钎料中污染元素含量上限要求。实际生产过程中,对钎料槽中Cu、Pb、Fe等杂质要进行严格控制。钎料中的Cu主要来源于电路板镀层和元件镀层,SAC合金更趋向于溶解铜,速度是SnPb合金表8无铅钎料中污染元素含量上限上限/%现象Pb0.100法律规定Bi0.250无光泽,与铅使用会增加剥离Cu0.300会随钎料槽的使用而增加Cd0.002氧化增加粘度Zn0.005氧化排流不良,乳化锡渣Al0.002增加锡渣率0.0005?0.020造成焊点砂质In0.100降低熔点As0.030产生半润湿Au0.010钎料变得不活波,焊点无光泽的2倍,是SnC…     

Ag和RE对SnAgCuRE无铅钎料拉伸性能的影响

利用正交试验法,对SnAgCuRE系钎料合金的拉伸性能进行了检验。结果表明:SnAgCuRE系钎料合金的拉伸性能与Ag和RE的添加量密切相关,即拉伸强度会随Ag含量增大而提高;延伸率受RE影响最大,并在w(RE)为0.1%时延伸率和拉伸强度都达到最佳。当w(RE)达到0.5%时,会导致延伸率的下降。     

稀土改性的Sn-58Bi低温无铅钎料

研究了微量稀土对Sn-58Bi低温钎料的改性作用.试验添加质量分数为0.1 ?组混合稀土的无铅材料,并对比Sn-58Bi和Sn-58Bi0.5Ag合金.观察了钎料显微组织的变化并做了定量分析,采用DSC测试了钎料的熔化温度,同时测量了钎料的润湿性能、接头强度与硬度.结果表明,微量稀土添加细化了Sn-58Bi钎料合金的显微组织,对钎料的熔化温度几乎没有影响,能显著改善Sn-58Bi钎料的润湿性能和接头剪切强度,而且改善的程度优于添加微量Ag对Sn-58Bi钎料的作用.     

Wettability of electroless Ni in the under bump metallurgy with lead free solder

This study investigates the wettability of several lead-free solders, including Sn, Sn−Ag, and Sn−Bi, on electroless Ni (EN) with various phosphorus content. The role of phosphorus on solder wettability is studied. Microstructure evolution in the lead-free solder/EN joint is investigated with the aid of electron probe microanalyzer (EPMA) to relate metallurgical reactions between the solder and the EN. The SN solder exhibits better wettability on EN, while the Si−Bi solder has a larger contact angle. Wettability degrades as the phosphorus content in EN decreases. The dependence of wetting angle on the phosphorous content can be attributed to the surface roughness and density of EN, along with the interfacial reaction between the solders and EN. An EPMA analysis reveals the presence of a Sn−Bi−Ni−P solid solution at the interface of solder/EN joints due to the interdiffusion of major constituent Ni and Sn. The interaction zone of the solid solution increases with increasing temperature. Wettability of Pb-free solders on EN degrades with the presence of NiO due to oxidation or the existence of Ni₃P due to precipitation after annealing. For an adequate wetting behavior in the Sn (Sn−Bi, Sn−Ag)/EN joint, EN deposited with phosphorus contents in the range of 9 to 12 wt% is suggested.     

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.     

Microstructure, Thermal and Wetting Properties of Sn-Bi-Zn Lead-Free Solder

The microstructures, phase transformations, and wettability of Sn-Bi-Zn solder alloys were investigated by scanning electron microscopy, x-ray diffraction, and differential scanning calorimetry (DSC). The results show that the alloys are composed of primary Sn-rich phase or Zn-rich phase, (Sn + Zn) eutectic structure, and (Sn + Bi + Zn) ternary eutectic structure. The microstructural characterization of Sn-xBi-Zn alloys indicates that, with increasing Bi content, more of the eutectic (Sn-Bi-Zn) structures is formed. DSC profiles reveal that the eutectic peak of the samples did not differ very much, but the reaction temperature of the alloys decreases with increased Bi content. The spreading rates of solders increased with the addition of Zn, which affects the interfacial reactions between the solders and copper.     

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.     

High-Reliability Low-Ag-Content Sn-Ag-Cu Solder Joints for Electronics Applications

Sn-Ag-Cu (SAC) alloy is currently recognized as the standard lead-free solder alloy for packaging of interconnects in the electronics industry, and high- Ag-content SAC alloys are the most popular choice. However, this choice has been encumbered by the fragility of the solder joints that has been observed in drop testing as well as the high cost of the Ag itself. Therefore, low-Ag-content SAC alloy was considered as a solution for both issues. However, this approach may compromise the thermal-cycling performance of the solders. Therefore, to enhance the thermal-cycling reliability of low-Ag-content SAC alloys without sacrificing their drop-impact performance, alloying elements such as Mn, Ce, Ti, Bi, In, Sb, Ni, Zn, Al, Fe, and Co were selected as additions to these alloys. However, research reports related to these modified SAC alloys are limited. To address this paucity, the present study reviews the effect of these minor alloying elements on the solder joint reliability of low-Ag-content SAC alloys in terms of thermal cycling and drop impact. Addition of Mn, Ce, Bi, and Ni to low-Ag-content SAC solder effectively improves the thermal-cycling reliability of joints without sacrificing the drop-impact performance. Taking into consideration the improvement in the bulk alloy microstructure and mechanical properties, wetting properties, and growth suppression of the interface intermetallic compound (IMC) layers, addition of Ti, In, Sb, Zn, Al, Fe, and Co to low-Ag-content SAC solder has the potential to improve the thermal-cycling reliability of joints without sacrificing the drop-impact performance. Consequently, further investigations of both thermal-cycling and drop reliability of these modified solder joints must be carried out in future work.     

Evaluation of Lead- Free Solder Joints in Electronic Assemblies

The feasibility of printed circuit board assembly with lead-free solder alloys was investigated. Studies were conducted with two baseline eutectic binary alloys, SnBi and SnAg, and three new lead-free solder formulations: (1) 91.8Sn-4.8Bi-3.4Ag (wt%) developed at Sandia Laboratories, (2) 77.2Sn-20In-2.8Ag developed at Indium Corp. of America, and (3) 96.2Sn-2.5Ag-0.8Cu-0.5Sb provided by AIM Inc. The basic physical properties (melting temperature, wetting, mechanical strength) pertinent to each of the newly developed alloys are described. The feasibility of 0.4 mm pitch assembly was established with each of the lead-free solder alloys investigated, although the processing windows were generally found to be narrower. All solder joints exhibited good fillets, in accordance with the workmanship standards. Wetting of the lead-free solders was significantly improved on immersion tin vs imidazole finished circuit boards. The laminates did not suffer thermal degradation effects, such as warpage, delamination, or severe discoloration (reflow was performed under an inert atmosphere). It is thus concluded that the manufacturability performance of the new solder formulations is adequate for surface mount applications.     

Influence of Ag micro-particle additions on the microstructure, hardness and tensile properties of Sn-9Zn binary eutectic solder alloy

In this study, an addition of Ag micro-particles (8-10 μm) with a content in the range between 0 and 1.5 wt.% to Sn-9Zn eutectic solder, were examined in order to understand the effect of Ag additions as the particulate reinforcement on the microstructural and mechanical properties as well as the thermal behavior of the newly developed composite solders. Here, an approach to prepare a micro-composite solder alloy by mixing Ag micro-particles with a molten Sn-Zn solder alloy was developed. The composite solder was prepared by mechanically mixing Ag micro-particles into the Sn-9Zn alloy melt to ensure a homogeneous distribution of the reinforcing particles. The distribution of the Ag micro-particles in the matrix was found to be fairly uniform. The Ag particles reacted with the Zn and formed ε-AgZn₃ intermetallic compounds (IMC) in the β-Sn matrix. It was found that the more Ag particles added to the Sn-9Zn solder, the more Ag-Zn compound formed. In the Sn-9Zn/XAg composite solder, the microstructure was composed of AgZn₃ IMC and α-Zn phase in the β-Sn matrix. Interestingly, as the Ag particles in the composite solder increased, the α-Zn phase was found to be depleted from the matrix. The average tensile strength of the composite solders increased with the Ag micro-particles content up to a certain limit. Beyond this limit, the addition of Ag particles actually decreased the strength.     

Effect of Ag micro-particles content on the mechanical strength of the interface formed between Sn–Zn binary solder and Au/Ni/Cu bond pads

In this study, addition of Ag micro-particles with a content in the range between 0 and 4 wt.% to a Sn–Zn eutectic solder, were examined in order to understand the effect of Ag additions on the microstructural and mechanical properties as well as the thermal behavior of the composite solder formed. The shear strengths and the interfacial reactions of Sn–Zn micro-composite eutectic solders with Au/Ni/Cu ball grid array (BGA) pad metallizations were systematically investigated. Three distinct intermetallic compound (IMC) layers were formed at the solder interface of the Au/electrolytic Ni/Cu bond pads with the Sn–Zn composite alloys. The more Ag particles that were added to the Sn–Zn solder, the more Ag–Zn compound formed to thicken the uppermost IMC layer. The dissolved Ag–Zn IMCs formed in the bulk solder redeposited over the initially formed interfacial Au–Zn IMC layer, which prevented the whole IMC layer lifting-off from the pad surface. Cross-sectional studies of the interfaces were also conducted to correlate with the fracture surfaces.     

无铅焊料在清华大学的研究与发展

清华大学材料科学与工程系电子材料与封装技术研究室研制了6个系列的无铅焊料:Sn-3.5Ag添加Cu或Bi; Sn-3.5Ag-1.0Cu添加In或Bi; Sn-Ag-Cu-In添加Bi; Sn-Ag-Cu添加Ga; Sn-Zn添加Ga; Sn-Zn添加多种元素。重点介绍了Sn-Zn添加多种元素。对6个系列无铅焊料的研究取得了较好的实验结果,得到比较理想的低温焊料体系,有的合金熔点已非常接近铅锡共晶焊料熔点183℃。     

Mechanical Properties and Electrochemical Corrosion Behavior of Al/Sn-9Zn-<Emphasis Type="Italic">x</Emphasis>Ag/Cu Joints

The effect of Ag content on the wetting behavior of Sn-9Zn-xAg on aluminum and copper substrates during soldering, as well as the mechanical properties and electrochemical corrosion behavior of Al/Sn-9Zn-xAg/Cu solder joints, were investigated in the present work. Tiny Zn and coarsened dendritic AgZn₃ regions were distributed in the Sn matrix in the bulk Sn-9Zn-xAg solders, and the amount of Zn decreased while that of AgZn₃ increased with increasing Ag content. The wettability of Sn-9Zn-1.5Ag solder on Cu substrate was better than those of the other Sn-9Zn-xAg solders but worse than that of Sn-9Zn solder. The wettability of Sn-9Zn-1.5Ag on the Al substrate was also better than those of the other Sn-9Zn-xAg solders, and even better than that of Sn-9Zn solder. The Al/Sn-9Zn/Cu joint had the highest shear strength, and the shear strength of the Al/Sn-9Zn-xAg/Cu (x = 0 wt.% to 3 wt.%) joints gradually decreased with increasing Ag content. The corrosion resistance of the Sn-9Zn-xAg solders in Al/Sn-9Zn-xAg/Cu joints in 5% NaCl solution was improved compared with that of Sn-9Zn. The corrosion potential of Sn-9Zn-xAg solders continuously increased with increasing Ag content from 0 wt.% to 2 wt.% but then decreased for Sn-9Zn-3Ag. The addition of Ag resulted in the formation of the AgZn₃ phase and in a reduction of the amount of the eutectic Zn phase in the solder matrix; therefore, the corrosion resistance of the Al/Sn-9Zn-xAg/Cu joints was improved.