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℃。     

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.     

电子元件、组件

TN60 2004030494铜锢钊硫对Sn一Ag基无铅焊料性能的影响/林培豪,刘心宇,成钧(桂林电子工业学院)11电子元件与材料‘一2 003,22(10).一33-34研究了Cu、In、Bi、S元素对Sn一Ag基无铅焊料熔点和铺展性的影响.结果表明:Sn一A片Cu三元合金成分为9 5.5%Sn3.5%Agl%Cu时具有较低熔点(215℃)和好的铺展性;加入适量的In可降低Sn一Ag合金的熔点和改善铺展性能;随二(B劝的增加Sn-Ag一Bi三元合金熔点降低、铺展性变好;Sn一Ag合金熔点随、(S)的增加而升高,加入少量S能改善Sn一Ag合金的铺展性.图8参5(刚)影响,发现随着硫酸浓度增加,温度对隧道…     

Sn-Sb-Cu(Bi)系无铅钎料的研究

本文研究了Sn-Sb-Cu(Bi)系无铅钎料的润湿性、显微组织以及熔化特性,对Sb、Cu、Bi等元素在Sn基钎料中的作用进行了阐述,发现了几种有应用潜力的合金,有望取代现有广泛使用的SnAg(Cu)系钎料.     

纳米颗粒增强无铅复合焊料的研究现状

熔化温度、润湿性及长期使用过程中的可靠性决定了无铅焊料的应用范围.通过添加适量纳米颗粒可显著提高无铅焊料的性能,特别是添加适量纳米Ag颗粒后SnCu焊料蠕变断裂寿命是未添加时的13倍.介绍了添加纳米颗粒对无铅焊料的物理化学性能的影响;探讨了纳米颗粒增强无铅复合焊料微观结构和力学性能;展望了纳米颗粒增强手段对焊料应用的前...     

纳米Sn-Ag钎料合金熔化温度及形成焓的研究

考虑表面效应,基于Lindemann熔化准则,利用Miedema模型对Sn-Ag纳米钎料合金的熔化温度及形成焓进行计算.Sn-Ag纳米合金微粒的熔化温度及形成焓均依赖于尺寸和组元成分;对于Sn3.5 Ag纳米钎料合金,当微粒尺寸大小为5nm时,其熔化温度下降约为7％;而合金形成焓随晶粒粒径的减小而增加,合金稳定性降低;对于Sn3.5Ag钎料合金,当粒径尺寸为0.1μm时,合金形成焓完全为正值,对Sn-Ag钎料合金组织形成存在产生很大影响.     

微量元素对焊料特性的影响

在Sn-20Bi焊料中添加微量Ag、In、Ga和Sb,观察焊料的熔化特性和显微组织的变化.结果表明当Ag的质量分数为0.7%、In为0.1%、Ga为0.5%时焊料的熔点都分别有所降低,Bi的偏析明显减小;Sb不宜作为单独的第三组元加入,但与Ag、In、Ga一起加入时Sb能起到很好的固溶强化且有抑制Sn的相变的作用.通过最佳配比制成的Sn-Bi-X焊料,其熔点与Sn-37Pb接近,而且已不存在Bi的偏析,接近于实用.     

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。     

Sn—Ag—Cu无铅焊料性能研究

环保和微电子器件高度集成化的发展驱动了高性能无铅焊料的研究和开发,Sn—Ag－Cu系无铅焊料由于具有良好的焊接性能和使用性能,已逐渐成为一种通用电子无铅焊料。文章通过实验的方法,研究了8种不同配比的Sn—Ag—Cu焊料中银、铜含量对合金性能（包括熔点、润湿性和剪切强度）的影响,并对焊料的显微组织进行对比与分析,得出低银焊料的可靠性比高银焊料好,同时Sn－2．9Ag—1．2Cu的合金具有较低的熔点且铺展性好,为确定综合性能最佳的该系焊料合金提供了依据。     

P对Sn-Cu无铅钎料性能的影响

添加了P到Sn-Cu系无铅钎料中,测定了钎料的熔化温度、抗氧化性能和接头蠕变疲劳寿命。结果表明:在Sn0.7Cu中添加微量的P,提高了无铅钎料的抗氧化性能,对熔化温度基本无影响。Sn0.7Cu0.005P无铅钎料合金熔化温度的峰值为226.7℃,在恒定应力为2MPa的蠕变疲劳试验中,钎料接头蠕变疲劳寿命为337.357min。     

La对Sn-Ag-Cu无铅钎料组织与性能的影响

研究了微量稀土La对Sn-3.0Ag-0.5Cu无铅钎料显微组织、力学性能、断口形貌、润湿性能和熔点的影响.结果表明:La的质量分数为0.1%可使钎料合金晶粒细化,并显著提高钎料合金力学性能和润湿性能;添加La的质量分数为0.4%将形成粗大LaSn3初生枝晶相,降低力学性能和润湿性能;微量La使钎料合金的熔点轻微增加.     

42Sn58Bi—96.5Sn3.5Ag系焊点疲劳性能的研究

本文研究了热处理时间对不同组分的４２Ｓｎ５８Ｂｉ－９６．５Ｓｎ３．５Ａｇ焊料疲劳性能的影响,研究发现适当的热处理时间能提高焊点的机械强度,延长焊点的疲劳寿命。     

Lead-free Sn-Ag and Sn-Ag-Bi solder powders prepared by mechanical alloying

A mechanical alloying (MA) process was used to produce lead-free solder pastes of Sn-3.5Ag and the Sn-3.5Ag-4Bi system. Because of the high energy induced by repeated fracturing and welding, the grinding media played an important role during the MA process. A ceramic container was used to provide stronger impact force, which could induce phase transformation better than a Teflon container. In addition, it was found that 1-cm balls could fracture Bi particles and promote their dissolution into the Sn matrix. On the contrary, the milling process tended to achieve homogeneous mixing when using 3-mm balls. The MA powders, after milling with 3-mm balls, showed a small endothermic peak from the differential scanning calorimetry (DSC) profile at around 138°C, which was the eutectic temperature of Sn-Bi. The melting points of the MA powders in the ceramic container were measured to be 221°C and 203°C, respectively, for Sn-3.5Ag and Sn-3.5Ag-4Bi from the DSC curves. The reduced melting point ensured the complete melting during reflow with a peak temperature of 240°C. The formation of Ag₃Sn was also observed from the x-ray diffraction peaks, indicating successful alloying by MA. The solder pastes could, thus, be produced by adding flux into the MA powders. The wetting property of the solder joint was also evaluated. The as-prepared solder pastes on electroless Ni-P/Cu/Si showed good metallurgical bonding with a contact angle less than 20°.     

铜铟铋硫对Sn-Ag基无铅焊料性能的影响

研究了Cu、In、Bi、S元素对Sn-Ag基无铅焊料熔点和铺展性的影响。结果表明:Sn-Ag-Cu三元合金成分为95.5%Sn3.5%Ag1%Cu时具有较低熔点(215℃)和好的铺展性;加入适量的In可降低Sn-Ag合金的熔点和改善铺展性能;随w(Bi)的增加Sn-Ag-Bi三元合金的熔点降低、铺展性变好;Sn-Ag合金的熔点随w(S)的增加而升高,加入少量S能改善Sn-Ag合金的铺展性。     

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。     

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.     

Early Interfacial Reaction and Formation of Intermetallic Compounds in the Sn-3.5Ag/Cu Soldering System

The early interfacial reaction in the Sn-3.5Ag/Cu soldering system and the system’s premelting behavior were found and characterized by differential scanning calorimetry incorporated into the reflow process. The results show that the early interfacial reaction occurs by way of melting and wetting of the solder layer adjacent to the Cu substrate at a temperature nearly 4°C below the actual melting point of Sn-3.5Ag solder due to solid-state diffusion of Cu atoms into the Sn-3.5Ag binary solder. Consequently, the early interfacial reaction brings about formation of Cu-Sn intermetallic compounds (IMCs) at a temperature below the melting point of Sn-3.5Ag, and a prolonged early interfacial reaction can lead to change of the Cu-Sn IMC morphology from planar-like to scallop-like and promote excessive growth of IMCs at the interface.     

Comparative study of microstructures and properties of three valuable SnAgCuRE lead-free solder alloys

Lead-free solders with excellent material properties and low cost are essential for the electronics industry. It has been proved that mechanical properties of SnAgCu alloys can be remarkably improved with a minute addition of rare earth (RE) elements. For comparison and optimization, three valuable solder candidates, Sn3.8Ag0.7Cu0.05RE, Sn3Ag0.5Cu0.05RE, and Sn2.9Ag1.2Cu0.05RE, were chosen due to the excellent properties of their own SnAgCu basic alloys. Wetting properties, melting temperature, bulk tensile properties, and joint tensile and shear properties were investigated. In addition, the microstructures of solder joints were observed and the effects of microstructure on mechanical properties were analyzed. Experimental results indicated that the tensile and shear strengths of solder joints were decreased from Sn3.8Ag0.7Cu0.05RE, Sn2.9Ag1.2Cu0.05RE, to Sn3Ag0.5Cu0.05RE, in order. Such difference in mechanical properties could be attributed to the influence of slightly coarse or strong Cu₆Sn₅ scallops in the reaction layer as well as superior eutectic network and large volume percentage of large primary intermetallic compounds (IMCs) inside the solder joints. It is also suggested that the size and volume percentage of large primary IMCs inside the solder be controlled. In addition, serration morphology was observed at the edge of large primary and eutectic IMCs in the three solder joints, which could be related to the content of Ag, Cu, and RE. The serration morphology was proved to be beneficial to mechanical properties theoretically. Furthermore, the three alloys investigated possessed similar wetting properties, melting temperatures, and bulk tensile properties.     

Wetting characteristics of Pb-free solder alloys and PWB finishes

For a successful transition to Pb-free manufacturing in electronics assembly, it is critical to understand the behavior of Pb-free solders (in bulk and paste form) and their interaction with the Pb-free printed wiring board (PWB) finishes. This paper presents the results obtained from solder paste spread tests and wetting balance experiments with several Pb-free solder alloys and Pb-free PWB finishes. The solder alloys studied were Sn3.4Ag4.8Bi, Sn4.0Ag0.5Cu, Sn3.5Ag and Sn0.7Cu. Eutectic Sn37Pb was used as a reference. The PWB surface finishes were Sn, NiAu, Ag and OSP. Wetting balance experiments were conducted in air while the spread tests were performed in air and nitrogen to understand the effect of reflow atmosphere on the spreading. Surface analysis techniques such as Nomarski phase contrast microscopy, Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to characterize the as-received PWB finishes. Sequential electrochemical reduction analysis (SERA) was also performed on the as-received PWB test coupons and on the Sn test coupons after multiple reflow cycles. The effect of multiple reflow cycles on the wetting performance, spreading and the surface composition of the PWB finishes was studied.