高温高铅焊料无铅化的研究进展

微电子封装工业中应用于高温领域的高铅焊料的无铅化是一个国际化难题。对目前高温无铅焊料的研究进展进行了综述,包括80Au-20Sn、Bi基合金、Sn-Sb基合金和Zn-Al基合金。从各种焊料的熔化行为、力学性能、导电导热性能、润湿性、界面反应和可靠性等方面,总结了这些高温无铅焊料的特性以及在应用中各自存在的问题。通过比较,认为Sn-Sb基合金在高温领域取代高铅焊料将有很大的应用前景。     

新型Sn-Ag-Bi-Cu-In系无铅钎料合金研究

通过正交试验设计形成Sn-Ag-Bi-Cu-In系无铅钎料合金,并对钎料合金的熔化温度、可焊性、密度及剪切强度等进行研究.研究发现,Sn-Ag-Bi-Cu-In系钎料合金熔化温度接近传统的熔化温度,固-液温度差小;钎料密度约为传统Sn63Pb37的87%;试样铺展面积为72.02mm2,与Sn63Pb37焊锡的铺展面积76.85 mm2非常接近;钎料的剪切强度远大于传统Sn63Pb37钎料的剪切强度,其断裂形貌为沿晶脆断.     

中国无铅钎料专利研究报告

本文涵盖了自1995年至2005年所有涉及到无铅钎料的中国专利。报告的钎料范围是用于表面组装技术，有明确限定成分和成分质量比的Sn基无铅钎料（无铅焊料）。报告的主要内容包括无铅钎料专利的申请者情况及申请和授权情况；在申请专利钎料中Sn-Zn系、Sn-Ag系、Sn-Bi系和Sn-Cu系的数量分布情况以及钎料所含元素情况；国外申请者申请和授权情况；制备方法的情况。最后指出了我国的无铅钎料专利领域存在的问题和发展方向。     

Sn-Zn系无铅焊料抗氧化性和润湿性研究现状

Sn—Zn无铅焊料由于熔点接近Sn—Pb、价格低廉、无毒性、力学性能优良等特点,倍受人们的关注。然而由于Zn的表面活性高,在钎焊过程中焊料容易氧化,导致了润湿性能下降。本文综述合金元素对Sn—Zn无铅焊料氧化性能、润湿性的影响。并对Sn—Zn焊料今后的研究方向进行了简要分析。     

无铅兼容PCB基板的研究进展——无铅兼容PCB基板的性能及其表征

无铅焊料产生的高温高热对PCB基板的制造技术具有很大的冲击力和影响力，本文介绍了无铅焊料及其与Sn63／Pb37的对比特点，总结了无铅兼容PCB基板的性能表征方法。     

新型无铅焊料的研制

由于目前使用的Sn3.5AgCu无铅焊料,温度较高、润湿性较差.在Sn3.5AgCu无铅钎料中添加金属元素Ga、Bi,并改变Ag的含量,对其合金进行熔化温度、润湿性、力学性能和微观组织研究.研究表明,添加Ga、Bi并改变Ag含量有利于降低Sn3.5AgCu合金的熔化温度和改善其润湿性,并提高了力学性能.     

无铅再流焊装置新的使用方法

1、引言 在电子领域,限制使用无铅焊料己成为一种义务,任何Sn—Pb焊料均由无铅焊料所代替。然而,在替代过程中,确立对替代焊料与器件的评价方法,整合支撑制造过程稳定可靠的制造技术,要付出相当大的努力,这其中涉及到很多问题,如工艺条件的改变方法、怎样选定装置与焊料、如何进行组装等。这里,将根据先进的研究成果和各种SMT研究交流所获得的有关无铅焊接的内容作一介绍。     

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。     

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%。     

铜焊盘与锡合金焊点界面物相分析及可靠性探讨

Sn60Pb40焊料与铜焊盘的焊接界面中金属间化合物Cu6Sn5的形成与长大以及在热循环过程中的组织粗化是影响焊点可靠性的重要因素。作者根据SMT工艺的实际情况，使用Au—Sn共晶焊料、Sn60Pb40焊料分别涂覆在铜合金基板表面，并分别在320℃、240℃下保温1min，冷却形成焊点，利用X射线研究分析了两种不同焊盘基材与Sn60Pb40钎料、Au—Sn共晶钎料的钎焊界面的物相。运用经典相变理论、低周疲劳失效的机理以及“柯肯达尔”效应，就优异焊点的形成、物相产生、温度循环后组织粗化与增加Ni阻挡层，对提高焊接接点的温度循环可靠性的作用进行了分析与探讨。     

The effect of solder paste composition on the reliability of SnAgCu joints

As the electronics industry is moving towards lead-free manufacturing processes, more effort has been put into the reliability study of lead-free solder materials. Various tin–silver–copper-based solders have become widely accepted alternatives for tin–lead solders. In this study, we have tested three different SnAgCu solder compositions. The first consisted of a hypoeutectic 96.5Sn/3.0Ag/0.5Cu solder, the second of a eutectic 95.5Sn/3.8Ag/0.7Cu solder, and the third of a hypereutectic 95.5Sn/4.0Ag/0.5Cu solder. A eutectic SnPb solder was used as a reference. The test boards were temperature-cycled (−40 to +125 °C) until all samples failed. The results of the temperature cycling test were analyzed, and cross-section samples were made of the failed joints. Scanning electron and optical microscopy were employed to analyze the fracture behavior and microstructures of the solder joints. The reliability of lead-free solders and the effect of microstructures on joint reliability are discussed.     

Isothermal aging effects on flex cracking of multilayer ceramic capacitors with standard and flexible terminations

Multilayer ceramic capacitors (MLCCs) are known to experience flex cracking when subjected to bending stresses. An experimental study was conducted to determine the susceptibility to flex cracking of flexible- and standard-termination surface mount MLCCs assembled with lead-free or tin–lead solders and aged at two different temperatures for 200 h. Experimental results showed that MLCCs mounted on printed circuit boards with lead-free solder are less susceptible to flex cracking compared with MLCCs mounted on boards with eutectic tin–lead solder. Two factors which make capacitors assembled with lead-free solder less susceptible to flex cracking were discussed: the lower tensile stresses inside the capacitor body which are a result of the differing elastic–plastic mechanical properties of the solder, and the higher residual compressive stresses after solder reflow assembly which are a result of the higher solidification temperature for the Sn3.0Ag0.5Cu lead-free solder. Flexible-termination MLCCs showed much more resistance to flex cracking in comparison to standard-termination MLCCs assembled with both lead-free and tin–lead solders. Aging at elevated temperatures had little effect on flex cracking susceptibility of MLCCs assembled with tin–lead solder. For MLCCs assembled with lead-free solder, aging at 150 °C increased the susceptibility to flex cracking in comparison with un-aged MLCCs.     

电子封装无铅化趋势及瓶颈

欧盟通过法令限制电子用品中铅等有害物质的使用,含铅电子产品不久将退出市场,电子封装的无铅化已成必然趋势。焊料的无铅化是无铅封装的关键,目前无铅焊料的研究集中在Sn基焊料和导电胶粘剂两个方向。文中介绍了三种典型无铅焊料体系的不足之处,以及银导电胶研究中的三个难题。另外,关于无铅焊料还没有一个统一的标准。     

Effects of thermomechanical cycling on lead and lead-free (SnPb and SnAgCu) surface mount solder joints

Accelerated reliability tests have been performed on leadless and leaded lead-free and lead containing SMT component assemblies. Results so far have shown that lead-free reflow soldering is a viable alternative for conventional lead based reflow soldering. The selected ternary eutectic solder alloy SnAg3.8Cu0.7 requires higher processing temperatures which could restrict the use of certain board and component types, but other than that no major modifications seem necessary. Although better SnAg3.8Cu0.7 bulk mechanical properties were obtained compared to the near eutectic lead bearing bulk solder properties, reflowed solder joints did not reflect this difference. In general, quite similar reliability results were obtained as found for the lead based solders. Dependent on board and component metallisations and use environment, the reliability of the lead-free solders could perform better or worse than the lead based solders. Temperature dependent aspects such as solderability and mechanical behaviour of the lead-free assemblies could play a role in this. Although microstructural differences can be seen between the lead-free and lead bearing solder joints, similar joint failure mechanisms occur. Resistor solder joint cracks propagate from underneath the component through either transgranular (lead-free) grains or along intergranular (lead) grain boundaries between lead-rich and tin-rich areas and into coarsened regions near the component terminations. Gullwing lead cracks were seen propagating from the heel fillet along the lead/solder interfacial intermetallic mostly (some cracks started in the heel fillet and propagated through the solder body dispersed with coarsened spherical Ag₃Sn intermetallic particles). Package design and leadframe material seem to play a more important role in the fatigue mechanism than the change in microstructure of the solder joint.     

Metallurgical reactions in composite 90Pb10Sn/lead-free solder joints and their effect on reliability of LTCC/PWB assembly

Use of 90Pb10Sn solder as a noncollapsible sphere material with 95.5Sn 4Ag0.5Cu and SnInAgCu lead-free solders is investigated. Practical reflow conditions led to strong Pb dissolution into liquid solder, resulting in >20 at.% Pb content in the original lead-free solders. The failure mechanism of the test joints is solder cracking due to thermal fatigue, but the characteristic lifetime of 90Pb10Sn/SnInAgCu joints is almost double that of 90Pb10Sn/95.5Sn4Ag0.5Cu in a thermal cycling test (TCT) over the temperature range from −40°C to 125°C. It is predicted that this is mainly a consequence of the better fatigue resistance of the SnPbInAgCu alloy compared with the SnPbAgCu alloy. Indium accelerates the growth of the intermetallic compound (IMC) layer at the low temperature co-fired ceramic (LTCC) metallization/solder interface and causes coarsening of IMC particles during the TCT, but these phenomena do not have a major effect on the creep/fatigue endurance of the test joints.     

Influence of Bonding Temperature and Applied Load on the Bonding Integrity and Optical Performance of Face-Down Bonded Ridge-Waveguide Lasers

The effects of bonding temperature and applied load on the mechanical integrity of 80Au-20Sn solder joints and the optical performance of laser diodes (LDs) are presented. Insufficient solder wetting at 280°C and poor joint integrity at an applied load below 0.196 MPa resulted in solder failure during die shear test. As the bonding temperature and applied load increased, the joint integrity and the optical performance improved. Shear testing further showed fracture in the LD due to the high mechanical strength of 80Au-20Sn solder and good adhesion properties of the solder joint. Microstructure studies showed good metallurgical stability with little interfacial intermetallic compound (IMC) formed. However, beyond an applied load of 0.523 MPa, the LD performances degraded due to modification of the bandgap energy in the active region. From our experimentation, a bonding window with good bonding integrity and high optical performance was, nevertheless, achieved.     

New, creep-resistant, low melting point solders with ultrafine oxide dispersions

Nano-sized, nonreacting, noncoarsening oxide dispersoids have been incorporated into solder alloys to create a new, improved solder structure with an ultrafine grain size of ∼200–500 nm. The new solders exhibit significantly enhanced creep resistance combined with increased strength. The well-known thermal instability problem with ultrafine-grained structure appears to have been overcome in these solder alloys and the microstructure was seen to be quite stable upon high temperature exposure (e.g. 120°C). This is attributed to the presence of very fine dispersoid particles which impede grain boundary sliding and dislocation movement. The dispersions are seen to have a profound effect on the mechanical deformation characteristics of the solders with respect to creep. As much as three orders of magnitude reduction in the steady state creep rate has been achieved. The new solders also exhibit improved ductility under high strain rate deformation and improved strength (4–5 times higher tensile strength) at low strain rates. It is demonstrated that with a dispersion of TiO₂ particles, the Pb-Sn eutectic solder with a melting point of 183°C can be made more creep-resistant than the 80Au-20Sn eutectic solder with a much higher melting point of 278°C. The new creep-resistant solders can be useful for optical and optoelectronic packaging in which dimensional stability of the assembled structure is essential.     

Reliability of high temperature solder alternatives

European RoHS directives, enacted in response to concerns about the toxicity of lead, are driving the substitution of Pb-free solders for Pb-containing solders at the component to board level. While European RoHS regulations currently exempt high Pb solders used as component solders and die attaches for automotive and other high temperature applications, there is a strong drive to find Pb-free alternatives for these high temperature electronic applications, as well. This paper presents constitutive and reliability information on one of the widely used high lead solder materials as a baseline, and discusses potential alternative technologies for high temperature solders with the goal of identifying a cost-effective lead-free solder that can be used at temperatures greater than 200 °C.