Sn晶须形态的研究

添加微量稀土可以有效地改善钎料的综合性能.然而当钎料中添加过量的稀土时,钎料内部会形成体积较大的稀土相.如果将稀土相暴露于空气中,其将发生氧化,氧化产生的压应力将加速稀土相表面Sn晶须的生长.研究了CeSn3与YSn3与ErSr3稀土相表面Sn晶须的生长情况.研究结果表明,稀土相表面出现了Sn晶须的快速生长现象,且试验中发现了一些特殊形态的Sn晶须.     

稀土相ErSn3表面Sn晶须的快速生长

将稀土相ErSn3分别暴露于空气与真空环境中,研究在时效处理过程中ErSn3表面Sn晶须的生长情况。结果表明：大气环境中,在稀土相ErSn3的表面出现了Sn晶须的生长现象,且室温条件下Sn晶须的分布不均,生长速度慢,而高温条件下Sn晶须的分布均匀,生长速度快;真空环境中,在稀土相ErSn3的表面未出现Sn晶须的生长现象。由于在大气环境中稀土相ErSn3发生了氧化,氧原子向ErSn3晶格内部的扩散引起的体积膨胀提供了Sn晶须生长的驱动力,因此,大气环境中在ErSn3的表面会出现Sn晶须的生长现象,而真空环境中则不会出现     

稀土相RE-Sn表面Sn晶须的生长规律

将稀土相CeSn3、LaSn3、(La0.4Ce0.6)Sn3及ErSn3暴露于空气中,研究在时效处理过程中其表面Sn晶须的生长规律。结果表明:室温时效过程中,在稀土相的表面均出现了Sn晶须的生长现象,且稀土相LaSn3的表面倾向于形成包状和扭结状的Sn晶须,稀土相CeSn3和(La0.4Ce0.6)Sn3的表面倾向于形成针状和扭结状的Sn晶须,而稀土相ErSn3的表面倾向于形成大尺寸的杆状和棒状Sn晶须。150℃时效过程中,稀土相CeSn3、LaSn3和(La0.4Ce0.6)Sn3的表面没有出现Sn晶须的生长现象,而稀土相ErSn3的表面出现了大量的小尺寸线状Sn晶须。综上所述,稀土相的氧化倾向决定了其表面Sn晶须的生长规律。     

Sn-3.8Ag-0.7Cu-1.0Er无铅钎料中Sn晶须变截面生长现象

在Sn-3.8Ag-0.7Cu无铅钎料中添加质量分数为1%的稀土Er会在其内部形成尺寸较大的稀土相ErSna.暴露于空气中ErSn3将发生氧化,同时在其表面会出现Sn晶须的快速生长现象.室温时效条件下,在氧化的ErSn3表面会生长出少量的杆状Sn晶须,Sn晶须的截面尺寸会发生连续变化;高温时效条件下,在氧化的ErSn3表面会生长出大量的针状Sn晶须,Sn晶须的截面尺寸会发生阶梯式变化.提出了ErSn3氧化过程中体积应变能是一个变量的模型,可以解释观察到的现象.     

稀土Y加速Sn晶须生长规律

氧原子向稀土相YSn3晶格内部的扩散使YSn3产生体积膨胀,而周围钎料基体对体积膨胀的抑制作用使其内部产生巨大的压应力,此压应力为Sn晶须的生长提供了驱动力;与此同时,稀土相YSn3氧化过程中释放出的自由Sn原子为Sn晶须的生长提供了生长源.对空气中室温与150℃时效条件下稀土相YSn3表面Sn晶须的生长进行了研究.结果表明,室温时效条件下,稀土相YSn3表面Sn晶须的生长速度缓慢且分布不均;高温时效条件下,稀土相YSn3表面Sn晶须的生长速度较快且巨大的压应力使钎料基体发生了隆起现象.     

稀土Ce加速Sn晶须生长的研究

稀土被认为是金属中的"维他命",在钎料中添加微量的稀土Ce可以显著地改善钎料合金的综合性能.然而,当钎料中添加过量的稀土时,将会发现Sn晶须的快速生长现象.结果表明,如果将Sn3.8Ag0.7Cu1.0Ce钎料内部的稀土相暴露于空气中,稀土相将发生氧化而产生体积膨胀,钎料基体对体积膨胀的抑制作用将使稀土相内部产生巨大的压应力从而加速Sn晶须的生长.     

CROSS SECTION CHANGING GROWTH PHENOMENON OF Sn WHISKER IN Sn–3.8Ag–0.7Cu–1.0Er LEAD–FREE SOLDER

在Sn--3.8Ag--0.7Cu无铅钎料中添加质量分数为1%的稀土Er会在其内部形成尺寸较大的稀土相ErSn₃. 暴露于空气中ErSn₃将发生氧化, 同时在其表面会出现Sn晶须的快速生长现象. 室温时效条件下, 在氧化的ErSn₃表面会生长出少量的杆状Sn晶须, Sn晶须的截面尺寸会发生连续变化; 高温时效条件下, 在氧化的ErSn₃表面会生长出大量的针状Sn晶须, Sn晶须的截面尺寸会发生阶梯式变化. 提出了ErSn₃氧化过程中体积应变能是一个变量的模型, 可以解释观察到的现象.     

Sn晶须生长的双应力区模型

利用FIB(Focused Ion Beam)将发生氧化的稀土相ErSn3剖开,研究其表面Sn晶须的生长机制。结果表明:时效过程中稀土相ErSn3发生了不均匀氧化,在其内部形成了大量的"快速氧化通道"及"氧化区"。由于在Sn晶须的根部及附近同时存在两个"氧化区",且它们通过"快速氧化通道"相连。因此,提出了Sn晶须生长的"双压应力区"模型,即Sn晶须的生长需要形成两个压应力区,其根部的"低压应力区"将为Sn晶须的形成提供驱动力,而"高压应力区"将为Sn晶须的生长提供Sn原子。     

Sn基无铅钎料晶须生长行为的研究

研究了有机-无机笼形硅氧烷齐聚物(POSS)对Sn基无铅钎料晶须生长行为的影响。分别采用纯Sn和Sn3.0Ag0.5Cu(SAC305)作为基体,加入3%(质量分数)的POSS硅三醇制备复合钎料。样品在-45~85℃的高低温循环条件下进行晶须生长加速实验,并观察样品表面及界面显微组织的演变。结果表明,POSS可在加速条件下稳定钎料基体,同时通过提高钎料的强度和硬度,来缓解钎料在热循环应力作用下产生的塑性形变,进而有效抑制2种钎料的晶须生长。     

Ag和Zn对Sn58Bi钎料润湿性及焊点组织的影响

采用感应熔炼方法制备钎料,研究了Ag,Zn元素添加对Sn58Bi钎料润湿性与焊点组织的影响,并对时效处理后的焊点界面金属间化合物(Intermetallic compounds,IMCs)的组成及生长规律进行了分析。结果表明,添加的Ag或Zn可与Sn分别生成Ag3Sn,Ag5Zn8,并可显著减少钎料中枝晶含量与细化钎料组织,但不能显著促进Sn58Bi钎料的润湿性。而共同添加的Ag,Zn并不能使得钎料组织发生细化并降低钎料的润湿性。共同添加的Ag和Zn使得焊点界面处形成Cu8Zn5+Ag5Zn8的复合IMCs层,该复合IMCs层可显著的减小IMCs的初始厚度,并降低其生长速度。     

电迁移诱发镀层锡须生长行为分析

分析了0.3×104 A/cm2恒定电流密度和四种不同加载时间（0,48,144和240 h）电迁移条件对6.5 μm厚镀锡层表面锡须生长行为的影响,以及不同电流密度对阴极裂纹宽度的影响.结果表明,电迁移加速了镀层表面锡须的形成与生长,随着电迁移时间的延长,锡须长度不断增加.此外,电迁移导致在阴极首先出现了圆形空洞,随后在两极均形成了圆形空洞,并且在阴极处还发现有微裂纹存在,随着电流密度增加,阴极裂纹宽度也随之增加,电流密度为0.5×104 A/cm2时,平均最大裂纹宽度约为9.2 μm.     

锡晶须生长机理研究的现状与问题

介绍锡晶须的发现过程以及机制研究和预防策略,总结锡晶须生长过程中已经被一些研究人员发现的特点,如晶须形貌的多样性、生长过程的阶段性以及生长位置的不确定性等。回顾从最初发现锡晶须到现在所提出的用于解释锡晶须生长机理的理论模型,其中主要是位错机制、压应力机制、再结晶机制、氧化膜破裂机制以及活性锡原子机制。在对于这些理论模型的问题进行评述后,对如何进一步探索晶须的生长机理提出一些看法。     

外加载荷对镀锡层锡须生长行为的影响

首先研究了三种不同厚度镀锡层（3,5,13 μm）在相同试验条件（70℃时效24 h后室温放置60天）下的锡须生长情况,并在此基础上首次采用精密动态力学分析仪（DMA Q800）研究了精确控制相同载荷条件下拉、压两种外力对相同厚度镀锡层（3 μm）锡须生长行为的影响.结果表明,相同时效条件下,镀锡层越薄,锡须生长的可能性越大;相同的外加载荷和试验温度作用下,承受压力作用镀锡层,其表面锡须生长比承受拉力时生长更快,并且主要呈柱状生长.     

稀土相表面特殊形态锡晶须生长现象

在Sn3.8Ag0.7Cu钎料中添加过量的稀土Ce和Er元素会在其内部形成尺寸较大的稀土相CeSn3和ErSn3.将钎料合金Sn3.8Ag0.7Cu1.0Ce/Er的铺展试样沿中心剖开,利用金相水砂纸及专用抛光液抛光后,将制备好的试样在空气中分别进行室温与150℃时效处理.分析了时效处理过程中稀土相CeSn3及ErSn3表面锡晶须的生长行为.结果表明,在稀土相的表面出现了大量规则的针状及线状锡晶须,它们在生长过程中始终保持了恒定的截面.试验中还发现了一些特殊形态的锡晶须,如锡晶须的分枝、合并以及锡晶须的搭接现象.     

镀层表面锡晶须自发生长现象的研究进展

镀层表面锡晶须自发生长是材料科学中一个受到长期关注的科学现象.随着近年来电子器件无铅化的发展,锡晶须问题日益突出.对于高密度电子封装技术,由晶须自发生长引起的短路和电子故障问题对电子产品的可靠性构成了潜在的威胁.因此,研究锡晶须的生长规律,阐明锡晶须的生长机理,探寻抑制锡晶须生长的技术手段成为当前研究的热点.总结了近年来国内外对锡晶须生长现象的一些相关研究,主要包括锡晶须的生长行为、各种影响锡晶须生长的因素、近年来晶须生长机制方面的新进展、锡晶须生长趋势的评估方法以及工业上抑制晶须生长的一些技术措施等.     

Effect of strongly oxidizing environment on whisker growth form tin coating

The effect of a strongly oxidizing environment (105 °C/100%RH) on tin whisker formation has been studied with Ni and Ag underlayered samples between the tin surface coating and the bronze base material of the electronic components leads. Using nickel or silver underlayer between the copper substrate and the tin coating can be useful for preventing whiskers. The underlayer blocks the formation of Cu₆Sn₅ intermetallics which is one of the root causes of whisker growth. The silver underlayered samples started extreme whiskering after 2200 h; on the Ni underlayered samples only hillocks have been observed. The shape of the whiskers did not resemble to the usually known whisker appearance. The oxidizing environment creates tin-oxide fast and causes thick layers of SnO_x to appear on the surface of the samples and also on the whiskers. This caused the periodic appearance of large amounts of whiskers; but it blocks the length of them. This combined effect results in only large amounts of short whiskers and even causing the thickness of the tin layer to shrink by 80%. The series of tests has also showed that the nickel underlayered samples resisted whiskering better than the silver underlayered samples.     

The effect of different post-electroplating surface modification treatments on tin whisker growth

There are very few studies that have investigated directly the effect of an oxide film on tin whisker growth, since the ‘cracked oxide theory’ was proposed by Tu in 1994. The current study has investigated the effect of both a molybdate conversion coating and a tungstate conversion coating on tin whisker growth from Sn–Cu electrodeposits on Cu, and compared it with that from an electrochemically formed oxide produced from a potassium bicarbonate-potassium carbonate electrolyte. X-ray photoelectron spectroscopy (XPS) has been used to investigate the effect of both immersion time and applied potential on the thickness and composition of the oxide film. The XPS studies show that the oxide film formed using either of the conversion coating baths is significantly thicker than that produced from the potassium bicarbonate-potassium carbonate bath. Initial observations suggest that both the tungstate-based conversion coatings and the molybdate-based conversion coatings significantly reduce whisker growth by over 80% for all conversion coating systems compared with a native air-formed oxide and provide improved mitigation compared with the electrochemically formed oxides previously investigated.     

Effect of direct current and pulse plating parameters on tin whisker growth from tin electrodeposits on copper and brass substrates

Abstract

Electroplated tin finishes are widely utilised in the electronics industry due to their advantageous properties such as excellent solderability, electrical conductivity and corrosion resistance. However, the spontaneous growth of tin whiskers during service can be highly deleterious, resulting in localised electrical shorting or other harmful effects. The formation of tin whiskers, widely accepted as resulting from the formation of compressive stresses within the electrodeposit, has been responsible for a wide range of equipment failures in consumer products, safety critical industrial and aerospace based applications. The numbers of failures associated with tin whiskers is likely to increase in the future following legislation banning the use of lead in electronics, the latter when alloyed with tin, being an acknowledged tin whisker mitigator. Using a bright tin electroplating bath, the effect of process parameters on the characteristic structure of the deposit has been evaluated for deposition onto both brass and copper substrates. The effect on whisker growth rate of process variables, such as current density and deposit thickness, has been evaluated. In addition, the effect of pulse plating on subsequent whisker growth rates has also been investigated, particularly by varying duty cycle and pulse frequency. Whisker growth has been investigated under both ambient conditions and also using elevated temperature and humidity to accelerate the growth of whiskers. Studies have shown that whisker formation is strongly influenced by pulse plating parameters. Furthermore, increasing both current density and thickness of the deposit reduce whisker growth rates. It is also observed that whisker formation is greatly accelerated on brass substrates compared with copper. The basis for this observation is explained.     

Effect of layer properties on stress evolution,intermetallic volume,and density during tin whisker formation

Compressive stress due to intermetallic (IMC) growth appears to be the main driving force for whisker formation, but many of the underlying mechanisms relating the IMC to stress and whisker formation are not understood. To better understand these fundamental processes, we have measured IMC, stress and whisker evolution in Sn layers deposited on Cu. We present systematic results of the effect of changing the Sn layer structure by modifying the grain size, thickness, Pb content, microstructure, and IMC morphology/growth kinetics. We have also made corresponding measurements of the mechanical properties of the Sn with similar changes in the structure and composition without the growth of IMC. We show that modifications that enhance the stress relaxation in the Sn also lead to reduced whisker growth.