氧化对含稀土无铅钎料表面锡须生长的影响

通过环境试验(室温、湿热和"无氧"试验)和扫描电镜组织分析对比研究了相同时效时间(30天)、三种不同氧化条件下锡须在Sn-Zn-Ga-Pr无铅钎料表面的生长行为.发现在室温环境下,锡须呈典型的针状生长;在湿热条件下,锡须呈丘状生长;而在氮气氛围的近似无氧条件下仅发现有少量锡粒在稀土相PrSn3表面产生.基于稀土相氧化驱动锡须生长理论,分析认为三种环境条件下锡须生长行为的不同是由于稀土相氧化程度不同造成的.湿热条件下稀土相快速氧化和腐蚀,从而比在室温和"无氧"条件下产生更多的压应力和活性Sn原子,为丘状锡须的生长提供了条件;而在氮气氛围下,稀土相氧化非常缓慢,驱动力和锡源都较少,因而只有少量短锡须和锡粒生长.     

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.     

Pr元素对Sn-Zn-Ga钎料锡须生长的影响

研究了锡须生长与稀土含量之间的关联性,对影响锡须生长的相关因素进行了初步分析,着重研究时效时间与冷却速率对锡须生长的影响规律,并对块状钎料合金表面锡须形成的生长机制进行了初步探讨.结果表明,当Sn-Zn-Ga-xPr钎料中镨的添加量达到0.7%(质量分数)时,钎料表面在室温时效12 h后会生长出锡须.随着时效时间的延长,Sn-Zn-Ga-0.7Pr钎料锡须长度增长,且在时效时间45 d左右达到电子元器件失效的临界值.此外研究发现不同冷却速率对锡须的生长有很大差异,对Sn-Zn-Ga-xPr钎料锡须生长机制进行了初步的理论分析.     

锡镀层表面晶须问题的研究现状与进展

随着电子封装无铅化的趋势,选择无铅锡基镀层已成为必然.但是,纯锡及锡基合金镀层具有自发生长锡晶须的倾向,因此研究并阐明锡晶须的生长机理,并采取有效的预防措施,成为目前人们关注的焦点.回顾了锡晶须研究的历史和现状,综述了关于锡晶须的形貌特征、影响锡晶须生长的各种因素及目前对锡晶须生长机理的认识等问题,介绍并分析了几种工业界预防锡晶须生长的主要措施,包括合金化、去应力退火、电镀隔离层、热风整平或热熔.讨论并提出了一些需要研究的课题.     

通过添加POSS颗粒抑制锡基无Pb焊层的晶须生长

在Sn,Sn-3.0Ag-0.5Cu和Sn42-Bi58钎料中添加具有纳米结构的笼形硅氧烷齐聚物(POSS)作为增强相,研究了增强相在恒温恒湿(85℃,相对湿度85%)条件下对锡基无Pb焊层晶须生长行为的影响.结果表明,在恒温恒湿条件下,锡基无Pb焊层晶须生长的驱动力是Sn的氧化物生成引起体积膨胀从而对周围焊层产生的压应力;添加POSS可以有效缓解金属Sn的氧化进程,抑制Sn的氧化物生成,从而减缓晶须生长;在Sn,Sn3.0Ag0.5Cu和Sn58Bi焊层中,Sn焊层晶须生长能力最强,Sn58Bi焊层晶须生长能力最弱.     

SnAgCu／Cu界面热循环及时效条件下化合物的生长行为

通过对等温时效与温度循环两种条件下钎料与基板间金属间化合物（IMC）生长的对比．研究了界面IMC生长的规律。采用了两条低温极限不同保温时间和循环周期相同的循环曲线,等温时效温度采用循环高温峰值温度。结果表明,随着循环周期的增加,界面IMC层的厚度增加,且低温极限温度越低时IMC生长越快。与时效条件下界面IMC生长的对比表明,在高温阶段保温时间相同时,时效条件下界面IMC的生长速率快于循环条件。     

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.     

酸性氯化物型化学镀锡的增厚工艺研究

对酸性氯化物型化学镀锡的增厚工艺进行了研究.讨论了镀液中Sn2＋浓度、NaH2PO2浓度、（NH2）2CS含量及络合剂B等组分对化学镀沉积速度的影响,并提出了最佳的工艺条件;同时,利用扫描电镜（SEM）和电子能谱（EDS）对镀层表面形貌和镀层成分进行了分析.结果表明：在一定工艺条件下可获得厚度为7.5μm左右的银白色无光化学镀锡层,镀层表面晶粒大小均匀细致,镀层含锡量为95.6%质量分数.     

SAC305/Cu微焊点界面金属间化合物生长速率

界面金属间化合物(IMC)的生长速率是影响钎焊接头可靠性的重要因素. 文中研究了焊点尺寸、时效温度及镍镀层对SAC305/Cu微焊点界面IMC生长速率的影响. 结果表明,焊球尺寸为200,300,400和500 μm,时效温度为100,130,160 ℃条件下,界面IMC层厚度生长速率随时效时间平方根数值的升高而增长. 焊点尺寸由小变大,界面IMC层厚度更薄,IMC的生长速率也更小. 随着时效温度的升高,界面IMC生长速率增大. 镍镀层对界面IMC的生长速率有明显的抑制作用,即降低IMC生长速率,使其增厚变缓.     

双向脉冲法电沉积低应力晶须抑制型锡镀层

以甲基磺酸锡为镀锡液的主盐,采用Stoney镀层应力测试方法,以及锡晶须生长趋势评价标准(JEDEC标准JESD22Al21.01),研究了双向脉冲电沉积参数对纯锡镀层拉应力大小及其晶须生长特性影响的规律。利用扫描电子显微镜(SEM)表征了锡镀层晶须生长前后的微观形貌,优选出了锡镀层应力低、锡晶须生长趋势小的双向脉冲电沉积参数(平均电流密度为10 A/dm~2,占空比为0.7,逆向脉冲系数为0.5,频率为10 Hz)。结果表明,通过调控双向脉冲参数,可控制纯锡镀层内应力的大小,进而制备出可抑制锡晶须生长的纯锡镀层。     

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。     

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.     

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     

Microstructure and growth mechanism of tin whiskers on RESn3 compounds

An exclusive method was developed to prepare intact tin whiskers as transmission electron microscope specimens, and with this technique in situ observation of tin whisker growth from RESn₃ (RE = Nd, La, Ce) film specimen was first achieved. Electron irradiation was discovered to have an effect on the growth of a tin whisker through its root. Large quantities of tin whiskers with diameters from 20 nm to 10 μm and lengths ranging from 50 nm to 500 μm were formed at a growth rate of 0.1–1.8 nm s^?1 on the surface of RESn₃ compounds. Most (>85%) of these tin whiskers have preferred growth directions of 〈1 0 0〉, 〈0 0 1〉, 〈1 0 1〉 and 〈1 0 3〉, as determined by statistics. This kind of tin whisker is single-crystal β-Sn even if it has growth striations, steps and kinks, and no dislocations or twin or grain boundaries were observed within the whisker body. RESn₃ compounds undergo selective oxidation during whisker growth, and the oxidation provides continuous tin atoms for tin whisker growth until they are exhausted. The driving force for whisker growth is the compressive stress resulting from the restriction of the massive volume expansion (38–43%) during the oxidation by the surface RE(OH)₃ layer. Tin atoms diffuse and flow to feed the continuous growth of tin whiskers under a compressive stress gradient formed from the extrusion of tin atoms/clusters at weak points on the surface RE(OH)₃ layers. A growth model was proposed to discuss the characteristics and growth mechanism of tin whiskers from RESn₃ compounds.     

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.     

热扩散对镀锡银钎料界面组织及熔化特性的影响

对带锡镀覆层的银钎料进行热扩散处理,采用差示扫描量热仪(DSC)、扫描电镜(SEM)、X射线衍射仪(XRD)研究热扩散工艺对其熔化温度和扩散界面组织、物相的影响. 结果表明,在扩散时间一定条件下,随着扩散温度升高,扩散界面层厚度增加;随着扩散温度升高或扩散时间延长,钎料的固、液相线温度均降低,熔化温度区间缩小;扩散界面层物相主要由棒状Ag₃Sn相和块状Cu₃Sn相组成;最佳热扩散工艺为220 ℃,24 h. 经最佳工艺处理后,扩散界面层厚度为9.1 μm,钎料中Sn含量为7.2%,此时钎料熔化温度区间为642.34 ℃~676.37 ℃. 与传统熔炼合金化方法相比,钎料中Sn含量提高近31%.     

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。