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.     

Sn晶须的形态机制

将稀土相CeSn3与ErSn3暴露于空气中,研究在时效处理过程中稀土相表面Sn晶须的形态机制.结果表明:时效过程中在稀土相表面出现的绝大多数Sn晶须均是具有恒定截面的规则Sn晶须;同时也发现少数特殊形态的不规则Sn晶须,如卷曲状的Sn晶须、变截面的Sn晶须、分枝及搭接的Sn晶须等;由于稀土相的氧化所产生的体积膨胀提供Sn晶须生长的驱动力,而稀土相的氧化极不均匀,因此,认为Sn晶须在生长过程中其根部受力状态的改变是导致特殊形态Sn晶须出现的根本原因.     

SnAgCuCe/Er无铅钎料表面锡晶须的形态及特性

在Sn-3.8Ag-0.7Cu无铅钎料中添加1%(质量分数)的稀土铈或铒会在其内部形成尺寸较大的稀土相CeSn3和ErSn3.暴露于空气中的CeSn<,3和ErSn3将发生氧化,同时在其表面会出现锡晶须的快速生长现象.文中研究了稀土相CeSn3与ErSn3表面锡晶须的生长行为.结果表明,在CeSn3与ErSn3表面形成了大量的传统圆柱状锡晶须,同时,在其表面还出现了一些特殊形态的锡晶须,如带纹状的锡晶须、扭曲状的锡晶须、变截面的锡晶须、锡晶须的分枝、合并及搭接现象等.     

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     

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.     

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。     

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.     

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.     

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.     

Mechanisms for Sn whisker growth in rare earth-containing Pb-free solders

It has recently been documented that Pb-free solder alloys doped with trace amounts of rare earth (RE) elements show a very strong propensity to grow Sn whiskers. In this work, we have investigated the effect of the addition of 2 wt.% Ce, La or Y on the whiskering behavior of Sn–3.9Ag–0.7Cu. Hillock-type whiskers around particle peripheries were observed in water-quenched alloys with smaller RESn₃ particles, while furnace-cooled alloys with larger RESn₃ particles formed needle-like whiskers from within the particle. Phase separation between Sn and RE oxides occurred during oxidation of the RESn₃ intermetallics. A focused ion beam serial sectioning approach was used to visualize the Sn whiskers and the oxide structure. We show that the driving force for whisker growth is related to the compressive stresses that develop in these particles during the oxidation of the RE intermetallic phases.     

The Inhibition of Tin Whiskers on the Surface of Sn-8Zn-3Bi-0.5Ce Solders

Through the refinement of the (Ce, Zn)Sn₃ intermetallic phase, the formation of tin whiskers, previously observed on the surface of a Sn-3Ag-0.5Cu-0.5Ce solder, was prevented in a Sn-9Zn-0.5Ce alloy. However, whisker growth can still occur on the surface of Sn-8Zn-3Bi-0.5Ce solder after air storage at room temperature and at 150 °C due to the formation of large (Ce, Zn)Sn₃ intermetallic clusters. Further experiments showed that decreasing the Bi-content in this Sn-8Zn-0.5Ce alloy to 1 and 2 wt.% can recover the beneficial effects of Zn additions on the refinement of the (Ce, Zn)Sn₃ phase and obviously reduce the appearance of tin whiskers. In addition, alloying the Sn-8Zn-3Bi-0.5Ce solder with 0.5 wt.% Ge, which increases the oxidation resistance of the (Ce, Zn)Sn₃ intermetallic clusters, can also effectively inhibit tin whisker growth.     

Sn whisker growth during thermal cycling

Pure Sn plating on ceramic chip capacitors was tested by thermal cycling both in air and in vacuum for up to 3000 cycles and the whisker growth mechanism was clarified. A thin crystalline SnO layer is formed on the surface of Sn plating and whiskers, which exhibits a high level of cracking. Thermal cycling whiskers exhibit two distinct features: fine striation rings on the whisker side face vertical to the whisker growth axis; and deep grooves at the root of the whiskers. One ring of the fine striations corresponds to each thermal cycle. The formation of the grooves can be attributed to thermal cycle cracking along grain boundaries of Sn followed by oxidation and growth of whiskers from the root grains. The characteristic winding feature observed for thermal cycling whiskers can be attributed to the formation of root grooves with severe oxidation. Whisker growth in vacuum is faster than in air. Whiskers grown in vacuum are thinner and longer than whiskers grown in air, while the whisker density is not influenced by atmosphere. The interval of striation rings is wider for vacuum-grown whiskers as compared with air-grown whiskers.     

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.     

Correlation Between Surface Morphology Evolution and Grain Structure: Whisker/Hillock Formation in Sn-Cu

Sn whisker and hillock formation is a reliability risk that has become increasingly important as the electronics industry has moved toward Pb-free manufacturing. To prevent them, we would like to understand what makes specific sites susceptible to deform into whiskers. We have used in situ scanning electron microscopy (SEM)/electron backscattering diffraction (EBSD) to monitor simultaneously the evolution of surface morphology and grain orientation in Sn surfaces in order to correlate whisker/hillock initiation with the underlying microstructure. Because rough films are difficult to measure with EBSD, we developed a unique procedure to make Sn-Cu samples with ultra-flat surfaces so that a large fraction of Sn grains can be indexed over repeated scans. We find that whiskers/hillocks grow from existing grains (not re-nucleated grains) with orientations close to (001). They often rotate from the as-deposited structure so that the orientation after growth does not indicate the orientation from which the whisker initiated. We measured the interface structure after removal of the Sn layer by chemical etching and found that there is no excessive accumulation of intermetallic compound around the whisker/hillock roots. Cross-sectional measurements revealed that a large fraction of the whiskers/hillocks have oblique boundaries underneath the surface, supporting the idea that these allow whiskers/hillocks to grow with lower stress.     

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.