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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Tin whisker mitigation by means of a post-electroplating electrochemical oxidation treatment

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 [K.-N. Tu: Phys. Rev., 1994, 49, (3), 2030–2034]. The current study has investigated the effect of an electrochemically produced oxide on tin whisker growth, for both Sn–Cu electrodeposits on Cu and pure Sn electrodeposits on brass. X-ray photoelectron spectroscopy (XPS) has been used to investigate the effect of the applied electrochemical oxidation potential on the oxide film thickness. Focused ion beam has been used to prepare cross sections from electrodeposited samples to investigate the influence of the electrochemically formed oxide film on deposit microstructure during long-term room temperature storage. The XPS studies show that the thickness of electrochemically formed oxide film is directly influenced by the applied potential and the total charge passed. Whisker growth studies show that the electrochemical oxidation treatment mitigates whisker growth for both Sn–Cu electrodeposits on Cu and pure Sn electrodeposits on brass. For Sn electrodeposits on brass, the electrochemically formed oxide greatly reduces both the formation of zinc oxide at the surface and the formation of intermetallic compounds, which results in the mitigation of tin whisker growth. For Sn–Cu electrodeposits on Cu, the electrochemically formed oxide has no apparent effect on intermetallic compound formation and acts simply as a physical barrier to hinder tin whisker growth.