Sn-Zn-Ga-Pr钎料表面锡须的自发生长

结合扫描电镜与电子能谱分析了稀土元素对无铅钎料显微组织的影响.结果表明,当无铅钎料中的稀土添加过量,会诱发锡须在无铅合金表面的自发生长.在向Sn-9Zn-0.5Ga基体合金中添加0.7%(质量分数)的稀土元素镨(Pr)后,仅需室温时效12 h,合金组织中的稀土相表面即发生了锡须的自发生长.随着时效时间的延长,锡须会继续长大,其最终长度可达100μm.最后对过量稀土元素添加导致锡须生长的力学原因作了初步探讨,分析认为稀土相氧化所产生的微观压应力可能为锡须的生长提供了驱动力.     

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.     

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.     

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.     

Effect of adding 1 wt% Bi into the Sn–2.8Ag–0.5Cu solder alloy on the intermetallic formations with Cu-substrate during soldering and isothermal aging

Intermetallic compound (IMC) formations of Sn–2.8Ag–0.5Cu solder with additional 1 wt% Bi were studied for Cu-substrate during soldering at 255 °C and isothermal aging at 150 °C. It was found that addition of 1 wt% Bi into the Sn–2.8Ag–0.5Cu solder inhibits the excessive formation of intermetallic compounds during the soldering reaction and thereafter in aging condition. Though the intermetallic compound layer was Cu₆Sn₅, after 14 days of aging a thin Cu₃Sn layer was also observed for both solders. A significant increase of intermetallic layer thickness was observed for both solders where the increasing tendency was lower for Bi-containing solder. After various days of aging, Sn–2.8Ag–0.5Cu–1.0Bi solder gives comparatively planar intermetallic layer at the solder–substrate interface than that of the Sn–2.8Ag–0.5Cu solder. The formation of intermetallic compounds during aging for both solders follows the diffusion control mechanism and the diffusion of Cu is more pronounced for Sn–2.8Ag–0.5Cu solder. Intermetallic growth rate constants for Sn–2.8Ag–0.5Cu and Sn–2.8Ag–0.5Cu–1.0Bi solders were calculated as 2.21 × 10⁻¹⁷ and 1.91 × 10⁻¹⁷ m²/s, respectively, which had significant effect on the growth behavior of intermetallic compounds during aging.     

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.     

Tin whiskers studied by synchrotron radiation scanning X-ray micro-diffraction

A large number of Sn whiskers have been found on the Pb-free solder finish on leadframes used in consumer electronic products. Some of the whiskers on eutectic SnCu finishes are long enough to short the neighboring legs of the leadframe. Tin whisker growth is known to be a stress relief phenomenon. We have performed synchrotron radiation X-ray micro-diffraction analysis to measure the local stress level, the orientation of the grains in the finish around a whisker, and the growth direction of whiskers. The compressive stress in the solder finish is quite low, less than 10 MPa; nevertheless, there exists a stress gradient around the root of a whisker. From the orientation map and pole figure, we found that the growth direction of whiskers is [0 0 1] and there exists a preferred orientation of [3 2 1] grains on the solder finish. In one of the whisker analyzed, we found that the normal orientation of the grain just below the whisker is different; it is [2 1 0].     

Suppressing effect of 0.5 wt.% nano-TiO2 addition into Sn-3.5Ag-0.5Cu solder alloy on the intermetallic growth with Cu substrate during isothermal aging

This study investigated the effects of adding 0.5 wt.% nano-TiO₂ particles into Sn3.5Ag0.5Cu (SAC) lead-free solder alloys on the growth of intermetallic compounds (IMC) with Cu substrates during solid-state isothermal aging at temperatures of 100, 125, 150, and 175 °C for up to 7 days. The results indicate that the morphology of the Cu₆Sn₅ phase transformed from scallop-type to layer-type in both SAC solder/Cu joints and Sn3.5Ag0.5Cu-0.5 wt.% TiO₂ (SAC) composite solder/Cu joints. In the SAC solder/Cu joints, a few coarse Ag₃Sn particles were embedded in the Cu₆Sn₅ surface and grew with prolonged aging time. However, in the SAC composite solder/Cu aging, a great number of nano-Ag₃Sn particles were absorbed in the Cu₆Sn₅ surface. The morphology of adsorption of nano-Ag₃Sn particles changed dramatically from adsorption-type to moss-type, and the size of the particles increased.The apparent activation energies for the growth of overall IMC layers were calculated as 42.48 kJ/mol for SAC solder and 60.31 kJ/mol for SAC composite solder. The reduced diffusion coefficient was confirmed for the SAC composite solder/Cu joints.     

Sn-9Zn-xPr钎料钎焊性能及显微组织

研究了稀土元素Pr的添加量对Sn-9Zn无铅钎料的润湿性能、显微组织和焊点力学性能的影响.结果表明,镨的加入不仅改善了钎料的润湿性能和抗氧化性能,而且细化了钎料基体中的富锌相,使得界面组织更为稳定,有利于焊点可靠性的改善;Sn-9Zn无铅钎料中镨的添加量为质量分数0.08%时,钎料的润湿性能最佳,综合性能最好;当镨的添...     

Morphology and growth kinetics of Ag3Sn during soldering reaction between liquid Sn and an Ag substrate

For the soldering of recycled Ag sputtering targets, the interfacial reaction between liquid Sn and an Ag substrate at temperatures ranging from 250 –425°C has been investigated. Experimental results show that a scallop-shaped layer of Ag₃Sn intermetallic compounds formed during the soldering reaction. Kinetics analysis indicated that the growth of such interfacial Ag₃Sn intermetallic compounds is diffusion-controlled with activation energy of 70.3kJ/mol. During the reaction, the Ag substrate dissolves into the molten Sn solder and causes the appearance of needle-shaped Ag₃Sn precipitates in the Sn matrix.     

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.     

Sn-9Zn/Cu无铅焊点ZnO须自发生长

研究了Sn-9Zn/Cu无铅焊点ZnO须自发生长行为.结果表明,在室温条件下Sn-9Zn/Cu无铅焊点因为富锌相的氧化,在富锌相表面自发生长出大量的ZnO须,ZnO须呈现针状、块状、花朵状等不同形态;对ZnO须进行FIB测试,发现在富锌相中出现明显的空洞,主要是因为Zn元素扩散导致的.另外,证实在Zn元素扩散与氧发生反应的过程中,富锌相发生体积收缩,诱使结构中出现明显的拉应力,拉应力为ZnO须生长提供驱动力.     

Interfacial reactions between Sn-2.5Ag-2.0Ni solder and electroless Ni(P) deposited on SiCp/Al composites

A novel Sn-2.5Ag-2.0Ni alloy was used for soldering SiCp/Al composites substrate deposited with electroless Ni(5%P) (mass fraction) and Ni(10%P) (mass fraction) layers. It is observed that variation of P contents in the electroless Ni(P) layer results in different types of microstructures of SnAgNi/Ni(P) solder joint. The morphology of Ni3Sn4 intermetallic compounds (IMCs) formed between the solder and Ni(10%P) layer is observed to be needle-like and this shape provides high speed diffusion channels for Ni to diffuse into solder that culminates in high growth rate of Ni3Sn4. The diffusion of Ni into solder furthermore results in the formation of Kirkendall voids at the interface of Ni(P) layer and SiCp/Al composites substrate. It is observed that solder reliability is degraded by the formation of Ni2SnP, P rich Ni layer and Kirkendall voids. The compact Ni3Sn4 IMC layer in Ni(5%P) solder joint prevents Ni element from diffusing into solder, resulting in a low growth rate of Ni3Sn4 layer. Meanwhile, the formation of Ni2SnP that significantly affects the reliability of solder joints is suppressed by the low P content Ni(5%P) layer. Thus, shear strength of Ni(5%P) solder joint is concluded to be higher than that of Ni(10%P) solder joint. Growth of Ni3Sn4 IMC layer and formation of crack are accounted to be the major sources of the failure of Ni(5%P) solder joint.     

Measurement of deformations in SnAgCu solder interconnects under in situ thermal loading

Optical microscopy was used to discern the different grain orientations and grain boundaries on the polished cross-sections of near-eutectic lead-free board-level SnAgCu (SAC) solder interconnects. Strain distributions with submicron accuracy of the deformations on the cross-sections of the solder interconnects were measured when the package was subjected to thermal loading from room temperature to 100 °C. The results were correlated with the locations of different grains, grain boundaries and larger primary intermetallics. It revealed anisotropic nature of deformations in different grains of the SAC solder, which is similar to the thermomechanical behavior of pure Sn. The strain distribution in a solder interconnect varied significantly in different grain orientations. The primary intermetallics (Ag₃Sn plates) also behaved very differently from the surrounding Sn matrix under the thermal loading. The demonstrated strain localization along the grain boundaries and bigger primary intermetallics provides a clue for the path of fatigue crack growth that leads to a failure because of anisotropic thermomechanical response of SAC solder during thermal cycling.     

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.     

Microstructure evolution in Cu pillar/eutectic SnPb solder system during isothermal annealing

The reaction between Cu pillar and eutectic SnPb solder during isothermal annealing was studied systematically. Intermetallic compounds (IMCs), such as Cu₆Sn₅ and Cu₃Sn, were formed in between Cu and SnThe parabolic rate law was observed on IMC formation, which indicated that the growth of IMCs was controlled by atomic diffusion (a diffusion-limited process). Annealing at 165 °C for 160 h decreased the growth rate of Cu₆Sn₅, and at the same time increased the growth rate of Cu₃Sn. This was when Sn in solder was exhausted completely. The activation energies for the growth of Cu₃Sn and Cu₆Sn₅ were measured to be 1.77 eV and 0.72 eV, respectively. The Kirkendall void that formed at the interface between Cu pillar and solder obeyed the parabolic rate law. The growth rate of the Kirkendall void increased when the Sn in solder was consumed in its entirety.     

Whisker Formation on SAC305 Soldered Assemblies

This article describes the results of a whisker formation study on SAC305 assemblies, evaluating the effects of lead-frame materials and cleanliness in different environments: low-stress simulated power cycling (50–85°C thermal cycling), thermal shock (–55°C to 85°C), and high temperature/high humidity (85°C/85% RH). Cleaned and contaminated small outline transistors, large leaded quad flat packs (QFP), plastic leaded chip carrier packages, and solder balls with and without rare earth elements (REE) were soldered to custom designed test boards with Sn3Ag0.5Cu (SAC305) solder. After assembly, all the boards were cleaned, and half of them were recontaminated (1.56 µg/cm² Cl^?). Whisker length, diameter, and density were measured. Detailed metallurgical analysis on components before assembly and on solder joints before and after testing was performed. It was found that whiskers grow from solder joint fillets, where the thickness is less than 25 µm, unless REE was present. The influence of lead-frame and solder ball material, microstructure, cleanliness, and environment on whisker characteristics is discussed. This article provides detailed metallurgical observations and select whisker length data obtained during this multiyear testing program.     

Microstructural evolution of intermetallic compounds in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn and 1.5In)/Cu solder joints during liquid aging

In this paper, the microstructural evolution of IMCs in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn, 1.5In)/Cu solder joints and their growth mechanisms during liquid aging were investigated by microstructural observations and phase analysis. The results show that two-phase (Ni₃Sn₄ and Cu₆Sn) IMC layers formed in Sn–3.5Ag–0.75Ni/Cu solder joints during their initial liquid aging stage (in the first 8 min). While after a long period of liquid aging, due to the phase transformation of the IMC layer (from Ni₃Sn₄ and Cu₆Sn phases to a (Cu, Ni)₆Sn₅ phase), the rate of growth of the IMC layer in Sn–3.5Ag–0.75Ni/Cu solder joints decreased. The two Cu₆Sn₅ and Cu₅Zn₈ phases formed in Sn–3.5Ag–1.0Zn/Cu solder joints during the initial liquid aging stage and the rate of growth of the IMC layers is close to that of the IMC layer in Sn–3.5Ag/Cu solder joints. However, the phase transformation of the two phases into a Cu–Zn–Sn phase speeded up the growth of the IMC layer. The addition of In to Sn–3.5Ag solder alloy resulted in Cu₆(Sn_x,In_1?x)₅ phase which speeded up the growth of the IMC layer in Sn–3.5Ag–1.5In/Cu solder joint.     

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.     

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.