稀土铈在Sn-Zn无铅钎料表面的高温氧化行为

通过俄歇电子能谱法和X射线光电子能谱法研究了Sn-9Zn-0.15Ce和Sn-9Zn-0.002Al-0.2Ga-0.25Ag-0.15Ce两种钎料表面Ce元素的分布和存在形式.结果表明,铈在Sn-9Zn-0.15Ce钎料表面0~40 nm范围内的富集区浓度达到30%(原子分数)左右,是基体内部的250倍,主要以CeO2和Ce2O3形态存在.在Sn-9Zn-0.15Ce钎料中复合添加镓和铝后,Ga元素在钎料表面0~6 nm范围内富集,Al元素在表面2~20 nm范围内富集并主要以氧化态形式存在.Ce元素富集在距离钎料表面2~60 nm的范围内,处于Ga,Al元素富集层的下方;由Ga,Al元素富集层构成的致密保护膜可显著降低表面铈被氧化的概率.     

复合添加Ga,Al,Ag对Sn-9Zn钎料性能的影响

采用润湿平衡法研究了合金元素Ga,Al,Ag复合添加对Sn-9Zn钎料润湿性的影响.结果表明,Ga,Al,Ag的最佳添加量分别为0.2,0.002,0.25(质量分数,%);添加合金元素后钎料的高温抗氧化性能显著提高.俄歇电子能谱分析表明,Sn-9Zn-0.2Ga-0.002Al-0.25Ag钎料表面Al高度富集并形成一层致密的氧化膜,可阻挡氧向液态钎料内部扩散,减少钎料的氧化.Sn-9Zn-0.2Ga-0.002Al-0.25Ag钎料与Cu/Ni/Au基板之间的金属间化合物由一层平坦的AuZn3和颗粒状的AuAgZn2化合物组成.另外,微焊点力学试验表明,采用Sn-9Zn-0.2Ga-0.002Al-0.25Ag钎料时,电子元器件与基板间微焊点的力学性能比Sn-9Zn钎料略有提高.     

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.     

Electrochemical corrosion behaviour of Pb-free Sn-8.5Zn-0.05Al-XGa and Sn-3Ag-0.5Cu alloys in chloride containing aqueous solution

The electrochemical corrosion behaviour of Pb-free Sn-8.5Zn-0.05Al-XGa and Sn-3Ag-0.5Cu alloys was investigated in 3.5% NaCl solution by using potentiodynamic polarization techniques. The results obtained from polarization studies revealed that there was a negative shift in the corrosion potential with increase in Ga content from 0.02 to 0.2 wt% in the Sn-8.5Zn-0.05Al-XGa alloy. These changes were also reflected in the corrosion current density (I_corr) value, corrosion rate and linear polarization resistance (LPR) of the four element alloy. However, for Sn-3Ag-0.5Cu alloy a significant increase in the corrosion rate and corrosion current density was observed as compared to the four element alloys. SIMS depth profile results established that ZnO present on the outer surface of Sn-8.5Zn-0.05Al-0.05Ga alloy played a major role in the formation of the oxide film. Oxides of Sn, Al and Ga contributed a little towards the formation of film on the outer surface of the alloy. On the other hand, Ag₂O was primarily responsible for the formation of the oxide film on the outer surface of Sn-3Ag-0.5Cu alloy.     

Ag,Al,Ga对Sn-9Zn无铅钎料润湿性能的影响

采用润湿平衡法测试了Sn-9Zn-X(X为Ag,Al,Ga)无铅钎料分别配合ZnCl2-NH4Cl钎剂和免清洗助焊剂,在空气和氮气保护的两种条件下的润湿性能,分析研究了合金元素Ag,Al,Ga的添加量对Sn-9Zn-X无铅钎料润湿性的影响规律.结果表明,合金元素Ag,Al,Ga在Sn-9Zn中的最佳添加量(质量分数)分别为0.3%,0.005%～0.02%,0.5%.采用氮气保护可以显著改善Sn-9Zn-X无铅钎料的润湿性,而Sn-9Zn-X无铅钎料配合ZnCl2-NH4Cl钎剂时具有较好的润湿性,甚至优于Sn-3.5Ag-0.5Cu在相同条件下的润湿性.这一研究结果表明,通过研发适合于Sn-Zn系无铅钎料的高性能助焊剂,从而改善Sn-Zn系钎料的润湿性能是完全可行的.     

微量稀土元素铈对Sn-Ag-Cu无铅钎料物理性能和焊点抗拉强度的影响

研究了微量稀土元素铈对Sn-3．5Ag-0．5Cu无铅钎料的物理性能、润湿性能、焊点抗拉强度和显微组织的影响。结果表明，添加微量的铈后，钎料的导电性能提高，密度下降；铈含量（质量分数）在0．03％和0．05％时可以改善钎料的润湿性；特别是0．03％质量分数时晶粒组织最为细小均匀，焊点抗拉强度也最高；当铈含量（质量分数）大于0．1％时对钎料的性能产生不利影响，润湿时间升高，焊点抗拉强度大幅降低，因此稀土元素铈的最佳含量（质量分数）应为0．03％。     

Solderability and intermetallic compounds formation of Sn-9Zn-xAg lead-free solders wetted on Cu substrate

The eutectic Sn-9Zn alloy was doped with Ag (0 wt.%-1 wt.%) to form Sn-9Zn-xAg lead-free solder alloys. The effect of the addition of Ag on the microstructure and solderability of this alloy was investigated and intermetallic compounds (IMCs) formed at the solder/Cu interface were also examined in this study. The results show that, due to the addition of Ag, the microstructure of the solder changes. When the quantity of Ag is lower than 0.3 wt.%, the needle-like Zn-rich phase decreases gradually. However, when the quantity of Ag is 0.5 wt.%-1 wt.%, Ag-Zn intermetallic compounds appear in the solder. In particular, adding 0.3 wt.% Ag improves the wetting behavior due to the better oxidation resistance of the Sn-9Zn solder. The addition of an excessive amount of Ag will deteriorate the wetting property because the glutinosity and fluidity of Sn-9Zn-(0.5, 1)Ag solder decrease. The results also indicate that the addition of Ag to the Sn-Zn solder leads to the precipitation of ε-AgZn₃ from the liquid solder on preformed interfacial intermetallics (Cu₅Zn₈). The peripheral AgZn₃, nodular on the Cu₅Zn₈ IMCs layer, is likely to be generated by a peritectic reaction L + γ-Ag₅Zn₈ → ɛ-AgZn₃ and the following crystallization of AgZn₃.     

Effects of Al, Ga, and Ag on the anti-oxidation and wetting reactions of Sn-9Zn-X solders

The effects of Ca, Al, and Ag on the anti-oxidation of Sn-9Zn-X solders and the interface reactions between the solders and Cu substrate were investigated by Auger electron spectroscopy (AES) and scanning electron microscope (SEM) analysis, respectively. The mechanism of improving the wettability of Sn-g Zn lead-flee solder by adding Ca, Al, and Ag was also revealed. The AES analysis indicated that Al and Ca might enrich on the molten solder surface which resulted in improving the anti-oxidation of Sn-gZn-O. O05Al and Sn-gZn-O. 3C, a alloys. The addition of Ca reduced the apparent activation energy and promoted the interface reaction. With the addition of 0.3 wt. % Ag, some scallop-like intermetallic compounds (IMCs) formed at the interface, according to the energy dispersive spectroscopy (EDS) analysis, these scallop-like IMCs might be the mixture of Ag-Zn and Cu-Sn compounds.     

Interfacial Reactions and Bonding Strength of Sn-xAg-0.5Cu/Ni BGA Solder Joints

The present study details the microstructure evolution of the interfacial intermetallic compounds (IMCs) layer formed between the Sn-xAg-0.5Cu (x = 1, 3, and 4 wt.%) solder balls and electroless Ni-P layer, and their bond strength variation during aging. The interfacial IMCs layer in the as-reflowed specimens was only (Cu,Ni)₆Sn₅ for Sn-xAg-0.5Cu solders. The (Ni,Cu)₃Sn₄ IMCs layer formed when Sn-4Ag-0.5Cu and Sn-3Ag-0.5Cu solders were used as aging time increased. However, only (Cu,Ni)₆Sn₅ IMCs formed in Sn-1Ag-0.5Cu solders, when the aging time was extended beyond 1500 h. Two factors are expected to influence bond strength and fracture modes. One of the factors is that the interfacial (Ni,Cu)₃Sn₄ IMCs formed at the interface and the fact that fracture occurs along the interface. The other factor is Ag₃Sn IMCs coarsening in the solder matrix, and fracture reveals the ductility of the solder balls. The above analysis indicates that during aging, the formation of interfacial (Ni,Cu)₃Sn₄ IMCs layers strongly influences the pull strength and the fracture behavior of a solder joint. This fact demonstrates that interfacial layers are key to understanding the changes in bonding strength. Additionally, comparison of the bond strength with various Sn-Ag-Cu lead-free solders for various Ag contents show that the Sn-1Ag-0.5Cu solder joint is not sensitive to extended aging time.     

In对Al-Mg-Ga-Sn-(In)铝合金阳极组织及电化学性能的影响

在Al基体中添加Mg、Ga、Sn、In合金元素,通过正交试验设计了9组铝-空气电池阳极材料。采用动电位极化试验、析氢试验和恒电流放电试验对铝合金阳极的电化学性能进行优化,通过扫描电镜和能谱测试仪观察了合金的显微组织及成分。结果表明,没有添加In元素的1号合金(Al-0.5Mg-0.05Sn-0.05Ga)、5号合金(Al-Mg-0.1Sn-0.2Ga)和9号合金(Al-2Mg-0.2Sn-0.1Ga)铝阳极具有较差的放电性能和较高的自腐蚀速率,而添加0.05wt% In元素的7号铝阳极(Al-2Mg-0.05Sn-0.2Ga-0.05In)具有最好的放电电压(平均电位-1.968 V)和抗腐蚀性能 (自腐蚀速率0.193 mL·cm^-2·min^-1)。对比去腐蚀产物后的合金表面形貌,发现5号合金的腐蚀表面布满较深的腐蚀坑,这增加了铝合金的自腐蚀,而7号合金的表面具有较浅的腐蚀坑,这减缓了电解液中离子传递和自腐蚀速率。 因此,7号铝合金适合用作铝-空气电池阳极材料。     

Effect of Nd and La on surface tension and wettability of Sn-8Zn-3Bi solders

Maximum bubble pressure measurement was employed to evaluate surface tension of Sn-8Zn-3Bi- （0-0.15）Nd and Sn-8Zn-3Bi-（0 -0. 15）La solder melts. Wetting balance method was used to measure wetting force and wetting time on Cu substrate of the two group solders. The experimental results show that minute amount of Nd or La addition to Sn-8Zn-3Bi solder causes significant decrease of the surface tension of the solder melts at 200 - 240 ℃ and Nd addition is more effective on reduction of surface tension than that of La. Nd or La addition has the effect on enhancing the wetting force of the solder melts on Cu substrate, which results from the de- crease of interracial tension between the solder melt and Cu substrate. The wetting force reaches the maximum when 0.1% Nd is added to the base alloy. The contact angle between Sn-8Zn-3Bi base solders and Cu substrate decreases with the addition of Nd or La and the minimum of the contact angle is obtained from the solder with 0.1% Nd addition.     

稀土Pr对低银Sn-0.3Ag-0.7Cu-0.5Ga钎料蠕变行为影响的研究

为进一步促进电子封装用低银无铅钎料的发展,本文采用纳米压痕法研究了新型含Pr低银Sn-0.3Ag-0.7Cu-0.5Ga (SAC-Ga)钎料显微组织与蠕变性能之间的关系。结果表明,SAC-Ga、SAC-Ga-0.06Pr、SAC-Ga-0.5Pr三种钎料的蠕变位移分别为1717 nm、1144 nm、1472 nm;稀土Pr可通过细化Cu₆Sn₅金属间化合物并促使其均匀分布从而明显提高SAC-Ga钎料的蠕变强度;与SAC-Ga-0.06Pr钎料相比,SAC-Ga-0.5Pr由于过量稀土Pr的表面氧化而导致其蠕变强度有所下降。此外,本文采用Dorn模型研究了含Pr的SAC-Ga钎料的室温蠕变行为并计算了对应的钎料蠕变应力指数n;阐明了Pr对SAC-Ga钎料蠕变强度的强化机理,即当位错遇到细小且均匀分布的Cu₆Sn₅ 金属间化合物时,位错移动只能采用绕过机制,从而提高了含Pr低银钎料的抗蠕变性能。     

Effect of rare earth metal Ce addition to Sn-Ag solder on interfacial reactions with Cu substrate

The effect of adding a small amount of rare earth cerium (Ce) element to low Ag containing Sn-1wt%Ag Pb-free solder on its interfacial reactions with Cu substrate was investigated. The growth of intermetallic compounds (IMCs) between three Sn-1Ag-xCe solders with different Ce contents and a Cu substrate was studied and the results were compared to those obtained for the Ce-free Sn-1Ag/Cu systems. In the solid-state reactions of the Sn-1Ag(-xCe)/Cu solder joints, the two IMC layers, Cu₆Sn₅ and Cu₃Sn, grew as aging time increased. Compared to the Sn-1Ag/Cu joint, the growth of the Cu₆Sn₅ and Cu₃Sn layers was depressed for the Ce-containing Sn-1Ag-xCe/Cu joint. The addition of Ce to the Sn-Ag solder reduced the growth of the interfacial Cu-Sn IMCs and prevented the IMCs from spalling from the interface. The evenly-distributed Ce elements in the solder region blocked the diffusion of Sn atoms to the interface and retarded the growth of the interfacial IMC layer.     

The effect of alloying element gallium on the polarization characteristics of Pb-free Sn-Zn-Ag-Al-XGa solders in NaCl solution

The polarization characteristics of Sn-8.5Zn-0.5Ag-0.1Al-XGa lead-free solders were investigated in 3.5% NaCl solution where X ranges from 0.05-1.5 wt%. The results show that Ga affects the anodic polarization behaviour of the solders. Passivation behaviour is observed for all the investigated Sn-8.5Zn-0.5Ag-0.1Al-XGa solders. Increase in the Ga content from 0.05 to 0.25 wt% increases the ability for passivation but the oxide film formed due to passivity is not so protective. However Ga content > 0.25 wt% enhances corrosion and decreases the protective power of the passive film. The magnitude of the passivation current densities depend on the composition of the solders and the potentials applied. Layers of oxides of tin and zinc are responsible for the passivation behaviour. XRD and SEM results revealed the formation of corrosion products like SnO, ZnO, SnO₂ at different potentials during the polarization study.     

EFFECT OF LASER INPUT ENERGY ON AuSnx INTERMETALLIC COMPOUNDS FORMATION IN SOLDER JOINTS WITH DIFFERENT THICKNESS OF Au SURFACE FINISH ON PADS

Formation of AuSnx intermetallic compounds （IMCs） in laser reflowed solder joints was investigated. The results showed that few IMCs formed at the solder/0. 1μm Au interface. Needlelike AuSn4 IMCs were observed at the solder/0.5μm Au interface. In Sn-2.0Ag-O,75Cu-3,0Bi and Sn-3.5Ag-O.75Cu solder joints, when the laser input energy was increased, AuSn4 IMCs changed .from a layer to needlelike or dendritic distribution at the solder/0.9μm Au interface. As for the solder joints with 4.0 μm thickness of Au surface finish on pads, AuSn4 , AuSnx, AuSn IMCs, and Au2Sn phases formed at the interface. Moreover, the content of AuSnx IMCs, such as, AuSn4 and AuSn2, which contained high Sn concentration, would become larger as the laser input energy increased. In the Sn-37Pb solder joints with 0.9 μm or 4.0 μm thickness of the Au surface finish on pads, AuSn4 IMCs were in netlike distribution. The interspaces between them were filled with Pb-rich phases.     

Wetting and interfacial reaction characteristics of Sn-1.2Ag-0.5Cu-xIn quaternary solder alloys

Through the use of a wetting balance technique, the wetting characteristics of Sn-1.2Ag-0.5Cu-xIn quaternary solder alloys with respect to the In content and soldering temperature were investigated to validate the applicability of compositions with a low Ag content as solder material. It was found that a small addition (0.4–0.6 wt.%) of In significantly improved the wetting properties of the Sn-1.2Ag-0.5Cu-xIn composition at soldering temperatures ranging from 230 °C to 240 °C due to the excellent wetting property of In. In an observation of the interfacial reaction, it was found that the added In element did not participate in the interfacial reaction with a Cu or Ni pad, unlike in the Sn-Ag-Cu-In case, which has a high In content. The package or boardside IMC layers in Sn-1.2Ag-0.5Cu-0.4In joints were thinner than those of Sn-3.0Ag-0.5Cu, especially after aging.     

Wetting Characteristics of Novel-type 63Sn-29.2Pb-6Zn-1Ag-0.38Cu-0.42Bi Solder Alloy

6061 aluminum alloy has many advantages, and soldering is the most attractive joining method for 6061 aluminum alloy. In order to expand application of 6061 aluminum alloy, a novel 63Sn-29.2Pb-6Zn-1Ag-0.38Cu-0.42Bi solder alloy was prepared. The melting characteristic and microstructure of the solder were analyzed by differential scanning calorimetry and scanning electron microscope. Its spreading on the 6061 aluminum alloy was also studied. The results show that its melting temperature range is 456.34-463.68 K, and the temperature interval between the solidus and the liquidus is 6.34 K. The solder on 6061 aluminum alloy had better wetting characteristics. A precursor film appears ahead of the spreading droplet. The microstructure at the interface between the solder and the 6061 aluminum alloy was analyzed. It was clear that the intermetallic compound, Ag₂Al phase, was formed at the interface between the solder and the 6061 aluminum alloy.     

Sn-0.3Ag-0.7Cu-xSb无铅钎料润湿性

研究了微量Sb元素对Sn-0.3Ag-0.7Cu无铅钎料润湿性的影响,采用润湿平衡法探讨了Sn-0.3Ag-0.7Cu-xSb钎料在不同氛围和不同钎剂条件下的润湿性能.结果表明,微量的Sb元素可以显著提高Sn-0.3Ag-0.7Cu无铅钎料润湿性.在氮气氛围条件下,Sn-0.3Ag-0.7Cu-xSb钎料的润湿性得到显著改善,主要基于氮气氛围减小熔融钎料的氧化.辅助不同的钎剂,钎料的润湿性差异较大,选择合适的钎剂可以明显提高Sn-0.3Ag-0.7Cu-xSb钎料的润湿性.     

Effect of cerium on microstructure and mechanical properties of Sn-Ag-Cu system lead-free solder alloys

The melting point, spreading property, mechanical properties and microstructures of Sn-3.0Ag-2.8Cu solder alloys added with micro-variable-Ce were studied by means of optical microscopy, scanning electron microscopy（SEM） and energy dispersive X-ray（EDX）. The results indicate that the melting point of Sn-3.0Ag-2.8Cu solder is enhanced by Ce addition; a small amount of Ce will remarkably prolong the creep-rupture life of Sn-3.0Ag-2.8Cu solder joint at room temperature, especially when the content of Ce is 0.1%, the creep-rupture life will be 9 times or more than that of the solder joint without Ce addition; the elongation of Sn-3.0Ag-2.SCu solder is also obviously improved even up to 15.7%. In sum, the optimum content of Ce is within 0.05%-0.1%.     

Sn-Zn-Bi-(P,Nd)无铅钎料的微观组织及性能

研究了复合加入P,Nd元素的Sn-8Zn-3Bi钎料的微观组织、力学性能、抗氧化性及润湿性.结果表明,单独加入元素P会导致Sn-8Zn-3Bi钎料组织中出现初生Zn相,而同时加入元素P和Nd不仅能够抑制初生Zn相的形成,钎料组织也能够得到细化,因此钎料的塑性提高,断后伸长率达到48%.P,Nd元素的复合添加能够在钎料表面形成稳定的扩散阻挡层,抑制P元素在长时间加热条件下的烧损,进一步降低表面的氧化速度.由于钎料的抗氧化性提高,Sn-8Zn-3Bi-0.1P-0.05Nd钎料呈现出更好的润湿性.