Investigation of small Sn–3.5Ag–0.5Cu additions on the microstructure and properties of Sn–8Zn–3Bi solder on Au/Ni/Cu pads

The formation of intermetallic compounds and the shear strength of Sn–Zn–Bi solder alloys with various (0, 1, 3, 5 and 7 wt%) weight percentages of Sn–Ag–Cu were investigated on Au/Ni metallized Cu pads depending on the number of reflow cycles. In Sn–Zn–Bi solder joints, scallop-shaped AuZn₃ intermetallic compound (IMC) particles were found at the interfaces and in the solder ball regions, fine Bi- and needle-shaped Zn-rich phase were observed in the Sn matrix. After Sn–Ag–Cu additions, an additional Ag–Zn intermetallic compound layer was adhered to the top surface of the AuZn₃ layer at the interface and fine spherical-shaped AgZn₃ intermetallic compound particles were detected in the solder ball regions together with Bi- and Zn-rich phase volumes. After the addition of Sn–Ag–Cu, the shear strength of Sn–Zn–Bi solder joints increased due to the formation of the fine AgZn₃ intermetallic compound particles. The shear strengths of Sn–Zn–Bi and Sn–Zn–Bi/7 wt% Sn–Ag–Cu solder joints after one reflow cycle were about 44.5 and 53.1 MPa, respectively and their shear strengths after eight reflow cycles were about 43.4 and 51.6 MPa, respectively.     

电迁移对Ni/Sn3.0Ag0.5Cu/Cu焊点界面反应的影响

研究了温度为150℃,电流密度为5.0×10³A/cm²的条件下电迁移对Ni/Sn3.0Ag0.5Cu/Cu焊点界面反应的影响.回流焊后在Sn3.0Ag0.5Cu/Ni和Sn3.0Ag0.5Cu/Cu的界面上均形成了（Cu,Ni）₆Sn₅型化合物.时效过程中界面化合物随时效时间增加而增厚,时效800 h后两端的化合物并没有发生转变,仍为（Cu,Ni）₆Sn₅型.电流方向对Cu基板的消耗起着决定作用.当电子从基板端流向芯片端时,电流导致基板端Cu焊盘发生局部快速溶解,并导致裂纹在Sn3.0Ag0.5Cu/（Cu,Ni）₆Sn₅界面产生,溶解到钎料中的Cu原子在钎料中沿着电子运动的方向向阳极扩散,并与钎料中的Sn原子发生反应生成大量的Cu₆Sn₅化合物颗粒.当电子从芯片端流向基板端时,芯片端Ni UBM层没有发生明显的溶解,在靠近阳极界面处的钎料中有少量的Cu₆Sn₅化合物颗粒生成,电迁移800 h后焊点仍保持完好.电迁移过程中无论电子的运动方向如何,均促进了阳极界面处（Cu,Ni）₆Sn₅的生长,阳极界面IMC厚度明显大于阴极界面IMC的厚度.与Ni相比,当Cu作为阴极时焊点更容易在电迁移作用下失效.     

EVOLUTION OF MICROSTRUCTURE OF Sn-Ag-Cu LEAD-FREE FLIP CHIP SOLDER JOINTS DURING AGING PROCESS

Flip chip bonding has become a primary technology that has found application in the chip interconnection process in the electronic manufacturing industry in recent years. The solder joints of the flip chip bonding are small and consist of complicated microstructures such as Sn solution, eutectic mixture, and intermetallic compounds （IMCs）, whose mechanical performance is quite different from the original solder bulk. The evolution of microstructure of the flip chip solder joints under thermal aging was analyzed. The results show that with an increase in aging time, coarsening of solder bulk matrix and AuSn4 IMCs occurred within the solder. The IMCs that are formed at the bottom side of the flip chip bond were different from those on the top side during the aging process. （Cu, Ni, Au）0Sn5 were formed at the interfaces of both sides, and large complicated （Au,Ni, Cu）Sn4 IMCs appeared for some time near the bottom interface after aging, but they disappeared again and thus （Cu,Ni, Au ）0Sn5 IMC thickness increased considerably. The influence of reflow times during the flip chip bonding （as-bonded condition） on the characteristics of interfacial IMCs was weakened when subjected to the aging process.     

熔炼工艺和增强相含量对Sn基复合钎料显微组织的影响

分别研究了不同冷却速率和增强相添加量对内生法制备的Cu6Sn5颗粒增强型复合钎料以及Ni颗粒增强复合钎料显微组织的影响,并得出最佳的冷却工艺条件。结果表明:空冷条件(冷却速率为2℃/s)下制备的Cu6Sn5颗粒增强型复合钎料拥有最佳的显微组织形貌特征,其金属间化合物(IMC)尺寸最小,分布最均匀。对于外加法制备的Ni颗粒增强型复合钎料,其内部大尺寸IMC对周边三元共晶组织生长方向产生严重影响。此外,值得注意的是,当Ni质量分数为0.45%时,显微组织中出现了由IMC聚集形成的树叶和雪花形态。当Ni质量分数增加至2.0%时,由于Ni元素在钎料基体中固溶的作用,显微组织中出现了均匀分布的形状和大小不一的黑色斑点。     

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.     

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.     

工艺条件对颗粒增强复合钎料组织性能的影响

选用微米级Cu、Ni颗粒作为增强相外加到Sn-3.5Ag共晶基体钎料中制成颗粒增强Sn-Ag基复合钎料。主要利用电子显微镜研究不同工艺条件下,复合钎料钎焊接头内部增强颗粒周围金属间化合物(IMCs)形貌的演变情况,并分析了增强颗粒形态变化对复合钎料钎焊接头力学性能的影响。结果表明,随着升温速率的降低,Ni增强颗粒周围金属间化合物的形态由向日葵状转变为多边形状;Cu增强颗粒周围金属间化合物的形态始终保持大瓣向日葵状。此外,降温速率对Cu、Ni颗粒周围金属间化合物的形态没有影响。从而分析了不同工艺条件下增强颗粒周围金属间化合物形态的演变规律,以及对复合钎料钎焊接头剪切强度的影响。     

具有纳米结构的增强颗粒对SnBi焊点电迁移的影响

探究了颗粒增强无铅复合钎料的电迁移特性。试验采用具有纳米结构的笼型硅氧烷齐聚物(POSS)颗粒作为增强颗粒,制备SnBi基复合钎料。在25oC,104A/cm2条件下,对钎料一维焊点实施不同时间的通电试验,并对焊点表面形貌和内部显微组织进行观察。结果表明,相对于共晶SnBi焊点,POSS颗粒增强复合钎料焊点的电迁移现象明显受到抑制。通电336h后,复合钎料焊点表面变化很小,界面处聚集的富Sn和富Bi层厚度很小,表明POSS颗粒能够有效抑制通电焊点中的物质扩散。     

Ni元素含量对BiSbSnxNi钎料润湿性能和抗剪强度影响

研制开发高温无铅软钎料一直是钎焊领域一大难题.熔点为270℃左右的Bi5Sb8Sn钎料因润湿性能和抗剪强度达不到要求而受到限制.通过在Bi5Sb8Sn中添加不同含量Ni元素形成新型BiSbSnNi四元合金,来改善Bi5Sb8Sn合金的润湿性能和力学性能.结果表明,尽管Ni元素的添加使BiSbSnxNi钎料合金铺展面积均较基体钎料差.但Ni元素的最佳添加量为2%时,可以改善钎料中金属间化合物的生成,能够增大钎料的铺展面积.当Ni元素含量为3%时,钎料合金的抗剪强度最高.在Ni元素含量为4%时,IMC厚度明显增加,且出现条状的富铋相,对钎料焊接接头的抗剪强度产生不利影响.     

Improving the shear strength of Sn–Ag–Cu–Ni/Cu–Zn solder joints via modifying the microstructure and phase stability of Cu–Sn intermetallic compounds

This study focuses on the correlation between high-speed impact tests and the interfacial reaction in Sn-3.0Ag-0.5Cu-0.1Ni/Cu (wt%) and Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints. Adding Ni into the Sn–Ag–Cu solder alters the interfacial morphology from scallop type to layer type and exhibits high shear strength after reflow in both solder joints. However, the shear strength of Sn-3.0Ag-0.5Cu-0.1Ni/Cu solder joints degrades significantly after thermal aging at 150 °C for 500 h. It is notable that Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints still present higher shear strength after aging at 150 °C. The weakened shear strength in Sn-3.0Ag-0.5Cu-0.1Ni/Cu solder joints is due to stress accumulation in the interfacial (Cu,Ni)₆Sn₅ compound induced by the phase transformation from a high-temperature hexagonal structure (η-Cu₆Sn₅) to a low-temperature monoclinic structure (η'-Cu₆Sn₅). However, doping small amounts of Zn into (Cu,Ni)₆(Sn,Zn)₅ can inhibit the phase transformation during thermal aging and maintain strong shear strength. These experiments demonstrate that Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints can act as a stable connection in the micro-electronic packaging of most electronic products at their average working temperatures.     

结构变化对Cu/Sn-58Bi/Cu微焊点电迁移行为和组织演变的影响

利用SEM观察、聚焦离子束(FIB)微区分析和有限元模拟对比研究了直角型和线型Cu/Sn-58Bi/Cu微焊点在高电流密度下(1.5×10~4A/cm~2)的电迁移行为,从原子扩散距离和微区域电阻变化及阴阳极物相变化的角度研究了焊点结构变化对电迁移影响的机理.结果表明,2种焊点通电112和224 h后均发生了Bi向阳极迁移并聚集及Sn在阴极富集的现象;直角型焊点阳极由于Bi聚集后膨胀而产生压应力进而导致小丘状凸起和微裂纹出现,而阴极存在拉应力引发凹陷和微裂纹,且沿界面呈非均匀变化.微区组织分析表明,电迁移作用下焊点内部Bi原子的扩散速度大于Sn原子的扩散速度.观察分析和模拟结果还表明,具有结构不均匀性的直角型焊点中电子流易向电阻较小区域聚集而产生电流拥挤效应,这是引起直角型焊点电迁移现象严重的根本原因.     

升温速率对复合钎料显微组织和力学性能的影响

不同的钎焊工艺条件会对复合钎料中增强相颗粒（如Ni,Ag,Cu等金属颗粒）周围金属间化合物的形貌和尺寸产生影响,而增强相颗粒周围金属间化合物的尺寸又会对复合钎料的力学性能产生影响。在共晶Sn-3．5Ag钎料中外加微米级铜颗粒制成复合钎料,研究了不同的升温速率对复合钎料内部颗粒显微组织和力学性能的影响。结果表明,复合钎料中铜增强颗粒周围存在着厚度不均的金属间化合物层,不同的升温速率对这层金属间化合物的形貌基本没有影响,只会对其厚度尺寸有影响。此外,建立了不同升温速率与铜颗粒增强的Sn-Ag基复合钎料增强颗粒周围金属间化合物尺寸和力学性能的关系。     

Effect of bismuth on the growth kinetics of intermetallic compounds in Sn-3.5Ag solder joints: A growth kinetic model

The effect on the growth kinetics of the intermetallic compounds (IMCs) in solder/Cu joints, caused by adding Bi to eutectic Sn-3.5Ag solder alloy, was examined at the aging temperatures of 150°C and 180°C. The Cu₆Sn₅ layer growth was significantly enhanced, but the Cu₃Sn layer growth was slightly retarded by the addition of Bi, resulting in significant growth enhancement of the total (Cu₆Sn₅+Cu₃Sn) IMC layer with increasing Bi addition. The IMC layer growth in the Bi-containing solder joints was accompanied by the accumulation of Bi ahead of the Cu₆Sn₅ layer that resulted in the formation of a liquid layer at the Cu₆Sn₅/solder interface. A kinetic model was developed for the planar growth of the Cu₆Sn₅ and Cu₃Sn layers in the solder joints, accounting for the existence of interfacial reaction barriers. Predictions from the kinetic model showed that the experimental results could be well explained by the hypothesis that the formation of a Bi-rich liquid layer at the Cu₆Sn₅/solder interface reduces the interfacial reaction barrier at the interface.     

Effect of Zn addition in Sn-rich alloys on interfacial reaction with Au foils

To restrain the formation of AuSnx intermetallic components （IMCs） in solder joints, Zn was added into Sn-rich solders. The solder joints were fabricated by a laser reflow soldering method, and then they were aged at 125 ℃. The results show that the total thickness of AuSnx IMCs at the interface of pure Sn solder and Au foils reaches about 54 μm under the condition of 600 h aging. In Sn-1.5Zn solder joints, however, formation of AuSn4 IMCs is restrained greatly. As the content of Zn in the solder is increased to 3.5%（mass fraction）, no AuSn4 IMC is observed at the interface. Au-Zn phases form beside AuSn2 and AuSn IMCs layers. As for Sn-9.0Zn solder joints, Au-Zn and Au-Zn-Sn phases and few AuSnx IMCs form at the interface. Moreover, total thickness of the phases and IMCs is far less than that ofAuSnx IMCs in the pure Sn solder joints.     

Investigations of interfacial reactions of Sn–Zn based and Sn–Ag–Cu lead-free solder alloys as replacement for Sn–Pb solder

The interfacial reactions of Sn–Zn based solders and a Sn–Ag–Cu solder have been compared with a eutectic Sn–Pb solder. During reflow soldering different types of intermetallic compounds (IMCs) are found at the interface. The morphologies of these IMCs are quite different for different solder compositions. As-reflowed, the growth rates of IMCs in the Sn–Zn based solder are higher than in the Sn–Ag–Cu and Sn–Pb solders. Different types of IMCs such as γ-Cu₅Zn₈, β-CuZn and a thin unknown Cu–Zn layer are formed in the Sn–Zn based solder but in the cases of Cu/Sn–Pb and Cu/Sn–Ag–Cu solder systems Cu₆Sn₅ IMC layers are formed at the interface. Cu₆Sn₅ and Cu₃Sn interfacial IMCs are formed in the early stages of 10 min reflow due to the limited supply of Sn from the Sn–Pb solder. The spalling of Cu–Sn IMCs is observed only in the Sn–Ag–Cu solder. The size of Zn platelets is increased with an increase of reflow time for the Cu/Sn–Zn solder system. In the case of the Sn–Zn–Bi solder, there is no significant increase in the Zn-rich phases with extended reflow time. Also, Bi offers significant effects on the wetting, the growth rate of IMCs as well as on the size and distribution of Zn-rich phases in the β-Sn matrix. No Cu–Sn IMCs are found in the Sn–Zn based solder during 20 min reflow. The consumption of Cu by the solders are ranked as Sn–Zn–Bi > Sn–Ag–Cu > Sn–Zn > Sn–Pb. Despite the higher Cu-consumption rate, Bi-containing solder may be a promising candidate for a lead-free solder in modern electronic packaging taking into account its lower soldering temperature and material costs.     

Effects of in situ nickel particle addition on the microstructure and microhardness of Sn–Ag solder

Abstract

In this study, various amounts of Ni particles were added in situ to Sn–3·5 wt-%Ag lead free solder to form new composite solders. Copper substrates were then dipped into these solders and aged at 150°C for 0, 25, 225, or 1000 h. The microstructure and microhardness of the as solidified solder and the aged solder/copper couples were investigated. Experimental results revealed that the addition of Ni particles increased the microhardness of the composite solder. Ni additions of less than 3 wt-% yielded a microstructure of β-Sn grains surrounded by a eutectic mixture of Ag₃Sn and a Sn rich matrix. An intermetallic compound of Ni₃Sn₄ particles was dispersed throughout the eutectic. For 5 wt-%Ni addition, the Ni₃Sn₄ phase and the remaining Ni particles were agglomerated. In the case of copper substrate dipped with a thick layer of composite solder, water quenched and then aged at 150°C, the induced (Ni, Cu)₃Sn₄ particles coarsened and agglomerated. Additionally, the intermetallic (Cu, Ni)₆Sn₅ compound layer formed at the solder/Cu interface thickened with increasing Ni content.     

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.     

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.     

Evolution of AuSnx intermetallic compounds in laser reflowed micro-solder joints

To investigate the effect of Au thickness on evolution of AuSnx IMCs,pads with 0.1,0.5 and 4.0 μm thickness of Au surface finish were utilized.Laser reflowed solder joints were aged in 125℃ isothermal ovens.Results indicated that little IMC formed at the interface of solder and pad with 0.1 μm thickness of Au.Even in condition of 744 hours aging,thickness of IMCs did not increase obviously.As for the joints with 0.5 μm thickness of Au,most of AuSn4 IMCs stayed at the interface and were in needle-like or dendritic morphology.With the increase of aging time,AuSn4 IMCs became flat and changed to a continuous layer.In the joints with 4.0 μm thickness of Au on pads,AuSn,AuSn2,AuSn4 IMCs and Au2Sn phase formed at the interface.As aging time was increased,more Sn rich IMCs formed at the interface,and evolved to AuSn4 IMCs in condition of long time aging.Thickness of AuSn4 IMCs reached about 30 μm.     

Dissolution and interfacial reactions of thin-film Ti/Ni/Ag metallizations in solder joints

The dissolution and interfacial reactions involving thin-film Ti/Ni/Ag metallizations on two semiconductor devices, diode and metal-oxide-semiconductor field-effect transistor (MOSFET), a Sn–3.0Ag–0.7Cu solder, and a Au-layer on the substrates are studied. To simulate the dissolution kinetics of the Ag-layer in liquid solder during the reflow process, the computational thermodynamics (Thermo-Calc) and kinetics (DICTRA: DIffusion Controlled TRAnsformations) tools are employed in conjunction with the assessed thermochemical and mobility data. The simulated results are found to be consistent with the observed as-reflowed microstructures and the measured Ag contents in the solder. In the as-reflowed joints two different intermetallic compounds (IMC) are found near the diode/solder interface. Both are in the form of particles of different morphologies, not a continuous layer, and are referred to as IMC-I and IMC-II. The former corresponds to Ni₃Sn₄ with Cu atoms residing in the Ni sublattice. It is uncertain whether IMC-II is Cu₆Sn₅ phase with Ni atoms residing in the Cu sublattice or a Cu–Ni–Sn ternary phase. Near the as-reflowed MOSFET/solder interface, both particles and a skeleton-like layer of Ni₃Sn₄ are observed. The primary microstructural dynamics during solid state aging are the coarsening of IMC particles and the reactions involving the unconsumed (after reflow) Ni- and the Ti-layer with Sn and Au. While the reaction with the Ni-layer yields only Ni₃Sn₄ intermetallic, the reaction involving the Ti-layer suggests the formation of Ti–Sn and Au–Sn–Ti intermetallics. The latter is due to the diffusion of Au from the substrate side to the die side. It is postulated that the kinetics of Au–Sn–Ti layer is primarily governed by the diffusion of Au through the Ni₃Sn₄ layer by a grain boundary mechanism.