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.     

Evolution of Ag3Sn at Sn-3.0Ag-0.3Cu-0.05Cr/Cu joint interfaces during thermal aging

The intermetallic compounds (IMC) in the solder and at the interface of Sn-3.0Ag-0.5Cu (SAC)/Cu and Sn-3.0Ag-0.3Cu-0.05Cr (SACC)/Cu joints were investigated after isothermal aging at 150 °C for 0, 168 and 500 h. Different shaped Ag₃Sn phases were found near the IMC layer of the latter joint. Interestingly, fine rod-shaped and branch-like Ag₃Sn were detected near the interface after soldering and long Ag₃Sn changed into shorter rods and small particles during aging. It is investigated that the Cr addition and thermal aging have effect on the evolution of Ag₃Sn morphologies and it is controlled by interfacial diffusion. Energy minimization theory and the redistribution of elements are used to explain the morphological evolution of Ag₃Sn. Small Ag₃Sn particles were also found on the IMC layer after aging, unlike the large Ag₃Sn at that of SAC/Cu joints. In conclusion, a favorable morphology of the joint interface leads to better bonding properties for SACC/Cu joints against thermal aging than that for SAC/Cu.     

SnAgCu-xPr钎料组织及性能

研究了不同含量Pr元素（质量分数分别为0,0.05%,0.5%）对Sn-3.8Ag-0.7Cu无铅钎料凝固特性、润湿铺展性能以及微观组织的影响.结果表明,SAC,SAC-0.05Pr以及SAC-0.5Pr的凝固所需过冷度分别为20.6,5.0,5.1℃,说明适量Pr元素的加入能够显著降低SnAgCu钎料凝固所需的过冷度;同时,Pr元素的加入细化了钎料组织,降低钎料组织中初晶β-Sn的尺寸,抑制了SnAgCu/Cu焊点内部不同形貌大块化合物Ag3Sn初晶的形成;当Pr元素的添加量为0.05%时,钎料润湿性能最优、组织最佳;0.5%Pr元素的添加会在钎料以及焊点内部形成PrSn3相,对焊点的性能造成不利的影响.     

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.     

Interfacial reactions between high-Pb solders and Ag

Interfacial reactions between high-Pb solders (Pb-10Sn, Pb-5Sn, and Pb-3Sn, in wt.%) and immersion Ag layer at 350 °C are investigated. Upon decreasing the Sn concentration from 10 wt.% to 5 wt.%, the reaction product formed at the solder/Ag interface changes from the Ag₃Sn phase to the Ag₄Sn phase. When the Sn concentration reduces to only 3 wt.%, the reaction product is the Ag₄Sn phase at the initial stage of reaction but transforms to the (Ag) phase dissolved with Sn at the later stage of reaction. Pb penetrates across the (Ag) phase via grain boundary and forms a continuous Pb-rich layer between the (Ag) phase and the bottom Cu layer. The correlation between the phase transformation and the solder composition is discussed based on the calculated Sn-Pb-Ag isothermal section.     

Scaling effect on Ag3Sn growth behaviours in micro-joints for flip chip assemblies

The scaling effect on Ag₃Sn growth behaviours in Sn–3.0Ag–0.5Cu (SAC305) micro-joints of flip chip assemblies was investigated using thermal shock (TS) tests. After assembly reflow, the large plate-like Ag₃Sn compounds only emerged from the Cu interface of small joints, which was strongly related with a higher local Ag concentration in the remaining solder. During TS cycling, the growth of Ag₃Sn grains exhibited comparatively more pronounced growth in the solder matrix of small joints, due to the stronger strain-enhanced coarsening induced by more cycle stress and strain. Coarsening kinetic models based on TS experiments were employed to predict Ag₃Sn growth, the kinetic constants N were determined to clarify the correlation of the joints scaling and Ag₃Sn coarsening in depth.     

Effects of sulfide-forming element additions on the Kirkendall void formation and drop impact reliability of Cu/Sn–3.5Ag solder joints

Ternary Pb-free solders, Sn–3.5Ag–X, containing 0.5 wt.% of Zn, Mn and Cr, were reacted with Cu UBM, which was electroplated using SPS additive. Characteristics of Cu–Sn IMCs and Kirkendall void formation at the Cu/Sn–3.5Ag solder joints were significantly affected by the third element, and the potency to suppress Kirkendall voids at the solder joint increased in the order of Cr, Mn, Zn, which was indeed the order of the drop reliability improvement. From the AES analyses, it was suggested that the sulfide-forming elements in the solder diffused into the Cu UBM and reduced the segregation of S atoms to the Cu/Cu₃Sn interface by scavenging S, which led to the suppression of Kirkendall void nucleation at the Cu/Cu₃Sn interface and the drop reliability improvement. In the case of the Zn-containing solder joint, Cu₃Sn phase, known to be a host of Kirkendall voids, did not form at all even after extended aging treatments. The magnitude of the tensile stress at the Cu₃Sn/Cu interface which drove the Kirkendall void growth was estimated to be 10–100 MPa.     

Controlling Ag<Subscript>3</Subscript>Sn plate formation in near-ternary-eutectic Sn-Ag-Cu solder by minor Zn alloying

As a result of extensive studies, nearternary-eutectic Sn-Ag-Cu (SAC) alloys have been identified as the leading lead-free solder candidates to replace lead-bearing solders for ball-grid array module assembly. However, recent studies revealed several potential reliability risk factors associated with the alloy system. The formation of large Ag₃Sn plates in solder joints, especially when solidified at a relatively slow cooling rate, poses a reliability concern. In this study, the effect of adding a minor amount of zinc in SAC alloy was investigated. The minor zinc addition was shown to reduce the amount of undercooling during solidification and thereby suppress the formation of large Ag₃Sn plates. In addition, the zinc was found to cause changes in both the microstructure and interfacial reaction of the solder joint. The interaction of zinc with other alloying elements in the solder was also investigated for a better understanding of the role of zinc during solidification of the nearternary-eutectic alloys. For more information, contact Sung K. Kang, IBM T.J. Watson Research Center, 1101 Kitchawan Road, Route 134, P.O. Box 218, Yorktown Heights, NY 10598; (914) 945-3932; fax (914) 945-2141; e-mail kang@us.ibm.com.     

铋对SAC305−xBi/Cu焊接接头显微组织、热性能、力学性能和界面行为的影响

通过添加1％ 和2％(质量分数)的Bi提高SAC305焊接接头的性能,并研究Bi掺杂对SAC305?xBi/Cu焊接接头显微组织、热性能和力学性能的影响.Bi掺杂通过细化初始β-Sn和共晶相改善焊接接头的显微组织.当Bi含量低于2％ 时,Bi溶解到β-Sn基体中形成固溶体;而当Bi含量等于或高于2％时,β-Sn基体中形...     

Properties analysis of a new type of solder paste SACBN07

In this work,the wettability,aging and shear properties of a new type of lead-free solder paste Sn-07Ag-05Cu + BiNi (SACBN07) was investigated by conducting a series of comparison experiments with SAC305 and SAC0307 solder paste.The results show that weuability of SACBN07 is almost equal to SAC305,and better than that of SAC0307 solder paste.The thickness of intermetallic compound (IMC) layer in SACBN07/Cu is lower than that of other two types of solder joint after aging.And Cu3Sn layer of SACBN07/Cu is thinner than that of SAC305 and SAC0307.In addition,the SACBN07 solder joints perform the best shear strength among these three types of solder pastes.     

The Nucleation of Sn in Undercooled Melts: The Effect of Metal Impurities

The dependence of the solidification temperature on the concentration x of impurity atoms, M, of Sn-M _x alloys after cooling from the melt was measured separately for M = Co, Ni, Ag, and Cu. For a comparison, similar measurements were performed on SAC305-Ni _x alloys. Large variations in undercooling were observed. It was found that the Ag atoms dissolved in the Sn-Ag melt significantly lowered undercooling, although the presence of Ag₃Sn intermetallic compounds did not. While Cu₆Sn₅ intermetallic compounds in Sn-Cu melts did not significantly lower undercooling, the undercooling of a Sn-Cu melt in contact with a Cu interface was significantly reduced. The addition of Ni to Pb-free solder SAC305 caused a factor of two reduction in the undercooling, similar to that observed after the addition of Ni to high-purity Sn.     

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.     

Ti90及其优化合金的组织与力学性能研究

研究了钎焊与时效过程中,在Sn0.7Ag0.5Cu(SAC0705)钎料与Cu基板和石墨烯Cu基板界面处金属间化合物(IMC)的形成与演变。采用加热平台制备焊接试样并在120℃时效600h。结果表明,界面金属间化合物在时效过程中增厚。SAC0705/Cu和SAC0705/G-Cu 2种焊接界面金属间化合物均为Cu6Sn5。当钎料中添加Ni元素后,Cu6Sn5化合物转变为(Cu,Ni)6Sn5。随着钎料中Ni元素含量的增大,2种基板上的界面金属间化合物厚度先增加后减小。此外,随着Ni含量增大,化合物生长速率降低。石墨烯Cu基板表面的石墨烯层起到扩散阻挡层效果,因此,石墨烯Cu板上的化合物厚度小于常规Cu基板,同时其界面化合物生长速率较低。     

Size effect on IMC growth induced by Cu concentration gradient and pinning of Ag3Sn particles during multiple reflows

Size effect on growth kinetics of interfacial intermetallic compound (IMC), induced by Cu concentration gradient and pinning effect of Ag₃Sn particles during multiple reflows, was investigated in this article. The simulation results, for Cu distributions in solder bulks of different volumes after a single reflow for 60 s at 250 °C, show that Cu concentration gradient in liquid increases with the growing size of solder bump. On the contrary, resistive pressure of nano particles decreases gradually with the increasing bump size. In conclusion, the pinning effect of Ag₃Sn particles on IMC grains plays a dominant role in small samples, whereas the inhibiting effect of Cu concentration gradient is mainly functional in big samples. Combining the two factors, solder bump in an intermediate diameter of 800 μm benefits most and has the largest IMC thickness during multiple reflows.     

Sn-Ag-Cu solders and solder joints: Alloy development, microstructure, and properties

Slow cooling of Sn-Ag-Cu and Sn-Ag-Cu-X (X = Fe, Co) solder-joint specimens made by hand soldering simulated reflow in surface-mount assembly to achieve similar as-solidified joint microstructures for realistic shearstrength testing, using Sn-3.5Ag (wt.%) as a baseline. Minor substitutions of either cobalt or iron for copper in Sn-3.7Ag-0.9Cu refined the joint matrix microstructure, modified the Cu₆Sn₅ intermetallic phase at the copper substrate/solder interface, and increased the shear strength. At elevated (150°C) temperature, no significant difference in shear strength was found in all of the alloys studied. Ambient temperature shear strength was reduced by largescale tin dendrites in the joint microstructure, especially by the coarse dendrites in solute poor Sn-Ag-Cu.     

Reliability studies of Sn–9Zn/Cu solder joints with aging treatment

Sn–9Zn (in wt.%) solder ball was bonded to Cu pad, and the effect of aging on shear reliability was investigated. After reflow, the intermetallic compound (IMC) phase formed at the interface was Cu₅Zn₈, and the as-reflowed Sn–9Zn/Cu joint had sufficient shear strength. In the isothermal aging test, only Cu₅Zn₈ IMC was observed in the samples aged at temperatures between 70 and 120 °C. On the other hand, after aging at 150 °C for 250 h, Cu₆Sn₅ phase was observed at the interface between the interfacial Cu₅Zn₈ IMC layer and the Cu substrate. And, the layer-type Cu₅Zn₈ IMC layer was disrupted locally at the interface. In the ball shear test conducted after aging treatment, the shear strength significantly decreased after aging at all temperatures for initial 100 h, and then remained constant by further prolonged aging. The fracture mainly occurred at the interface between the solder and Cu₅Zn₈ IMC layer. The aged Sn–9Zn/Cu solder joint had an inferior joint reliability.     

Influence of copper addition on adhesive strength of Sn–3Ag–1·5Sb solder joints

Abstract

The present work investigates the effects of adding a small amount of Cu to Sn–3Ag–1·5Sb solders. The present results indicate that adding 0·5 and 1·0 wt-%Cu to Sn–3Ag–1·5Sb solders causes the liquidus temperature to decrease from its original value of 233·4°C to 231·6°C and to 231·4°C, respectively. Furthermore, it is noted that the addition of 1·0 wt-%Cu reduces the difference between the liquidus and solidus temperatures. It is shown that the added Cu reacts with the Sn content of the solder to form Cu₆Sn₅ particles in the β-Sn matrix, which are distributed non-uniformly since the Cu content is low. The experimental results also reveal that the growth rate of the solder joint interfacial intermetallic compound layers increases at higher levels of Cu addition. Finally, it is established that adding Cu to the Sn–3Ag–1·5Sb solder not only improves the adhesive strength of the solder joints, but also reduces the rate of degradation of the adhesive strength of the joints during thermal storage.     

Electrochemical corrosion behaviour of Sn–Ag–Cu (SAC) eutectic alloy in a chloride containing environment

The corrosion behaviour of the Sn_94.5Ag_3.8Cu_1.5 (SAC) eutectic alloy was investigated in 0.1 M NaCl solution by potentiodynamic polarization and impedance spectroscopy measurements and compared with that of the conventional Sn_73.9Pb_23.1 eutectic solder employed for a long time in the packaging of microelectronic components and devices. Scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) were used to characterize the SAC eutectic alloy prior to and after the electrochemical tests. The electrochemical results indicated that the Sn–Ag–Cu eutectic alloy exhibits better corrosion behaviour than the Sn–Pb eutectic solder in NaCl solution. The presence of a corrosion products layer constituted by tin oxy‐chloride was detected at the surface of both alloys investigated after the electrochemical tests. The better corrosion behaviour of SAC eutectic alloy compared to Sn–Pb eutectic solder is ascribed to the formation of a more compact surface film of corrosion products with improved protective properties owing to the presence of copper and silver, as revealed by EPMA.     

Ag<Subscript>3</Subscript>Sn plate formation in the solidification of near-ternary eutectic Sn-Ag-Cu

Near-ternary eutectic Sn-Ag-Cu alloys are leading lead-free candidate solders for various applications. These alloys yield three phases upon solidification: β-Sn,Ag₃Sn, and Cu₆Sn₅. Large, plate-like, pro-eutectic Ag₃Sn structures can grow rapidly within the liquid phase, potentially adversely affecting the mechanical behavior and reducing the fatigue life of solder joints. This article reports on the formation of such plates in Sn-Ag-Cu solder balls and joints and demonstrates how large Ag₃Sn plate formation can be minimized. For more information, contact S.K. Kang, IBM T.J. Watson Research Center, P.O. Box 218, Yorktown Heights, New York 10598; (914) 945-3932; fax (914) 945-2141; e-mail kang@us.ibm.com.     

Sn-3.0Ag-0.5Cu-XCo钎焊接头金属间化合物层电迁移现象的研究

研究了以Co颗粒为增强相的Sn3.0Ag0.5Cu钎料合金接头的电迁移特性。结果表明,50℃、104A/cm2条件下直至16d,Sn3.0Ag0.5Cu-0.2Co钎料接头无明显电迁移现象产生。将温度提高至150℃后,接头正、负极处金属间化合物(IMC)层的厚度产生明显差异,即电子风力引发的‘极化效应’。Sn3.0Ag0.5Cu钎料接头在通电1d和3d后,正、负极处IMC层的结构发生了相反的变化。而Sn3.0Ag0.5Cu-0.05Co接头在通电3d后,负极处产生明显裂纹。此外,Co的引入有效地缓解了IMC层的生长趋势,提高了接头显微组织的稳定性。