Sn基无铅钎料与Cu基板间化合物Cu_6Sn_5的研究进展

主要介绍了Sn基无铅钎料和Cu基板在界面处反应生成的金属间化合物Cu6Sn5与焊接点可靠性的关系。综述了近年来Cu6Sn5的研究进展,内容包括:Sn基无铅钎料在Cu基板上形成的Cu6Sn5的生长形态、晶体取向、生长动力学以及纳米颗粒对界面Cu6Sn5尺寸及形貌的影响。     

Interfacial reaction between the electroless nickel immersion gold substrate and Sn-based solders

The electroless nickel immersion gold (ENIG) surface finish is widely used in electronic packaging. The ENIG induced Au embrittlement has been investigated in SnPb/ENIG/Cu solder joint since several years ago. However, in Sn-based lead-free solder joint, discrepancies still exist about the influence of Au finish on the reliability of the solder joint. This study investigated the effects of ENIG surface finish on the interfacial reaction and thus the mechanical property of Sn-based solder joints. Experimentally, two types of ENIG with different thickness of Au layer were fabricated. The results indicated that the Au layer dissolved into the solder matrix readily in the soldering stage, and then affected the shear strength of the solder joint significantly. The Au migration occurred in the solder joint during isothermal aging. The Au migration is more apparent when the Cu₆Sn₅ type compound formed at the interface. The embrittlement caused by the weak interface between the (Au_1−xNi_x)Sn₄ and Ni₃Sn₄ layers cannot be observed in this study.     

锡基钎料与铜界面IMC的研究进展

对国内外电子封装"锡基钎料/铜基板"焊点体系界面IMC形成与生长机理的研究进展进行了回顾、评述,重点阐述了界面IMC的形成与生长行为、形成热力学和生长动力学,简要评述了相关因素对界面IMC生长行为的影响。最后,对无铅化电子封装互连焊点界面IMC研究的发展趋势进行了展望。     

Sn基钎料与Cu和Al基板的润湿性比较研究

采用润湿平衡法测量了四种Sn基钎料(Sn-37Pb、Sn-3.OAg-0.5Cu、Sn-0.7Cu与Sn-9Zn)分别在250,260和270℃与Cu、Al两种基板的润湿性能.结果表明:钎料与Al基板的润湿时间均比Cu基板长,除Sn-9Zn外,其他三种钎料与Cu基板的润湿力比Al基板大,并且随着温度升高,润湿性能提高,...     

Morphology and growth kinetics of intermetallic compounds in solid-state interfacial reaction of electroless Ni-P with Sn-based lead-free solders

A comparative study of solid/solid interfacial reactions of electroless Ni-P (15 at.% P) with lead-free solders, Sn-0.7Cu, Sn-3.5Ag, Sn-3.8Ag-0.7Cu, and pure Sn, was carried out by performing thermal aging at 150°C up to 1000 h. For pure Sn and Sn-3.5Ag solder, three distinctive layers, Ni₃Sn₄, SnNiP, and Ni₃P, were observed in between the solder and electroless Ni-P; while for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders, two distinctive layers, (CuNi)₆Sn₅ and Ni₃P, were observed. The differences in morphology and growth kinetics of the intermetallic compounds (IMCs) at the interfaces between electroless Ni-P and lead-free solders were investigated, as well as the growth kinetics of the P-enriched layers underneath the interfacial IMC layers. With increasing aging time, the coarsening of interfacial Ni₃Sn₄ IMC grains for pure Sn and Sn-3.5Ag solder was significantly greater than that of the interfacial (CuNi)₆Sn₅ IMC grains for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders. Furthermore, the Ni content in interfacial (CuNi)₆Sn₅ phase slightly increased during aging. A small addition of Cu (0.7 wt.%) resulted in differences in the type, morphology, and growth kinetics of interfacial IMCs. By comparing the metallurgical aspects and growth kinetics of the interfacial IMCs and the underneath P-enriched layers, the role of initial Cu and Ag in lead-free solders is better understood.     

Observed correlation of Sn oxide film to Sn whisker growth in Sn-Cu electrodeposit for Pb-free solders

Localized cracking of surface oxide has been proposed as a necessary step in the nucleation of Sn whiskers in Sn electrodeposited films. To evaluate the effects of the oxide film on Sn whisker growth, a bright Sn-Cu electrodeposited film was inserted into an ultrahigh vacuum Auger system, cleaned using an Ar⁻ ion beam to remove the oxide film, and aged in the 2×10⁻⁹ Pa Auger system chamber. Whiskers and other features present during Ar⁺ ion cleaning left visible “shadows” on the surface. During aging in the ultrahigh vacuum system, new whiskers, identified by the absence of the telltale shadows, nucleated and grew. Based on these observations, the presence or absence of an oxide film has a minimal effect on Sn whisker nucleation and growth.     

Comparison of Sn2.8Ag20In and Sn10Bi10In solders for intermediate-step soldering

We chose Sn−2.8Ag−20In and Sn−10Bi−10In (numbers are in weight percentages unless specified otherwise) as Pb-free solder materials for intermediate-step soldering. We then investigated how the two solders reacted with the under bump metallurgy (UBM) of Au/Ni (Au: 1.5 μm and Ni: 3 μm) at 210°C, 220°C, 230°C, and 240°C for up to 4 min. All, of the Au UBM was dissolved into the solder matrix as soon as the interfacial reaction started. The reaction formed Au(In, Sn)₂ in the case of SnAgIn, and it formed Au(Sn, In)₄ and Au(In, Sn)₂ in the case of SnBiIn. The formation mechanism of the intermetallic phases is explained thermodynamically. The exposed Ni layer reacted with the solder and formed Ni₂₈Sn₅₅In₁₇ in case of SnAgIn, and formed Ni₃(Sn, In)₄ in case of SnBiIn, at the solder joint interface. Under the same soldering conditions, the Ni₃(Sn,In)₄ layer in the SnBiIn/UBM is thicker than the Ni₂₈Sn₅₅In₁₇ layer in the SnAgIn/UBM. Because of the thicker intermetallic compound layer, the SnBiIn solder joint has weaker shear strength than the SnAgIn solder joint.     

Modeling the interdependence of processing and alloy composition on the evolution of microstructure in Sn-based lead-free solders in fine pitch flip chip

Market demands and legislation are driving the electronics-manufacturing sector to move rapidly toward a lead-free future, with Pb-containing electronics products to be banned in Europe after 2006. Although the related scientific research has been undertaken for a decade, a number of technical complications still exist, which are further exacerbated due to the concurrent developments in miniaturization and multifunctionality of microelectronic products. As the packaging joint geometry shrinks toward a microscopic scale, the joint fabrication and reliability become extremely sensitive to the composition and resulting microstructure generated from the chosen joining process and materials. The current level of understanding of such issues is still in its infancy and therefore requires further fundamental study. Thermodynamic modeling is employed in this work as a computational tool to study the sensitivity of processing ranges (e.g., reflow temperature) and the resultant reliability of the microjoints by changing the alloying elements and their content in Sn-based lead-free systems. The work is implemented using the MTDATA program developed by the National Physical Laboratory. With a newly developed database containing critically assessed thermodynamic data appropriate for lead-free solder systems, MTDATA allows the prediction of the liquid-solid transformation and phase formation, for example, as a function of chemical composition and temperature. The paper emphasizes the formation and mass fraction of intermetallic precipitates of different phases in the bulk solder joints and the modeling is also validated through experimental work and recent literature. The results are expected to assist the optimization of processing parameters and cost-effective production using lead-free solders.     

Effect of cooling rate on microstructure and shear strength of pure Sn,Sn-0.7Cu,Sn-3.5Ag,and Sn-37Pb solders

The microstructure and shear strength characteristics of pure Sn and the eutectic compositions of Sn-37Pb, Sn-0.7Cu, and Sn-3.5Ag prepared under identical reflow conditions but subjected to two different cooling conditions were evaluated at room temperature. For the four solders, the ultimate shear strength increased with increasing strain rate from 10⁻⁵ s⁻¹ to 10⁻¹ s⁻¹. Decreasing the cooling rate tended to decrease the ultimate shear strength for both the Sn-0.7Cu and Sn-3.5Ag solders. The effects of work hardening resulting from increased strain rate were more prevalent in quench-cooled (QC) samples.     

Using nanoindentation to investigate the temperature cycling of Sn37Pb solders

Using nanoindentation and energy dispersive X-ray spectrometry (EDS), we have conducted an investigation into corner failures to elucidate not only the nanomechanical properties of Sn37Pb solder balls but also the effects of temperature cycling tests (TCTs). We found that the hardness of Sn37Pb solder balls was greater in central locations [1.18 ± 0.05 GPa for room-temperature (RT) sample; 1.3 ± 0.05 GPa for TCT sample], but had standard values in corner locations (> 0.2 ± 0.02 GPa). The modulus increased after the TCTs. Nevertheless, the mechanical properties were closely related to the average area of the α-Pb phase. The average area of the Pb-rich region was more stable after the TCTs than that of the RT sample, due to the enhanced mechanical properties of the Sn37Pb solder, suggesting good reliability. From an analysis of average areas in the RT sample, it appears that the Pb-rich solid solution that formed led to weak SnPb bonds near the corner locations. Electron back-scattered diffraction measurements revealed that grains with grain boundaries formed as a result of accelerated TCT cycling. We conclude that SnPb recrystallization was initiated and propagated after the TCTs, followed by propagation to the interfacial region.     

An investigation into the reliability of power modules considering baseplate solders thermal fatigue in aeronautical applications

This work examines the thermal fatigue effects on different configurations of power modules used in harsh aeronautical environment. They are used in various applications where the temperature cycling due to the working environment is the most limiting fact. In this case, it is highlighted that the topology assembly choice is a critical point to reach the lifetime required for the final application. In addition, it is proposed to correlate the probabilistic finite elements calculus to the experimental accelerated ageing tests on test vehicle, in order to determine the best configuration of assembling stack consisting of baseplate/RoHS solder/metallized substrate.     

Degradation of electroless Ni(P) under-bump metallization in Sn3.5Ag and Sn37Pb solders during high-temperature storage

The interfacial reaction between electroless Ni(P) under-bump metallization (UBM) and solders is studied. A P-rich layer forms in the UBM along the solder side after reflow and thermal aging. Crack formation inside the P-rich layer can sometimes penetrate throughout the entire UBM layer structure. The Ni(P) UBM degradation occurs earlier in the Sn3.5Ag solder than in Sn37Pb because of its higher reflow temperature. Despite the formation of a P-rich layer and cracks inside the UBM, it still keeps its original function within the high-temperature storage period in this study. Explanations for the formation of the P-rich layer and cracks in the UBM are outlined along with explanations for the Ni(P) UBM degradation process.     

Isothermal aging effects on the microstructure and solder bump shear strength of eutectic Sn37Pb and Sn3.5Ag solders

The reliability of the eutectic Sn37Pb (63%Sn37%Pb) and Sn3.5Ag (96.5%Sn3.5%Ag) solder bumps with an under bump metallization (UBM) consisting of an electroless Ni(P) plus a thin layer of Au was evaluated following isothermal aging at 150 °C. All the solder bumps remained intact after 1500 h aging at 150 °C. Solder bump microstructure evolution and interface structure change during isothermal aging were observed and correlated with the solder bump shear strength and failure modes. Cohesive solder failure was the only failure mode for the eutectic Sn37Pb solder bump, while partial cohesive solder failure and partial Ni(P) UBM/Al metallization interfacial delamination was the main failure mode for eutectic Sn3.5Ag solder bump.     

The joint strength and microstructure of fluxless Au/Sn solders in InP-based laser diode packages

The joint strength and microstructure of fluxless Au/Sn solders in InP-based laser-diode packages after thermal-aging testing were studied experimentally and numerically. Specimens were aged at 150°C for up to 64 days. The joint strength decreased as aging time increased. The microstructure and fracture surface of the Au/Sn solder joints showed that the joint strength decrease was caused by both the enlargement of the initial voids and an increase in the number of voids as the aging time increased. Finite-element method (FEM) simulations of joint strength were in good agreement with experimental measurements. Both experimental and numerical results indicate that the enlargement of the initial voids and an increase in the number of voids, caused by stress concentration as the aging period increased, resulted in the weakness of joint strength. The effect of temperature-cycling testing on the power variation of the InP laser diodes using fluxless Au/Sn solders was also studied. It was shown that the laser diodes operated in the stable condition up to 500 cycles.     

The influence of thermal aging on joint strength and fracture surface of Pb/Sn and Au/Sn solders in laser diode packages

The joint strength and fracture surface of Pb/Sn and Au/Sn solders in laserdiode packages after thermal-aging testing were studied experimentally. Specimens were aged at 150°C for up to 49 days. The joint strength decreased as aging time increased. The microstructure and fracture surface of the Pb/Sn and Au/Sn solder joints showed that the joint strength decrease was caused by both the enlargement of the initial voids and an increase in the number of voids as aging time increased. The formation of Kirkendall voids with intermetallic-compound (IMC) growth of the Pn/Sn solder as aging time increased was also a possible mechanism for the joint-strength reduction. Finite-element method (FEM) simulations were performed on the joint-strength estimation of Pb/Sn and Au/Sn solders in thermal-aging tests. The coupled thermal-elasticity-plasticity model was used to simulate distributions of the thermal and residual stresses, creep deformation, and joint-strength variations in the solder joints under various thermal-aging tests. Simulation results were in good agreement with the experimental measurements that the solder-joint strength decreased as aging time increased. The result suggests that the FEM is an effective method for analyzing and predicting the solder-joint strength in laserdiode packages.     

Solid-state annealing behavior of two high-Pb solders, 95Pb5Sn and 90Pb10Sn,on Cu under bump metallurgy

The solid-state annealing behavior of two high-lead solders, 95Pb5Sn and 90Pb10Sn (in wt.%), was examined. After reflow, Cu₃Sn intermetallics formed on the Cu under bump metallurgy (UBM) for both solder alloys. However, solidstate annealing produced significantly different reaction morphologies for the two solder compositions. The Cu₃Sn intermetallics spalled off faster at higher temperatures in the 95Pb5Sn solder. In the case of 90Pb10Sn solder, the Cu₃Sn intermetallics continued to grow even after 1500 h at 170°C. The difference was explained by a two-step phenomenon—Sn diffusion from the bulk solder region to the solder/Cu₃Sn interface (J_Sn), and subsequent intermetallic formation (I_Cu3Sn) by interdiffusion of Cu and Sn. For 95Pb5Sn, the relation, J_Sn < I_Cu3Sn was postulated because of insufficient supply of Sn. The relation, J_Sn > I_Cu3Sn was suggested for the continuous intermetallic growth of the 90Pb10Sn solder. Although a small difference was expected between the two quantities in both solder alloys, the difference in the solid-state annealing behavior was dramatic.     

Influence of Ni concentration and Ni3Sn4 nanoparticles on morphology of Sn-Ag-Ni solders by mechanical alloying

The mechanical alloying (MA) process was employed as an alternative method to produce the lead-free solder pastes of Sn-3.5Ag-xNi (x=0.1, 0.5, 1.0, 1.5, and 2.0) in this study. When the Ni concentration was low (x=0.1, 0.5), MA particles agglomerated to a flat ingot with particle sizes >100 μm. For higher Ni concentration (x=1.0, 1.5, and 2.0), MA particles turned into fragments with particle sizes <100 μm. The particle size of the solders appeared to be dependent on the Ni concentration. To reduce the particle size of SnAgNi alloys with low Ni concentration, Ni₃Sn₄ nanoparticles were doped into Sn and Ag powders to derive a Ni₃Sn₄-doped solder. For the Ni₃Sn₄-doped solder, the particle size was smaller than that doped by the pure Ni. The distinction of milling mechanism between Ni₃Sn₄-doped solder and the pure Ni-doped solder by MA process was probed and discussed. In addition, differential scanning calorimetry (DSC) results ensured its feasibility in applying the solder material in the reflow process. Wettability tests between solders and Cu substrate also revealed that the wetting angles for Ni₃Sn₄-doped solder with low Ni concentration (0.1 and 0.5 wt.%) were smaller than those for pure Ni-doped solder. The wetting angles on both Cu substrate and electroplated Ni metallization for SnAgNi solders were also comparable with commercial Sn-3.5Ag and Sn-3.0Ag-0.5Cu solders. Favorable wettability of the as-derived solder in this study was clearly demonstrated.     

Formation of bulk Ag<Subscript>3</Subscript>Sn intermetallic compounds in Sn-Ag lead-free solders in solidification

A series of Sn-Ag solders were prepared by arc melting and their phase evolution was investigated as a function of cooling rates. It was found that bulk Ag₃Sn intermetallic compounds (IMCs) separated out only in the slowly cooled Sn-4.0Ag solder. This would be explained by the strong kinetic undercooling, arising from the rapid cooling conditions, which leads to the actual eutectic point shifts in the direction of higher Ag concentration. Thus, the eutectic and hypereutectic alloys experience a metastable hypoeutectic solidification route instead. All formed fractions of bulk Ag₃Sn IMCs in solders, measured by quantitative microstructural analysis and thermal analysis, are larger than those predicted by the equilibrium phase diagram. The reasoning for this could be attributed to fine Ag₃Sn phases, which cling to the primary Ag₃Sn crystal during the eutectic reaction for their matching crystalline orientation relationship. Furthermore, the fraction of bulk Ag₃Sn IMCs increases gradually with increasing the cooling rate in the slowly cooled Sn-4.0Ag alloy, which fits with the prediction of eutectic solidification theory: the increase of cooling rate would decrease the surface energy of fine Ag₃Sn particles and primary Ag₃Sn crystal, and make fine Ag₃Sn particles cling to primary Ag₃Sn crystal easily to form bulk Ag₃Sn IMCs.     

电子封装与组装焊点界面反应及微观组织研究进展

软钎焊焊点界面反应是连接金属的最古老的冶金工艺过程。随着倒装芯片(FC)、球栅阵列(BGA)和芯片级封装(CSP)等面封装技术的兴起,近年来Sn基钎料被广泛应用于微电子制造,包括芯片和基板之间的封装互连以及基板与印制电路板之间的组装互连。这就需要系统地研究Sn基钎料焊点界面反应及微观组织。从形态学、热力学和动力学的角度回顾总结了SnPb共晶钎料、高Pb钎料和无Pb钎料与Cu、Ni、Au/Ni/Cu、PdAg焊盘之间的界面反应。     

电子封装与组装焊点钎料合金力学行为研究进展

随着面封装技术的持续发展,古老的软钎焊技术被赋予新使命,Sn基钎料焊点被广泛用于实现芯片与基板之间以及基板与印制电路板之间的电气互连。目前电子封装与组装焊点的失效成为了影响电子产品可靠性的关键问题。这就需要系统地表征焊点服役条件下Sn基钎料合金的力学行为,并刻画其本构关系。本文从本构模型、寿命预测模型及断裂机制三个角度回顾总结了焊点Sn基钎料合金的力学行为方面的研究结果。