Evolution of mechanical and electrical properties of tin-lead and lead free solder to copper joint interface

Cu-(Sn37Pb) and Cu-(Sn3.5Ag0.5Cu) solder joints were prepared at the same reflow temperature of 230 °C. The microstructural observation of the solder assemblies in scanning and transmission electron microscopes confirmed the presence of η-Cu₆Sn₅ in case of the former, and Cu₃Sn + η-Cu₆Sn₅ for the latter in the reaction zone. The findings are correlated with the electrical and mechanical properties of the joints. Lead free solder-Cu joint exhibited lower reaction zone thickness and improved electrical conductivity (0.28 × 10⁶Ω^− 1 cm^− 1) and shear strength ∼ 68MPa compared to conventional lead-tin solder-Cu joint. The latter showed electrical conductivity and shear strength of 0.22 × 10⁶Ω^− 1 cm^− 1 and ∼ 55 MPa, respectively. The difference in reaction zone thickness is explained on the basis of melt superheat, with Sn being the primary diffusing species in the intermetallic layer.     

Calculations of diffusion in FCC binary alloys using on-the-fly kinetic Monte Carlo

We present a systematic, microscopic approach to diffusion for intermetallic alloys using accelerated molecular dynamics. On-the-fly kinetic Monte Carlo is combined with an efficient saddlepoint search to find the saddlepoints exiting a valley, based on energetics from the embedded atom method. With this technique, we compute the tracer diffusivities, migration energies, short-range order and long-range order as a function of composition and temperature for examples of moderately ordered (Cu₃Au), weakly ordered (Au–Ag) and weakly clustered (Cu–Ni) alloys. We find that away from any critical temperature, the calculations produce reliable results, but when critical behavior dominates the approach is overcome by critical fluctuations.     

Enhanced ductility and mechanical strength of Ni-doped Sn–3.0Ag–0.5Cu lead-free solders

In this paper, the tensile tests were conducted to investigate the effect of adding a small amount of Ni on the microstructure, thermal and mechanical properties of 3.0Ag–0.5Cu(SAC 305) solder. The results indicated that addition of Ni can effectively decrease both the undercooling and the onset melting temperature of SAC(305) solder alloy. The strength and ductility of the SAC(305) solder depend significantly on Ni content. In general, the SAC(305)–0.5%Ni solder reveals superior mechanical properties in terms of maximum strength and ductility when compared to the high Ni-content or plain solders. Microstructure analysis revealed that a new η-(Cu,Ni)₆Sn₅ intermetallic compound (IMC) phase containing large amount of Ni was generated, while the initial Cu₆Sn₅ phase was converted into (Cu,Ni)₆Sn₅ phase after 0.5%Ni addition. Besides, the fine fiber-like Ag₃Sn and finer dot-shaped precipitates rather than needle-like morphology have occurred at the surface of β-Sn matrix easily, which could provide more obstacles for dislocation pile up in the adjacent grains and enhanced the mechanical property. With increasing Ni addition, the Ni-doped SAC(305) solder showed a corresponding deterioration in their mechanical property due to the coarsening of (Cu,Ni)₆Sn₅ IMCs and increasing the inter-particle spacing of Ag₃Sn IMCs in the eutectic colony.     

Fatigue fracture of SnAgCu solder joints by microstructural modeling

The ongoing miniaturization trend in the microelectronic industry enforces component sizes to approach the micron, or even the nano scale. At these scales, the underlying microstructural sizes and the geometrical dimensions are comparable. The increasing influence of microscopic entities on the overall mechanical properties makes conventional continuum material models more and more questionable. In this study, the thermomechanical reliability of lead-free BGA solder balls is investigated by microstructural modeling. Microstructural input is provided by orientation imaging microscopy (OIM), converted into a finite element framework. Blowholes in BGA solder balls are examined by optical microscopy and a statistical analysis on their size, position and frequency is conducted. Combining the microstructural data with the appropriate material models, three dimensional local models are created. The fatigue life of the package is determined through a critical solder ball. The thermomechanical reliability of the local models are predicted using cohesive zone based fatigue damage models. The simulation results are validated by statistical analyses provided by the industry.     

Electrochemical migration of Sn-Pb and lead free solder alloys under distilled water

Electrochemical migration (ECM) is a potential reliability problem in electronic soldering which might become more dangerous in lead free electronic devices. In this paper, electrochemical migration tests on Sn-Pb and lead free solder alloys were conducted under distilled water by applying constant voltages with a power supply. The susceptibility of the solder alloys to ECM and the effect of the composition on ECM behavior were studied. It is found that both Sn-Pb and lead free solders investigated in present research have susceptibility on ECM. Dendrites grow from cathode to anode and show different morphologies with the different migration elements involved. In Sn-37Pb and Sn-36Pb-2Ag solders, the main migration element is Pb. While for Sn-Ag and Sn-Ag-Cu solder alloys, Sn leads the migration. For Sn-8Zn-3Bi, both Sn and Zn can migrate. Furthermore, the effect of applied voltage on the time to short and short resistance was also investigated. As could be expected, the higher the voltage is, the shorter the failure time is. The electrochemical migration mechanism of the solder alloys was also discussed. The author is now at Fraunhofer IZM, Berlin, Germany     

无铅焊料研究现状与发展展望

随着电子工业飞速发展以及人们环保意识的提高，以“绿色焊接”为主题的电子装配技术对无铅焊料的需求也尤为迫切。本文从焊料可焊性和焊接蛄构的可靠性等方面介绍了近年来国内外无铅焊料研究方面的最新成果；着重概括了为提高焊接性能而在配料组分、金属间化合物析出与组织控制等工作，重点阐明了稀土元素在焊料组织控制中的关键作用；针对我国稀土资源蕴藏丰富的特点，指出了元铅焊料进一步发展的方向。     

Fatigue life estimations of solid-state drives with dummy solder balls under vibration

An investigation of the effect of dummy solder balls on the fatigue life of a solid-state drive (SSD) under vibration was studied. Finite element analysis and forced vibration experiments of an SSD were conducted to evaluate the fatigue life of an SSD. Global–local analysis techniques were adopted in the finite element analysis to calculate the stress of the solder balls in the SSD. In the vibration experiments, the SSD with dummy solder balls was excited via a sinusoidal sweep vibration around the first resonant frequency until the SSD failed. Using the stress results from global–local analysis and the cycle to failure results from the experiment, an S–N curve was derived for the SSD. This study showed that the solder joints at the corners of the controller package were the most vulnerable components, and that applying the dummy solder balls to those areas decreased the stress of the solder balls and increased the fatigue life of the SSD.     

Electrochemical migration of lead free solder joints

Electrochemical migration (ECM) tests on lead bearing and lead free solder joints on Cu lamination on FR-4 board were conducted by applying constant voltage. This paper first studied the ECM of the soldered joints under distilled water after removing the fluxes. In addition, conditions under high temperature and high humidity were also set up to investigate the changes of the initial surface insulation resistance (SIR) with the residues of no clean fluxes. It is found under distilled water that dendrites of the solder joints take on different morphologies with the different migration elements. For the joints of Sn-37Pb and Sn-36Pb-2Ag solders, the main migration element is Pb. While that of Sn-3.5Ag and Sn-4Ag-0.5Cu solders, it is Cu that usually migrates and forms dendrites due to the poor wettability of the solder paste leads to part exposure of Cu substrate at the wetting brim. For Sn-3Ag-0.5Cu solder joints, Sn leads the migration. While for Sn-Zn-Bi solder joints, it is always Zn to migrate which means Zn is more mobile than Cu. The investigation on SIR shows the fluxes have great effect on the migration behavior. The failure time of the joints with the same solder alloy compositions have different failure time due to the different fluxes. The effect of the wettability and the role of Cu substrate on the ECM behavior of the solder joints are discussed in detail.     

Influence of tin and bismuth on machinability of lead free 6000 series aluminium alloys

Abstract

The present paper presents the microstructural characteristics of an extruded AA6012A-T6 (AlMgSiBiSn) alloy and the microstructural changes occurring during turning operations, analysing the mechanism involved in chip breaking. An experimental investigation has been conducted to determine the effects of different cutting speed and feedrate on the machinability of the alloy. The machinability of the AA6012A-T6 alloy, where Pb is substituted by Bi and Sn, has then been compared to the standard AA6012-T6 (AlMgSiPb) and AA6082-T6 (AlSiMg) alloys. The results indicate that the extensive plastic deformation induces a preferred orientation of the grain structure and secondary phases along the shear plane, and a local increase in the alloy temperature. Low melting point compounds, such as the Sn and Bi bearing particles, transform into a soft or liquid state, changing their initial compact shape to assume a needle-like morphology. The β-Mg₂Si and α-Al(FeMn)Si particles are not influenced by the working temperature and keep their initial shape. The AA6082-T6 alloy shows a very poor machinability, with long and continuous strips, while the AA6012A-T6 alloy reveals a good chip formation with small and discontinuous C shaped chips, similar to the AA6012-T6 (AlMgSiPb) alloy. In particular, a feedrate higher than 0·2 mm rev^?1 provides short and suitable chips, independently of cutting speed.     

On the advantages of using a hypoeutectic Sn-Zn as lead-free solder material

Hypoeutectic Sn-Zn may be a better choice than the eutectic Sn-9Zn as a lead-free solder. We checked the non-equilibrium melting behaviors of a series of Sn-Zn alloys (2.5-9 wt.% Zn) by differential thermal analysis, and found that at a heating rate of 5 °C/min, Sn-6.5Zn behaves the same way as the eutectic Sn-9Zn in melting. Dipping and spreading tests were carried out to characterize the wettability of Sn-Zn alloys on Cu. Both tests indicated that Sn-6.5Zn has significantly better wettability to Cu than Sn-9Zn does. The reaction layers formed during the spreading tests were examined. For all samples with 2.5-9 wt.% Zn, two reaction layers are formed at the interface, a thick and flat Cu₅Zn₈ layer adjacent to Cu and a thin and irregular Cu-Zn-Sn layer adjacent to the alloy. The total thickness of the reaction layers between the alloy and Cu was found to remarkably decrease with decrease of the Zn concentration.     

冷却速度对Sn-Ag无铅焊料微观组织和机械性能的影响

研究了不同冷却速度下无铅焊料Sn-3．5％(质量分数)Ag合金的微观形貌(冷却速度从0．08K／s到10^4K／s)。结果表明焊料合金中二次枝晶间距随冷却速度增加而逐渐减小，且符合公式：d=atf^n，其中d为二次枝晶间距，tf是冷却时间，a和n是由材料和其成分所决定的常数，通过计算得到对于Sn-3．5％(质量分数)Ag合金其a为3．7，而n为0．43。维氏硬度测试结果表明：快速冷却条件能使焊料合金晶粒细化，其中作为强化相的金属间化合物Ag3Sn分布更加细密，从而能使整个合金机械性能得到提高。     

Monte Carlo calculations on the beta-delta phase transition in nitrogen with a generalized free energy method

Monte Carlo simulations that utilize an (N, P, T) ensemble with periodic deformable boundary conditions cannot describe phase transitions properly when a large potential barrier is involved. An alternative method is to calculate the Gibbs free energy difference between phases; the transition occurs when the difference is equal to zero. The Gibbs free-energy difference can be calculated using a generalized free-energy method. This method is used to determine the- phase transition of solid nitrogen at room temperature. The Gibbs freeenergy difference between the and the phase was obtained at 4.0 GPa. The difference at other pressures could be determined with the equation of state. The transition pressure was found at about 6.2 GPa, 1.3 GPa above the experimental pressure.     

Influence of laminate type on tin whisker growth in tin-rich lead-free solder alloys

This paper describes variations in whisker growth on the surface of tin-rich, lead-free alloys soldered on a Cu layer depending on the laminate used for the printed circuit board, which can be either glass-epoxy or paper-phenol. The structure of the glass-epoxy laminate surface is characterized by spatial nonuniformity caused by the regular structure formed by regions of glass fibers and resin in the top layer of the laminate. The higher value of thermal expansion of the resin than of the glass fiber means that the area of the resin expands more than that of the glass fiber. This causes local compressive stress in the solder layer and as a result promotes whisker growth in the area of the alloy soldered on the Cu layer over the glass fiber. This effect does not occur on the surface of an alloy soldered on Cu layer over a paper-phenol laminate.     

Development and characterization of Au-Cu seal ring for lead free packaging of MEMS devices

Seal rings are developed for packaging of circular openings of sensors and the fluidic flow based Micro Electro Mechanical Systems. Lead free technique based on isothermal solidification is used in this course of study. Thick film Au and high purity Cu substrates have been used during the development practice. Indium is used as the interlayer metal. Interconnections of high thermal and mechanical stabilities are fabricated for variable process parameters. The effects of temperature, pressure and reaction time on the ultimate tensile strength (UTS) and ultimate shear strength (USS) are presented and reported in this paper. The thermal stabilities of the specimen seal rings are obtained in the 700-900 K temperature range. Effect of ageing for various cycles and shelf life in different environments are discussed.     

An investigation of nanoparticles addition on solidification kinetics and microstructure development of tin–lead solder

High strength solders can be engineered by adding trace amounts of nanopowders into solder paste. An experimental study was conducted for a better understanding of the solidification kinetics and microstructure development of such nano-composite tin–lead solders. The composite solder pastes were prepared by mechanically mixing nanopowders of either copper or TiO₂ with tin–lead powders (tens of microns in size). Solidification experiments of the composite solders were performed in an aluminum crucible with temperature variation during cooling and solidification being measured. For the titanium dioxide (TiO₂) nanopowders-reinforced composite solders, the test data reveals the occurrence of melt undercooling followed by recalescence at an increased melting temperature. However, for the copper nanopowders-reinforced composite solders, a reduced melting temperature coupled with two-stages of solidification was distinctly evident. Metallographic observations of the solidified composite solders revealed a reduction in both the grain size and spacing of the eutectic lamellae. This is responsible for the observed increase in microhardness.     

铜基引线框架材料的研究与发展

引线框架材料是半导体元器件和集成电路封装的主要材料之一，其主要功能为电路连接、散热、机械支撑等。随着IC向高密度、小型化、大功率、低成本方向发展，集成电路I/O数目增多、引脚间距减小，对引线框架材料提出了高强度、高导电、高导热等多方面性能上的要求。由于拥有良好的导电导热性能，铜合金已成为主要的引线框架材料。本文对电子封装铜合金引线框架材料的性能要求、国内外研究与发展等进行了综述。     

A spectral stochastic element free Galerkin method for the problems with random material parameter

This paper presents a spectral stochastic element free Galerkin method (SSEFGM) for the problems involving a random material property. The random material property and resulting system response quantity are represented by a probabilistic spectral expansion techniques (Karhunen–Loeve expansion and Polynomical Chaos series, respectively) and implemented into the element free Galerkin (EFG) analysis. Numerical solutions in 1D linear elastic problem with random elastic modulus are introduced, and compared with those of Monte Carlo simulation (MCS) so as to provide the validation of the proposed approach. The present SSEFGM approach can produce a probabilistic density distribution as well as a first‐ and second‐order statistical moments (mean and variance) of response quantity by a single calculation, which is distinguished from an iterative MCS. Moreover, the method is based on an element free analysis so that there is no need of nodal connectivities, which usually require more time and labourious task than main calculations. Thus the proposed SSEFGM approach can provide an alternative analysis tool for the problems contains a stochastic material property, and demands complex mesh structures. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of bismuth and silver on the corrosion behavior of Sn-9Zn alloy in NaCl 3 wt.% solution

The effect of silver (Ag) and bismuth (Bi) on the corrosion resistance of Sn-9Zn alloy in NaCl 3 wt.% solution was investigated using electrochemical techniques. The results showed that the addition of Bi and Ag lead to the increase of corrosion rate and the corrosion potential E_corr is shifted towards less noble values. After immersion, X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive of spectroscopy (EDS) analysis of the corroded alloy surface revealed the nature of corrosion products. EDS and XRD analyses confirmed the oxide of zinc (ZnO and Zn₅(OH)₈Cl₂H₂O) as the major corrosion product formed on the outer surface of in the tested three solder alloys.     

Re‐calibration of Engelmaier's Model for Leadless,Lead‐free Solder Attachments

In this paper, the solder attachment fatigue model created by Werner Engelmaier is re‐calibrated in order to make it applicable in conjunction with leadless, lead‐free solder attachments. Sn3.8Ag0.7Cu solder attached ball‐grid‐array components are addressed to three thermal cycling test profiles. Based on the results, both physical and statistical parameters are obtained and compared with the values relevant to tin–lead solder assemblies. The validity of the statistical distribution selection (two‐parameter Weibull) is studied. Acceleration factors correlating different test profiles are obtained, and they are found to be only weakly dependent on the test vehicle type. Copyright © 2006 John Wiley & Sons, Ltd.     

Failure Modes of Lead Free Solder Bumps Formed by Induction Spontaneous Heating Reflow

The shear failure modes and respective failure mechanism of Sn3.5Ag and Sn3.0Ag0.5Cu lead-free solder bumping on Au/Ni/Cu metallization formed by induction spontaneous heating reflow process have been investigated through the shear test after aging at 120℃ for 0, 1, 4, 9 and 16 d. Different typical shear failure behaviors have been found in the loading curves （shear force vs displacement）. From the results of interracial morphology analysis of the fracture surfaces and cross-sections, two main typical failure modes have been identified. The probabilities of the failure modes occurrence are inconsistent when the joints were aged for different times. The evolution of the brittle NiaSn4 and Cu-Ni-Au-Sn layers and the grains coarsening of the solder bulk are the basic reasons for the change of shear failure modes.