Phase equilibria and thermodynamic properties of Sn-Ag based Pb-free solder alloys

We have recently developed a thermodynamic database for micro-soldering alloys, alloy database for micro-solders (ADAMIS). ADAMIS which consists of the elements Ag, Bi, Cu, In, Pb, Sb, Sn, and Zn has been constructed by the calculation of phase diagrams (CALPHAD) method. The thermodynamic parameters for describing the Gibbs energy of the liquid and solid phases have been evaluated by optimizing the experimental data on phase boundaries and thermo-chemical properties. In this paper, the phase equilibria and the related thermodynamic properties pertaining to the Sn-Ag-X (X=Bi, In, Cu, and Zn) alloys are examined using ADAMIS. Typical examples of the isothermal and vertical section phase diagrams, liquidus surface, etc. for these promising lead-free solders are presented. In addition, ADAMIS is also applied to calculate the nonequilibrium solidification process using the Scheil model.     

Thermodynamic database for phase diagrams in micro-soldering alloys

A thermodynamic database for the calculation of phase diagrams in micro-soldering alloy systems, which include the elements Pb, Bi, Sn, Sb, Cu, Ag, and Zn has been developed using the CALPHAD method. The various thermodynamic parameters for describing the Gibbs energies of the different constituent phases have been evaluated by optimizing experimental data on phase boundary compositions and thermochemical properties such as activity, heat of mixing and enthalpy of formation. The resulting database provides the means whereby the liquidus and solidus surfaces, isothermal and vertical section diagrams, phase percentages and the mole fraction of the phase constitutions etc., in multi-component soldering alloys can be readily calculated. Related information such as the surface tension and viscosity of the liquid phase can also be predicted, thus rendering the database as a valuable tool for developing leadbearing and lead-free solders.     

Thermodynamic database on microsolders and copper-based alloy systems

Recent progress on the thermodynamic databases of calculated phase diagrams in microsolders and Cu-based alloys is presented. A thermodynamic tool, Alloy Database for Microsolders (ADAMIS), is based on comprehensive experimental and thermodynamic data accumulated with the calculation of phase diagrams (CALPHAD) method and contains eight elements, namely, Ag, Bi, Cu, In, Sb, Sn, Zn, and Pb. It can handle all combinations of these elements and all composition ranges. The elements of Al and Au have also been added to ADAMIS within a limited range of compositions. Furthermore, a database of Cu-based alloys, including binary (Cu-X), ternary (Cu-Fe-X, Cu-Ni-X, and Cu-Cr-X), and multicomponent (Cu-Ni-Cr-Sn-Zn-Fe-Si) systems, has also been developed. Typical examples of the calculation and application of these data-bases are presented. These databases are expected to be a powerful tool for the development of Pb-free solders and Cu substrate materials as well as for promoting the understanding of the interfacial phenomena between them in electronic packaging technology.     

Thermal Analysis of the Sn-Ag-Cu-In Solder Alloy

The tin-based alloy Sn-1.5Ag-0.7Cu-9.5In (composition in wt.%) is a potential candidate for lead-free soldering at temperatures close to 200°C due to the significant amount of indium. Samples of Sn-1.5Ag-0.7Cu-9.5In were prepared by controlled melting of the pure elements, followed by quenching to room temperature. The samples were analyzed by scanning electron microscopy/energy-dispersive x-ray spectroscopy (SEM/EDS) and electron backscatter diffraction. The solidified melt consisted of four different phases. Solidification behavior was monitored by heat-flux differential scanning calorimetry (DSC). The phase equilibrium has been further investigated by thermodynamic calculations. The observed phase compositions as well as DSC signals are reasonably explained using the calculation of phase diagrams (CALPHAD) approach.     

On the Sn-Bi-Ag ternary phase diagram

The selection and evaluation of Pb-free solders requires information that is best determined through a knowledge of ternary and higher order phase diagrams. As part of an ongoing program on Pb-free solder phase diagrams at the National Institute of Standards and Technology, a thermodynamic model is formulated for the Sn-Bi-Ag phase diagram. Thermodynamic functions for the various phases obtained by fitting measured data for the three constituent binary systems are extrapolated to the ternary system using the method of Muggianu. Modeling results are compared to preliminary experimental data for the ternary system and are applied in the calculation of the solidification path.     

Thermodynamic Assessment of Phase Equilibria in the Sn-Ag-Ni System with Key Experimental Verification

The phase transformations of the Sn-Ag-Ni system were investigated by means of differential scanning calorimetry (DSC). Based on the experimental data of phase equilibria and thermodynamic properties determined by the present work and previous literature, the thermodynamic assessments of the Sn-Ag-Ni system were carried out using the calculation of phase diagrams (CALPHAD) method. The thermodynamic parameters for describing the phase equilibria were optimized, and reasonable agreement between the calculations and experimental data was obtained in the Sn-Ag-Ni ternary system.     

Thermodynamic analysis and phase equilibria calculations for the In-Sb and Ga-Sb systems

A quasi sub-subregular solution model is used to describe the thermodynamic properties of the liquid phase in the In-Sb and Ga-Sb systems. The In-Sb and Ga-Sb phase diagrams are, then, calculated from the optimized model parameters for the liquid phases and the Gibbs energies of formation of the InSb and GaSb phases obtained from the literature. The calculated phase diagrams and thermodynamic properties are in reasonable agreement with the experimental data. Our calculations are also compared with those reported in the literature using associated solution models for the liquid phases. On leave from Indian Institute of Technology, Kanpur, UP, 208016, India     

Investigation of multi-component lead-free solders

Binary phase diagrams of interest for lead-free solder development have been entered into the THERMO-CALC data base. These may be used directly to calculate multi-component phase relations vs temperature provided there are no ternary or higher order interactions. Such occur in the Sn-Ag-Zn system and are being evaluated. Contact angles of a number of solder-flux combinations on copper were directly measured in spreading tests. With a rosin-isopropyl alcohol flux, the contact angles of binary eutectic solders were in degrees: Sn-Bi at 166°C, 40; Sn-Zn at 225°C, 60; Sn-Ag at 250°C, 45. These angles were little affected by a number of 1% ternary additions to the solder. The contact angles were 20 degrees or less when SnCl₂ was used as a flux. The SnCl₂ reacts with Cu to form Cu₃Sn. The most likely successful approach to obtain satisfactory wetting with lead-free solders appears to be development of a satisfactory flux.     

Thermodynamic Descriptions for the Cd-Te,Pb-Te,Cd-Pb and Cd-Pb-Te Systems

The thermodynamic behaviors of the Cd-Te, Pb-Te, Cd-Pb and Cd-Pb-Te systems are critically analyzed in this work by means of the calculation of phase diagrams (CALPHAD) method. The liquid phases containing Te are described by the associated solution model, which is capable of dealing with V-shaped curves of mixing enthalpies in solution phases, sharp maxima of liquidus curves in phase diagrams, and abrupt changes in activity plots. The binary compounds, CdTe and PbTe, are considered to be stoichiometric in the two binary systems, but they form a line compound described by (Cd,Pb)₁(Te)₁ in the ternary system. The fcc phase, in which only Cd and Pb elements are present, is treated with the substitutional solution model. The experimental data available in the literature are extensively assessed, from which the thermodynamic parameters necessary for each phase are obtained. Various calculated phase equilibria and thermodynamic properties are compared with the experimental data. The excellent agreement indicates that this work contributes to the study of phase stabilities in the Cd-Pb-Te system.     

Thermodynamic prediction of interface phases at Cu/solder joints

A thermodynamic method to predict the intermetallic compound which forms first at the substrate/solder interface during the soldering process has been suggested through calculations of metastable phase equilibria between the substrate and the liquid solder and by comparison of the driving forces of formation of individual intermetallic compound phases. It has been applied to the interfacial reaction between Cu substrate and Sn-Ag, Sn-Zn eutectic solders. The prediction from thermodynamic calculations was in good agreement with observed experimental results. The solid-state growth behavior of compound phases formed at the interface of Cu/Sn-Zn and Cu/Sn-Ag eutectic solder joints was explained and a schematic diffusion path suggested through calculated ternary phase diagrams.     

热力学计算在无铅钎料合金设计中的应用

依据CALPHAD方法进行相平衡计算过程中热力学模型的建立及其求解作了简要介绍，对热力学数据库的特征作了描述。对基于CALPHAD方法而开发的Thermo Calc系统的数据库及几个主要模块的功能作了概括的介绍。并针对在无铅钎料研究领域，利用ThermoCalc进行无铅钎料多元合金相平衡计算、预测液态钎料的表面张力和粘度以及钎料与基底之间形成的金属间化合物的驱动力的研究进展进行了总结。着重介绍了日本Tohoku大学材料系的研究人员开发的钎料合金热力学数据库。     

电子产品无铅化的环保新问题

电子制造过程无铅化已是大势所趋。但目前研发的无铅焊料也存在一些问题:如所添加的合金元素也会污染环境并危害人体健康;大部分添加的合金元素储量有限;无铅焊料生产加工所消耗的能量大大高于锡铅焊料等。指出研发新的绿色互连技术、采取有效的废弃物回收再利用措施才能从根本上解决电子产品废弃物对环境影响的问题。     

Phase equilibria of Sn-In based micro-soldering alloys

The phase equilibria of Sn-In-X (X=Ag, Bi, Sb, Zn), the most basic information necessary for the development of Pb-free micro-soldering alloys, were studied using the CALPHAD method. Thermodynamic analyses for describing the Gibbs energies of the constituent phases were made by optimizing the obtained data on the experimental phase diagrams, and such data in the literature, including data on thermochemical properties. The present results combined with the thermodynamic database which was recently developed by our group [I. Ohnuma et al., J. Electron. Mater. 28, 1164 (1999)] provide various information on phase equilibria such as liquidus and solidus surfaces, isothermal and vertical section diagrams, mole fractions of the phase constitutions, etc., and thermodynamic properties such as activity, heat of mixing, surface energy, viscosity, etc., in multi-component soldering alloy systems including the elements of Pb, Bi, Sn, Sb, Cu, Ag, Zn, and In. Typical examples for the phase diagrams and thermodynamic properties of Sn-In-X ternary systems are shown. The application of the database to the alloy design for Pb-free solders is also presented.     

Experimental Studies and Thermodynamic Assessment of Ternary Cu-Pd-Sn Phase Relations Focusing on the Sn-Rich Alloys

Recently, Pd surface finishes over Cu substrates have been widely used in microelectronic packaging to prevent pad oxidation before soldering and to improve the bondability with Cu wires. The interfacial reactions between these newly developed Pd-based substrates and Pb-free solders, particularly Sn-based solders, are of practical importance. To completely understand interfacial reactions and phase transformation phenomena, phase equilibrium information on solders, intermetallics, and substrate materials are required. In this study, the phase equilibria of the Cu-Pd-Sn ternary system at 200°C was investigated by scanning electron microscopy, electron probe microanalysis, and electron backscatter diffraction. Particular emphasis was placed on the Sn-rich corner of the isothermal section. To analyze the experimental results, a thermodynamic assessment was performed using the computer coupling of phase diagrams and thermochemistry method.     

从专利角度探讨Sn-Zn无铅焊料研究现状

无铅焊料的研发及专利权的保护是我国电子行业亟待解决的问题。文中结合中国专利权的特点,描述了世界各国在无铅焊料专利上的竞争以及Sn-Zn无铅焊料的专利申请状况,并据此分析了Sn- Zn无铅焊料的研发及应用状况、专利Sn-Zn无铅焊料的特点以及应用障碍,以期对我国自主知识产权的Sn-Zn无铅焊料的研发及无铅专利保护有所帮助。     

电子产品中的无铅焊料及其应用与发展

由于传统焊接技术使用的Sn-Pb焊料中的铅会对环境造成污染而被禁止使用,近年来无铅焊料成为了研究热点。文中介绍了运用于电子产品中的无铅焊料的发展背景、特点及要求。根据应用温度不同,无铅焊料可以分为低温、中温和高温无铅焊料。文章综述了它们各自的应用特点、场合及存在的问题和发展前景。     

Phase equilibria and the related properties of Sn-Ag-Cu based Pb-free solder alloys

We have recently developed a thermodynamic database for micro-soldering alloys which consists of the elements Pb, Bi, Sn, Sb, Cu, Ag, Zn, and In. In this paper, the phase equilibria and the related thermodynamic properties of the Sn-Ag-Cu base alloys are presented using this database, alloy systems being one of the promising candidates for Pb-free solders. The isothermal section diagrams of the Sn-Ag-Cu ternary system were experimentally determined by SEM-EDS, x-ray diffraction and metallographic techniques. Based on the present results as well as the previous data on phase boundaries and thermochemical properties, thermodynamic assessment of this system was carried out. The isothermal and vertical section diagrams, liquidus surface, mass fractions of the phase constitution, etc., were calculated. The predictions of surface energy and viscosity were also investigated. Moreover, a non-equilibrium solidification process using the Scheil model was simulated and compared with the equilibrium solidification behavior in some Sn-Ag-Cu base alloys. Calculated results based on the Scheil model were incorporated into a three-dimensional solidification simulation and the prediction of practical solidification procedures was performed.     

Sn-Ag-Cu无铅焊料的可靠性研究

欧盟对电子产品的RoHS法令的实施加快了电子封装钎焊无铅化的步伐。Sn-Ag-Cu焊料以其优良的机械性能和可焊性,逐渐得到了国际社会的认可。文章对无铅焊料的发展过程,Sn-Ag-Cu合金的性能进行了综述,重点介绍了Sn-Ag-Cu焊点的可靠性,包括试验法和有限元法。最后对Sn-Ag-Cu焊料的应用前景进行了展望。     

无铅软钎料的新进展

从环保角度出发,阐述了无铅钎料使用的必然性。介绍了国外无铅钎料的开发情况,尤其是近几年的进展。指出了现阶段研制的无铅钎料与市场要求的差距,提出相应对策。     

无铅焊料的蠕变行为研究进展

无铅焊料已经逐渐代替锡铅焊料广泛应用于电子产品连接技术。但其在环境中的物理和机械性能,尤其是蠕变性能却低于锡铅焊料合金,成为无铅焊料可靠性的主要问题。综述了近些年来无铅焊料蠕变性能的研究,包括蠕变机制、蠕变本构方程、焊点尺寸、无铅合金成分、金属间化合物以及微观组织结构对蠕变性能影响等主要研究热点,并对此领域的发展做出了展望。