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.     

Influence of 0.03?wt.% Carbon Black Addition on the Performance of Sn-3.5Ag Lead-Free Solder

In an effort to improve the performance of lead-free solder, Sn-3.5?wt.%Ag (Sn-3.5Ag) solder alloy with 0.03?wt.% carbon black was prepared under high pressure (5.5?GPa) and high temperature (1200°C). We have investigated the microstructure, melting behavior, and mechanical properties of the alloy using x-ray diffraction, differential scanning calorimetry (DSC), Vickers hardness testing, tensile testing, and scanning electron microscopy (SEM). The melting point was found to be unchanged, while the hardness and the tensile strength increased with the addition of carbon black. SEM images showed that the average thickness of the intermetallic compound (IMC) layer decreased with the addition of carbon black, indicating improvement in solder joint reliability.     

Experimental Investigation and Thermodynamic Assessment of Phase Equilibria in the Ag-Au-Sn System

The phase equilibria of the Ag-Au-Sn ternary system at 300°C, 400°C, and 500°C were experimentally investigated. The equilibrium compositions of the equilibrated alloys and diffusion couples between Ag _x Au_1−x (x = 0.25, 0.75) alloys and liquid Sn were determined by electron probe microanalysis (EPMA). The phase transformations were investigated by means of differential scanning calorimetry (DSC). Based on the experimental data of phase equilibria and thermodynamic properties, the thermodynamic assessment of the Ag-Au-Sn system was carried out based on the calculation of phase diagrams (CALPHAD) method. The thermodynamic parameters for describing the Gibbs free energies of the phases were optimized, and reasonable agreement between the calculations and experimental data was obtained.     

Phase Equilibria in the Sn-Ni-Zn Ternary System: Isothermal Sections at 200°C, 500°C,and 800°C

In the electronic packaging field, the Sn-Zn alloy system has been recommended as a high-temperature Pb-free solder. There is a need for thermodynamic data on the Sn-Ni-Zn ternary system. Such data would serve as a basis for understanding the interfacial reaction between Sn-Zn high-temperature solder and Ni substrates and for thermodynamically evaluating the proper composition level of Ni and Zn in Sn-based solder. This study has investigated the phase equilibria of the Sn-Ni-Zn ternary system at 800°C, 500°C, and 200°C (for Ni composition of less than 60 at.%). Scanning electron microscopy (SEM), x-ray diffraction (XRD), and electron probe microanalysis (EPMA) were used to identify the equilibrium phases. On the basis of the experimental data and thermodynamic parameters, the isothermal sections of the Sn-Ni-Zn ternary system have been described, considering the ternary solubility in the binary phases and newfound ternary phases τ1 (Sn₃Ni₄Zn₃) and τ2 (Sn₄Ni₄Zn₂).     

Microstructure and In Situ Observations of Undercooling for Nucleation of <Emphasis Type="Italic">β</Emphasis>-Sn Relevant to Lead-Free Solder Alloys

Difficult nucleation of β-Sn during solidification of tin and tin-based lead-free solder alloys can result in high degrees of undercooling of the liquid prior to solidification. The undercooling can produce solder joints with large grains, anisotropic behavior, and undesirable mechanical properties. This paper describes our examination of the amount of undercooling of tin on both graphite (non-wetting) and copper (wetting) surfaces using in situ x-ray diffraction. The microstructure was further characterized by optical microscopy, scanning electron microscopy, and electron backscattering diffraction imaging microscopy. Undercoolings as high as 61°C were observed for Sn solidified on graphite, while lower undercoolings, up to 30°C, were observed for Sn solidified on copper. The microstructure of the high purity Sn sample solidified on graphite showed very few grains in the cross-section, while the commercially pure Sn sample solidified with only one grain and was twinned. Tin solidified on copper contained significant amounts of copper in the tin, intermetallic phase formation at the interface, and a eutectic microstructure.     

Intermetallic Formation and Fluidity in Sn-Rich Sn-Cu-Ni Alloys

This paper investigates the phase equilibria and solidification behavior of Sn-Cu-Ni alloys with compositions in the range of 0 wt.% to 1.5 wt.% Cu and 0 wt.% to 0.3 wt.% Ni. The isothermal section at 268°C in the Sn-rich corner was determined. No evidence for a ternary phase was found, and the section is in good agreement with past experimental studies that report wide solubility ranges for (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄. The vacuum fluidity test was applied to compositions that are liquid at 268°C to map the variation in microstructure and flow behavior with composition in this system. Significant variations in fluidity length were measured among the Sn-Cu-Ni alloys, and the variations correlate with the microstructure that develops during solidification. The generated fluidity map enables the selection of Sn-Cu-Ni solder compositions that exhibit good fluidity behavior during solidification and form near-eutectic microstructures.     

Intermetallic compounds and adhesion strength between the Sn-9Zn-1.5Ag-0.5Bi lead-free solder and unfluxed Cu substrate

The intermetallic compounds (IMCs) formed at the interface between the Sn-9Zn-1.5Ag-0.5Bi lead-free solder alloy and unfluxed Cu substrate have been investigated by x-ray diffraction, optical microscopy, scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). The melting point and melting range of the Sn-9Zn-1.5Ag-0.5Bi solder alloy are determined as 195.9°C and 10°C, respectively, by differential scanning calorimetry (DSC). Cu₆Sn₅ and Cu₅Zn₈ IMCs are formed between the Sn-9Zn-1.5Ag-0.5Bi/unfluxed Cu substrate wetted at 250°C for 10 sec. The interfacial adhesion strength changes from 10.27±0.68 MPa to 8.58±0.59 MPa when soldering time varies from 10 sec to 30 sec at 250°C.     

Lead contamination of a transient liquid-phase-processed Sn-Bi lead-free solder paste

The influence of Pb contamination on the solidification behavior of a transient liquid-phase powder-processed Sn-Bi solder paste has been studied using differential scanning calorimetry. The development of low-temperature ternary reactions was found to be very sensitive to both the Pb and Bi content of the solder. Solders with high Bi content favored the formation of the ternary eutectic reaction. Solders with high Pb contents favored the formation of a ternary peritectic reaction. These results agree very well with solidification predictions present in the literature for ternary Sn-Bi-Pb alloys. In particular, the dependence of ternary reactions on composition is due to a change in solidification path. Alloy compositions which mark the transition from one path to the next were identified.     

Effects of Forming Processes on the Microstructure and Solderability of Sn-3.5Ag Eutectic Solder Ribbons as well as the Mechanical Properties of Solder Joints

Two kinds of Sn-3.5Ag eutectic solder ribbons of 0.13 mm thickness were prepared by a casting–rolling process and a rapid solidification process. The microstructure, phase constitution, melting characteristics, wetting behavior and soldering strength were compared using optical microscopy, scanning electron microscopy, x-ray diffraction, energy dispersive spectroscopy, differential scanning calorimetry and a MTS ceramic testing system. The results show that the microstructure of rapidly solidified solder is finer and more uniform, and the eutectic structure has a higher solid solubility and more homogeneous distribution of Ag in a Sn matrix. The solidus and liquidus temperature decreased, resulting in a 3.3% reduction of pasty range. In addition, the wettability and shear strength of the solder joints increased by 13.2% and 7.9%, respectively.     

Primary solidification phases of the Sn-rich Sn-Ag-Cu-Ni quaternary system

The eutectic and near-eutectic Sn-Ag-Cu solders are the most promising lead-free solders, and nickel is frequently used as the barrier layer material. Nickel dissolves into the molten Sn-Ag-Ni alloy during the soldering process, and the ternary solder becomes a Sn-Ag-Cu-Ni quaternary melt near the nickel substrate. Liquidus projection is the projection of the liquidus trough and it delineates the boundaries of various primary solidification phases. Information of liquidus projection is helpful for understanding the alloys’ solidification behavior. This study prepared the Sn-Ag-Cu-Ni alloys of various compositions at the Sn-rich corner. The alloys were melted at higher temperatures and solidified in air. The solidified alloys were metallographically examined to determine the phases formed, especially the primary solidification phases. No ternary or quaternary compounds were found. The knowledge of the primary solidification phases, phase formation sequences, and reaction temperatures determined in this study were put together with all of the available liquidus projections of the constituent ternary systems to determine the primary solidification phases of the quaternary Sn-Ag-Cu-Ni system at the Sn-rich corner.     

Characterization of the melting and wetting of Sn-Ag-X solders

There is tremendous interest at present with Pb-free solder assembly in the surface mount assembly industry in response to recent Japanese and European initiatives and proposed governmental restrictions regarding Pb usage and disposal. Many different solder alloys have been proposed as potential Pb-free solder replacements and the most promising of these fall into the general alloy families of tin-silver (Sn-Ag), tin-silver-copper (Sn-Ag-Cu) and tin-silver-bismuth (Sn-Ag-Bi). Published melting point data on some of these alloys indicates that they should be capable of reduced reflow temperatures relative to the commonly available Sn-3.5Ag alloy, which melts at 221°C. Differential scanning calorimetry (DSC) and reflow visualization was used to characterize the melting and wetting of the Pb-free alloys and generate the practical reflow temperature requirements. This was compared to the DSC data to gain insight on the meaning of the DSC melting data for surface mount applications. The results show that, in general, the wetting performance of the Sn-Ag-Bi alloys are more similar to Sn-Ag and Sn-Ag-Cu than would be predicted by the major onset melting temperature data as measured by the DSC     

Effects of Silver and Antimony Content in Lead-Free High-Temperature Solders of Bi-Ag and Bi-Sb on Copper Substrate

Replacing high-temperature leaded solders with lead-free alternatives is an important issue in the electronics industry. This study investigates the viability of lead-free Bi-Ag and Bi-Sb solder alloys, ranging in composition from 1.5 to 5 wt.% Ag and Sb. The effects of melting point, wetting angle, microstructure, and morphology were analysed by differential scanning calorimetry, optical microscopy, and scanning electron microscope–energy dispersive x-ray analysis. The results showed that all tested alloys had suitable melting temperatures, ranging from 271 to 276°C. The wetting angle increased by raising the Sb content, but, in contrast, by increasing the wt.% of Ag, the wetting angle decreased. A Cu-rich phase was present in all Bi-Ag alloys, The Cu-rich phase was also present in decreasing amounts with increasing Sb, but, with 5Sb, there was no Cu-rich phase, and a Cu3Sb intermetallic compound was present in the interface and as precipitates in the solder. Grooving along Cu grain boundaries was observed at the interface for the rest of the alloys.     

Experimental Determination and Thermodynamic Modeling of the Sn-Rich Corner of the Ternary Ni-Pd-Sn Phase Diagram at 250°C

The Sn-rich portion of the phase diagram for the Ni-Pd-Sn ternary system was preliminarily obtained by interpolation of the three constituent binary systems using the Muggianu method. Based on this proposition, 23 Ni-Pd-Sn alloys were prepared and annealed at 250°C. The annealed alloys were analyzed by scanning electron microscopy, electron probe microanalysis, electron backscatter diffraction, and x-ray diffraction. All the binaries adjacent to the Sn-rich corner (i.e., PdSn₄, PdSn₃, PdSn₂, and Ni₃Sn₄) were found to have remarkable ternary solubility. The experimental results presented herein, together with a thermodynamic interpolation of the ternary system based on the results from the binary systems, were used to calculate the ternary phase diagram using the calculation of phase diagrams (CALPHAD) method. A substitution model was used to describe the Gibbs free energies of the liquid and solid solution phases, and a sublattice model was used to describe intermetallic compounds. A consistent set of thermodynamic parameters was obtained, ultimately leading to a better fit between the calculated results and the experimental data for this system.     

Influence of Surface Segregation on Wetting of Sn-Ag-Cu (SAC) Series and Pb-Containing Solder Alloys

Wetting of Sn-Ag-Cu (SAC) series solder alloys to solid substrates is strongly influenced by surface segregation of low-level bulk impurities in the alloys. We report in situ and real-time Auger electron spectroscopy measurements of SAC alloy surface compositions as a function of temperature as the alloys are taken through the melting point. A dramatic increase in the amount of surface C (and frequently O) is observed with temperature, and in some cases the alloy surface is nearly 80 at.% C at the melting point. The C originates from low-level impurities incorporated during alloy synthesis and inhibits wetting because C acts as a blocking layer to reaction between the alloy and substrate. A similar phenomenon has been observed over a wide range of (SAC and non-SAC) alloys synthesized by a variety of techniques. That solder alloy surfaces at melting have a radically different composition from the bulk uncovers a key variable that helps to explain the wide variability in contact angles reported in previous studies of wetting and adhesion.     

Growth of Sn and intermetallic compounds in Sn-Ag-Cu solder

The microstructure of the Sn-Ag-Cu solder is examined by optical microscopy and scanning electron microscopy (SEM) for various compositions near the ternary eutectic for different cooling rates from the solder melt. Focus is on the size and orientation of Sn grains as indicated by cross-polarized, light optical microscopy, and pole figures from x-ray diffraction. We find that both composition and cooling rate have strong influences on Sn grain size, with Sn grain size increasing an order of magnitude as Cu concentration increases from 0% to 1.1%. Cyclic growth twinning, with twinning angles near 60°, is observed in Sn-Ag-Cu alloys near the composition Sn-3.9Ag-0.6Cu.     

Liquidus Projection and Solidification of the Sn-In-Cu Ternary Alloys

Sn-In alloys are promising low-melting-point Pb-free solders. Knowledge of the ternary Sn-In-Cu liquidus projection is important for Sn-In solder applications. Sn-In-Cu ternary alloys were prepared and their primary solidification phases and phase-transformation temperatures during heating were determined. The liquidus projection of the Sn-In-Cu ternary system was determined based on the primary solidification phase at different compositional regimes, the phase-transformation temperatures of the ternary alloys, the phase boundaries and reaction temperatures of the constituent binary systems, and the available ternary Sn-In-Cu data in the literature. No ternary compound was found in the as-cast alloys. The Sn-In-Cu liquidus projection has 11 primary solidification phase regions and seven ternary invariant reactions with the liquid phase, and η-(Cu₆Sn₅,Cu₂In) has a very large compositional regime as the primary solidification phase. A very interesting phenomenon that was also observed is that the solidification paths of some Sn-In-Cu alloys surpass the liquidus trough after their intersections.     

High-temperature variable melting point Sn-Sb lead-free solder pastes using transient liquid-phase powder processing

During this investigation, a high-temperature, variable melting point (VMP) Sn-Sb solder paste was developed. The solder was created by mixing pure Sn and Sb powders together with a flux to form a paste. The proper choice of flux composition and Sn powder size resulted in a Sn-10wt.%Sb solder paste that had an initial melting point of 232°C and solder ball formation at peak temperatures as low as 241°C. This represents a significant reduction in the process temperature that would normally be required for a prealloyed solder with a melting point of 250°C. When this solder paste is reheated, significant remelting does not take place until a temperature above 241°C is reached. In this way, the solder exhibits a VMP. Experiments indicate that this VMP behavior is due to isothermal solidification (or freezing) at the solder temperature owing to the partial transient liquid-phase (TLP) behavior of the solder powder paste.     

Early Interfacial Reaction and Formation of Intermetallic Compounds in the Sn-3.5Ag/Cu Soldering System

The early interfacial reaction in the Sn-3.5Ag/Cu soldering system and the system’s premelting behavior were found and characterized by differential scanning calorimetry incorporated into the reflow process. The results show that the early interfacial reaction occurs by way of melting and wetting of the solder layer adjacent to the Cu substrate at a temperature nearly 4°C below the actual melting point of Sn-3.5Ag solder due to solid-state diffusion of Cu atoms into the Sn-3.5Ag binary solder. Consequently, the early interfacial reaction brings about formation of Cu-Sn intermetallic compounds (IMCs) at a temperature below the melting point of Sn-3.5Ag, and a prolonged early interfacial reaction can lead to change of the Cu-Sn IMC morphology from planar-like to scallop-like and promote excessive growth of IMCs at the interface.     

Effect of Composition on Thermoelectric Properties in PbTe-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Composites

The solidification of alloys in the Bi₂Te₃-PbTe pseudobinary system at off- and near-eutectic compositions was investigated for their microstructure and thermoelectric properties. Dendritic and lamellar structures were clearly observed due to the phase separation and the existence of a metastable ternary phase. In this system, three phases with different compositions were observed: binary Bi₂Te₃, PbTe, and metastable PbBi₂Te₄. The Seebeck coefficient, electrical resistivity, and thermal conductivity of ternary alloys as well as binary compounds were measured. The phonon thermal conductivities of Pb-Bi-Te alloys were lower than those in binary PbTe and Bi₂Te₃, which could have resulted from the increased interfacial area between phases due to the existence of the metastable ternary phase and the resultant phase separation.     

A Study on the Physical Properties and Interfacial Reactions with Cu Substrate of Rapidly Solidified Sn-3.5Ag Lead-Free Solder

A rapidly solidified Sn-3.5Ag eutectic alloy produced by the melt-spinning technique was used as a sample in this research to investigate the microstructure, thermal properties, solder wettability, and inhibitory effect of Ag₃Sn on Cu₆Sn₅ intermetallic compound (IMC). In addition, an as-cast Sn-3.5Ag solder was prepared as a reference. Rapidly solidified and as-cast Sn-3.5Ag alloys of the same size were soldered at 250°C for 1 s to observe their instant melting characteristics and for 3 s with different cooling methods to study the inhibitory effect of Ag₃Sn on Cu₆Sn₅ IMC. Experimental techniques such as scanning electron microscopy, differential scanning calorimetry, and energy-dispersive spectrometry were used to observe and analyze the results of the study. It was found that rapidly solidified Sn-3.5Ag solder has more uniform microstructure, better wettability, and higher melting rate as compared with the as-cast material; Ag₃Sn nanoparticles that formed in the rapidly solidified Sn-3.5Ag solder inhibited the growth of Cu₆Sn₅ IMC during aging significantly much strongly than in the as-cast material because their number in the rapidly solidified Sn-3.5Ag solder was greater than in the as-cast material with the same soldering process before aging. Among the various alternative lead-free solders, this study focused on comparison between rapidly solidified and as-cast solder alloys, with the former being observed to have better properties.