Practically all microelectronic assemblies in use today utilize Pb–Sn solders for interconnection. With the advent of chip scale packaging technologies, the usage of solder connections has increased. The most widely used Pb–Sn solder has the eutectic composition. Emerging environmental regulations worldwide, most notably in Europe and Japan, have targeted the elimination of Pb usage in electronic assemblies, due to the inherent toxicity of Pb. This has made the search for suitable “Pb-free” solders an important issue for microelectronics assembly. Approximately 70 Pb-free solder alloy compositions have been proposed thus far. There is a general lack of engineering information, and there is also significant disparity in the information available on these alloys. The issues involved can be divided into two broad categories: manufacturing and reliability/performance. A major factor affecting alloy selection is the melting point of the alloy, since this will have a major impact on the other polymeric materials used in microelectronic assembly and encapsulation. Other important manufacturing issues are cost, availability, and wetting characteristics. Reliability related properties include mechanical strength, fatigue resistance, coefficient of thermal expansion and intermetallic compound formation. The data available in the open literature have been reviewed and are summarized in this paper. Where data were not available, such as for corrosion and oxidation resistance, chemical thermodynamics was used to develop this information. While a formal alloy selection decision analysis methodology has not been developed, less formal approaches indicate that Sn-rich alloys will be the Pb-free solder alloys of choice, with three to four alloys being identified for each of the different applications. Research on this topic continues at the present time at a vigorous pace, in view of the imminence of the issue.

Lead-free Solders in Microelectronics

Next-generation high-performance structural materials are required for lightweight design strategies and advanced energy applications. Maraging steels, combining a martensite matrix with nanoprecipitates, are a class of high-strength materials with the potential for matching these demands. Their outstanding strength originates from semi-coherent precipitates, which unavoidably exhibit a heterogeneous distribution that creates large coherency strains, which in turn may promote crack initiation under load. Here we report a counterintuitive strategy for the design of ultrastrong steel alloys by high-density nanoprecipitation with minimal lattice misfit. We found that these highly dispersed, fully coherent precipitates (that is, the crystal lattice of the precipitates is almost the same as that of the surrounding matrix), showing very low lattice misfit with the matrix and high anti-phase boundary energy, strengthen alloys without sacrificing ductility. Such low lattice misfit (0.03 ± 0.04 per cent) decreases the nucleation barrier for precipitation, thus enabling and stabilizing nanoprecipitates with an extremely high number density (more than 1024 per cubic metre) and small size (about 2.7 ± 0.2 nanometres). The minimized elastic misfit strain around the particles does not contribute much to the dislocation interaction, which is typically needed for strength increase. Instead, our strengthening mechanism exploits the chemical ordering effect that creates backstresses (the forces opposing deformation) when precipitates are cut by dislocations. We create a class of steels, strengthened by Ni(Al,Fe) precipitates, with a strength of up to 2.2 gigapascals and good ductility (about 8.2 per cent). The chemical composition of the precipitates enables a substantial reduction in cost compared to conventional maraging steels owing to the replacement of the essential but high-cost alloying elements cobalt and titanium with inexpensive and lightweight aluminium. Strengthening of this class of steel alloy is based on minimal lattice misfit to achieve maximal precipitate dispersion and high cutting stress (the stress required for dislocations to cut through coherent precipitates and thus produce plastic deformation), and we envisage that this lattice misfit design concept may be applied to many other metallic alloys.

Ultrastrong steel via minimal lattice misfit and high-density nanoprecipitation

Lead-free soldering has emerged as one of the key technologies for assembling in environmental-conscious electronics. Among several candidate alloys, the Sn–Ag–Cu alloy family is believed to be the first choice with the combination of other alloys such as Sn–Zn–Bi, Sn–Cu and Sn–Bi–Ag. Phase diagrams of lead-free alloy systems have been intensively examined by using careful thermal and microstructural analysis combined with the thermodynamic calculation such as the CLAPHAD method. The Cu6Sn5/Cu3Sn layers are formed at most lead-free solder alloy/Cu interfaces, while Cu–Zn compound layers are formed in the Sn–Zn/Cu system. Growth kinetics of intermetallic layers both in solid-state and in soldering are also discussed. Creep and fatigue phenomena are also reviewed. In many aspects of lead-free soldering, much more work is required to establish a sound scientific basis to promote their applications.

Advances in lead-free electronics soldering

The microstructures and tensile properties of three typical Sn–Ag–Cu alloys, Sn–30wt%Ag–05wt%Cu, Sn–35wt%Ag–07wt%Cu and Sn–39wt%Ag–06wt%Cu, prepared under three different cooling conditions were evaluated after casting The microstructures of all rapidly cooled specimens consisted of the eutectic phase of β-Sn with fine fibrous Ag3Sn dispersion surrounding primary β-Sn grains The slowly cooled Sn–35Ag–07Cu and Sn–39Ag–06Cu alloys exhibited additional large primary Ag3Sn platelets, while the Sn–30Ag–05Cu did not For all alloys, both ultimate tensile strength and 02% proof stress increased with increasing strain-rates in tensile tests Lowering cooling speed decreased tensile strength Elongation increased with an increasing strain rate from 10−5 to 10−2 s−1, and decreased slightly at 10−1 s−1 for the rapidly cooled specimens Elongation remarkably decreased for the slowly cooled Sn–35Ag–07Cu and Sn–39Ag–06Cu alloys, a degradation attributable to the formation of large primary Ag3Sn platelets

Effects of cooling speed on microstructure and tensile properties of Sn–Ag–Cu alloys

Review of non-reactive and reactive wetting of liquids on surfaces.

Because of the high homologous operation temperature of solders used in electronic devices, time and temperature dependent relaxation and creep processes affect their mechanical behavior In this paper, two eutectic lead-free solders (965Sn-35Ag and 91Sn-9Zn) are investigated for their creep and stress relaxation behavior The creep tests were done in load-control with initial stresses in the range of 10-22 MPa at two temperatures, 25 and 80°C The stress relaxation tests were performed under constant-strain conditions with strains in the range of 03-24% and at 25 and 80°C Since creep/relaxation processes are active even during monotonie tensile tests at ambient temperatures, stress-strain curves at different temperatures and strain rates provide insight into these processes Activation energies obtained from the monotonic tensile, stress relaxation, and creep tests are compared and discussed in light of the governing mechanisms These data along with creep exponents, strain rate sensitivities and damage mechanisms are useful for aiding the modeling of solder interconnects for reliability and lifetime prediction Constitutive modeling for creep and stress relaxation behavior was done using a formulation based on unified creep plasticity theory which has been previously employed in the modeling of high temperature superalloys with satisfactory results

Creep, stress relaxation, and plastic deformation in Sn-Ag and Sn-Zn eutectic solders

Aging characteristics and mechanical properties of 1600 MPa body-centered cubic Cu and B2-NiAl precipitation-strengthened ferritic steel

An investigation of a low-carbon, Fe-Cu–based steel, for Naval ship hull applications, with a yield strength of 965 MPa, Charpy V-notch absorbed impact-energy values as high as 74 J at –40 °C, and an elongation-to-failure greater than 15 pct, is presented. The increase in strength is derived from a large number density (approximately 1023 to 1024 m−3) of copper-iron-nickel-aluminum-manganese precipitates. The effect on the mechanical properties of varying the thermal treatment was studied. The nanostructure of the precipitates found within the steel was characterized by atom-probe tomography. Additionally, initial welding studies show that a brittle heat-affected zone is not formed adjacent to the welds.

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High-Strength Low-Carbon Ferritic Steel Containing Cu-Fe-Ni-Al-Mn Precipitates

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.

Semyon Vaynman

Papers

Creep, stress relaxation, and plastic deformation in Sn-Ag and Sn-Zn eutectic solders

Aging characteristics and mechanical properties of 1600 MPa body-centered cubic Cu and B2-NiAl precipitation-strengthened ferritic steel

High-Strength Low-Carbon Ferritic Steel Containing Cu-Fe-Ni-Al-Mn Precipitates

Investigation of multi-component lead-free solders

Stability and elastic properties of L12-(Al,Cu)3(Ti,Zr) phases: Ab initio calculations and experiments