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

The objective of this review is to study interfacial reactions between pure Sn or Sn-rich solders, and common base metals used in Pb-free electronics production. In particular, the reasons leading to the observed interfacial reactions products and their metallurgical evolution have been analyzed. Results presented in the literature have been critically evaluated with the help of combined thermodynamic–kinetic approach based on the concept of local equilibrium and microstructural knowledge. The following conclusions have been reached: Firstly, the formations of intermetallic compounds in solid/liquid reaction couples are primarily controlled by the dissolution processes of base metals. Other factors that need be considered are the thermodynamic driving force for the formation of intermetallic compounds, their structures and concentration profiles in liquid. Secondly, annealing of solder interconnections in solid state can drastically change the microstructures formed in the solid/liquid reactions, especially if only one of the components in the solder takes part in the interfacial reactions. Thirdly, additional elements can have three major effects on the binary reactions between a base metal and Sn: (i) they can increase or decrease the reaction/growth rates, (ii) the additives can change the physical properties of the phases formed, and (iii) they can form additional reaction products or displace the binary equilibrium phases by forming new reaction products. Finally, if the local stable or metastable equilibrium is established at the interface, stability information together with kinetic considerations can provide a feasible approach to analyze interfacial reactions, which can have significant impact on the reliability of soldered electronics assemblies.

Interfacial reactions between lead-free solders and common base materials

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

IN view of the interest attaching to the vaporisation and diffusion of solids, the following observations may be worthy of record.

The Diffusion of Solids

Due to the inherent toxicity of lead (Pb), environmental regulations around the world have been targeted to eliminate the usage of Pb-bearing solders in electronic assemblies. This has prompted the development of “Pb-free” solders, and has enhanced the research activities in this field. In order to become a successful solder material, Pb-free alloys need to be reliable over long term use. Although many of these alloys possess higher strength than the traditional Sn–Pb ones, there still exist reliability problems such as electromigration and creep. Also, the solderability of many Pb-free alloys is inferior to that of Sn–Pb and any improvement or replacement will be welcomed by industry. In order to develop new Pb-free solders with better properties, trace amounts of rare earth (RE) elements were selected by some researchers as alloying additions into Sn-based solders. These solder alloys are mainly Sn–Ag, Sn–Cu, Sn–Zn and Sn–Ag–Cu. In general, the resulting RE-doped solders are found to have better performances than their original ones. The improvements include better wettability, creep strength and tensile strength. In particular, the increase in creep resistance in some RE-doped alloys gives creep rupture time increases by over four times for Sn–Ag and seven times for Sn–Cu and Sn–Ag–Cu. Like other Sn-based alloys, their creep rates are controlled by dislocation pipe diffusion in the Sn matrix. Also, it was found that the creep rate of these Sn-based alloys can be represented by a single empirical equation. With the addition of RE elements, solders for bonding on difficult substrates such as on semiconductors, diamond, and optical materials have also been developed. This report summarizes the effect of RE elements on the microstructure, mechanical properties, wetting behavior of certain Pb-free solder alloys. As an illustration of the advantage of RE doping, interfacial studies were carried out for electronic interconnections with RE-doped Pb-free alloys. It was found that the intermetallic compound (IMC) layer thickness and the amount of interfacial reaction were reduced in a Ball Grid Array (BGA) package. These results indicate that RE elements would play an important role in providing better electronic interconnections.

Properties of lead-free solder alloys with rare earth element additions

The presence of an intermetallic is often an indication of good wetting in a solder joint. However, excessive intermetallic growth and the brittleness of the intermetallic layer may be detrimental to joint reliability. This study examined the growth and mechanical behavior of interfacial intermetallics between copper and six solder alloys commonly used in electronics assembly. The solder alloys tested were 60Sn-40Pb, 63Sn-37Pb, 95Sn-5Sb, 96.5Sn-3.5Ag, 50Pb-50In, 50Sn-50In, and 40In-40Sn-20Pb. The 50Sn-50In and 40In-40Sn-20Pb exhibited faster solid state growth of the intermetallic layer at 100 °C as compared to the near-eutectic Sn-Pb control solder. The 50In-50Pb had a slower growth rate, relative to 63Sn-37Pb, at the aging temperature of 170 °C due to slower reaction rate kinetics of indium with copper. The 96.5Sn-3.5Ag and 95Sn-5Sb had similar intermetallic growth rates at 170 °C and 205 °C, and the aging was comparable to that of the 63Sn-37Pb alloy. The 95Sn-5Sb solder/copper intermetallic had a faster growth rate of the Cu3Sn layer than was observed in the Sn-Ag or Sn-Pb alloys. Modified fracture toughness and low load indentation tests were used to characterize the mechanical behavior of the intermetallics. The intermetallics were harder than both the base metal and the solder alloy. The fracture behavior of the joints in tension was dependent upon the strength of the solder alloy. Solders with low strengths failed in the solder by plastic deformation. The failure of solders with higher strengths was dependent upon intermetallic thickness. When the intermetallic was thin, fracture occurred in the solder or at the solder/ intermetallic interface. As the interfacial intermetallic thickened, the fracture path moved into the intermetallic layer.

Intermetallic growth and mechanical behavior of low and high melting temperature solder alloys

The use of soft solders, particularly those containing lead, dates back nearly 5,000 years. Solders similar to the materials used to seal the aqueducts of ancient Rome are now an important building block in the manufacture of high-speed computer assemblies. This history attests to the technological versatility of soft solders and, in particular, the solder alloys that contain lead. However, the health effects of prolonged exposure to lead have also been documented; measures to limit human exposure—at the work place and indirectly through the environment—are being considered. The successful introduction of lead-free solders into future electronic products will rely heavily upon their solderability, which can be evaluated by test procedures such as the meniscometer/wetting balance technique and the capillary flow test.

Issues in the replacement of lead-bearing solders

The growth kinetics of intermetallic compound layers formed between four hot-dipped solder coatings and copper by solid state, thermal aging were examined. The solders were l00Sn, 50In-50Sn, 100In, and 63Sn-37Pb (wt.%); the substrate material was oxygen-free, high conductivity Cu. The total intermetallic layer of the 100Sn/Cu system exhibited a combination of parabolic growth at lower aging temperatures and t0.42 growth at the higher temperatures. The combined apparent activation energy was 66 kJ/mol. These results are compared to the total layer growth observed with the 63Sn-37Pb/Cu system which showed parabolic kinetics at similar temperatures and an apparent activation energy of 45 kJ/mol. Both 100Sn and 63Sn-37Pb diffusion couples showed a composite intermetallic layer comprised of Cu3Sn and Cu6Sn5. The intermetallic compound layer formed between In and Cu changed from a CuIn2 stoichiometry at short annealing times to a Cu57In43 composition at longer periods. The growth kinetics were parabolic with an apparent activation energy of 20 kJ/mol. The intermetallic layer growth of the 50In-50Sn/Cu system exhibited extreme variations in the layer thicknesses which prohibited a quantitative assessment of the growth kinetics. The layer was comprised of two compounds: Cu26Sn13In8 which was the dominant phase and a thin layer of Cu17Sn9In24 adjacent to the solder.

Intermetallic compound layer formation between copper and hot-dipped 100In, 50In-50Sn, 100Sn, and 63Sn-37Pb coatings

An experimental study was performed which examined the solid state growth kinetics of the interfacial intermetallic compound layers formed between copper and the high temperature, tin-rich solders 96.5Sn-3.5Ag (wt.%) and 95Sn-5Sb. These results were compared with baseline data from the 100Sn/copper system. Both the 96.5Sn-3.5Ag and 95Sn-5Sb solders exhibited the individual Cu3Sn and Cu6Sn5 layers at the interface; the thickness of the Cu3Sn layer being a function of the aging time and temperature. The total thickness of the intermetallic compound layer formed in the 96.5Sn-3.5Ag solder/copper couple showed a mixture of linear and √t dependencies at the lower temperatures of 70,100, and 135°C, and a t0.42 dependence at 170 and 205°C. The combined apparent activation energy was 59 kJ/mol, the Arrhenius plot showed a knee between the low and high temperature data. The total layer thickness of the 95Sn-5Sb/copper system exhibited √t dependence at the three lower temperatures and t0.42 growth kinetics at 170 and 205°C. The combined apparent activation energy was 61 kJ/mol.

Solid state intermetallic compound growth between copper and high temperature, tin-rich solders—part I: experimental analysis

Bismuth additions of 1% to 10% were made to the 96.5Sn-3.5Ag (wt.%) alloy in an effort to develop a Sn-Ag-Bi ternary composition. A DSC evaluation of the melting properties of the 91.84Sn-3.33Ag-4.83Bi composition suggested the appearance of metastable, short-range order in the atomic structure as a result of low temperature, thermal aging. More extensive solid-state aging studies on 91.84Sn-3.33Ag-4.83Bi/Cu couples resulted in the growth of an intermetallic compound layer at the solder/substrate interface comprised of Cu3Sn and the Cu6Sn5 sub-layers. The growth kinetics of the total layer thickness (x) as a function of solid-state aging time (t) and temperature (T) were represented by the following expression: 

$$x - x_o = A t^n \exp ( - Q/RT)$$

where x0=0.57 × 10−6 m; A=6.22 × 10−3 m/sn; n=0.46±0.15; and Q=49±8 kJ/mol. TEM analysis of the 91.84Sn-3.33Ag-4.83Bi composition indicated that solid-solution and precipitation strengthening mechanisms were a likely consequence of the Bi additions. Contact angle measurements, Cu/solder/Cu solder joint shear strength tests, and microhardness evaluations were also performed on the Sn-Ag-Bi alloys; those results are reported in Part II.

Paul T. Vianco

Papers

Intermetallic growth and mechanical behavior of low and high melting temperature solder alloys

Issues in the replacement of lead-bearing solders

Intermetallic compound layer formation between copper and hot-dipped 100In, 50In-50Sn, 100Sn, and 63Sn-37Pb coatings

Solid state intermetallic compound growth between copper and high temperature, tin-rich solders—part I: experimental analysis

Properties of ternary Sn-Ag-Bi solder alloys: Part I-Thermal properties and microstructural analysis