Thermodynamics and phase diagrams of lead-free solder materials

Many of the existing and most promising lead-free solders for electronics contain tin or tin and indium as a low melting base alloy with small additions of silver and/or copper. Layers of nickel or palladium are frequently used contact materials. This makes the two quaternary systems Ag–Cu–Ni–Sn and Ag–In–Pd–Sn of considerable importance for the understanding of the processes that occur during soldering and during operation of the soldered devices. The present review gives a brief survey on experimental thermodynamic and phase diagram research in our laboratory. Thermodynamic data were obtained by calorimetric measurements, whereas phase equilibria were determined by X-ray diffraction, thermal analyses and metallographic methods (optical and electron microscopy). Enthalpies of mixing for liquid alloys are reported for the binary systems Ag–Sn, Cu–Sn, Ni–Sn, In–Sn, Pd–Sn, and Ag–Ni, the ternary systems Ag–Cu–Sn, Cu–Ni–Sn, Ag–Ni–Sn, Ag–Pd–Sn, In–Pd–Sn, and Ag–In–Sn, and the two quaternary systems themselves, i.e. Ag–Cu–Ni–Sn, and Ag–In–Pd–Sn. Enthalpies of formation are given for solid intermetallic compounds in the three systems Ag–Sn, Cu–Sn, and Ni–Sn. Phase equilibria are presented for binary Ni–Sn and ternary Ag–Ni–Sn, Ag–In–Pd and In–Pd–Sn. In addition, enthalpies of mixing of liquid alloys are also reported for the two ternary systems Bi–Cu–Sn and Bi–Sn–Zn which are of interest for Bi–Sn and Sn–Zn solders.