The objective of this review is to study the effect of minor alloying and impurity elements, typically present in electronics manufacturing environment, on the interfacial reactions between Sn and Cu, which is the base system for Pb-free soldering. Especially, the reasons leading to the observed interfacial reaction layers and their microstructural evolution are analysed. The following conclusions have been reached. Alloying and impurity elements can have three major effects on the reactions between the Sn-based solder and the conductor metal: Firstly, they can increase or decrease the reaction/growth rate. Secondly, additives can change the physical properties of the phases formed (in the case of Cu and Sn, ɛ and η). Thirdly they can form additional reaction layers at the interface or they can displace the binary phases that would normally appear and form other reaction products instead. Further, the alloying and impurity elements can be divided roughly into two major categories: (i) elements (Ni, Au, Sb, In, Co, Pt, Pd, and Zn) that show marked solubility in the intermetallic compound (IMC) layer (generally take part in the interfacial reaction in question) and (ii) elements (Bi, Ag, Fe, Al, P, rare-earth elements, Ti and S) that are not extensively soluble in IMC layer (only change the activities of species taking part in the interfacial reaction and do not usually participate themselves). The elements belonging to category (i) usually have the most pronounced effect on IMC formation. It is also shown that by adding appropriate amounts of certain alloying elements to Sn-based solder, it is possible to tailor the properties of the interfacial compounds to exhibit, for example, better drop test reliability. Further, it is demonstrated that if excess amount of the same alloying elements are used, drastic decrease in reliability can occur. The analysis for this behaviour is based on the so-called thermodynamic–kinetic method.

Impurity and alloying effects on interfacial reaction layers in Pb-free soldering

A review on thermal cycling and drop impact reliability of SAC solder joint in portable electronic products

Effects of nano-Al2O3 additions on microstructure development and hardness of Sn3.5Ag0.5Cu solder

The reactive diffusion between Sn–Ag solders and Cu was experimentally examined during soldering and isothermal annealing. Three sorts of solders with compositions of Sn–3.5Ag, Sn–3.5Ag–0.1Ni and Sn–3.5Ag–0.1Co were used for the experiment. Each solder was soldered on a Cu plate at 523 K (250 °C) for 1–60 s in a pure nitrogen gas, and then the solder/Cu diffusion couple was isothermally annealed at 423 K (150 °C) for 168–1008 h. Due to soldering, only Cu 6 Sn 5 is formed at the interface in each diffusion couple. On the other hand, Cu 3 Sn is produced between Cu 6 Sn 5 and Cu owing to the isothermal annealing. The composition of Cu 6 Sn 5 is (Cu 0.8 Ni 0.2 ) 6 Sn 5 and (Cu 0.93 Ni 0.07 ) 6 Sn 5 on the solder and Cu 3 Sn sides, respectively, in the (Sn–3.5Ag–0.1Ni)/Cu diffusion couple, and it is (Cu 0.9 Co 0.1 ) 6 Sn 5 and (Cu 0.99 Co 0.01 ) 6 Sn 5 on the solder and Cu 3 Sn sides, respectively, in the (Sn–3.5Ag–0.1Co)/Cu diffusion couple. Different rate-controlling processes were suggested for the (Sn–3.5Ag)/Cu, (Sn–3.5Ag–0.1Ni)/Cu and (Sn–3.5Ag–0.1Co)/Cu diffusion couples. Finally, thermodynamic models were herein adopted to explore influences of the additives on the thermodynamic interaction of the component elements and the driving force for the growth of intermetallics.

Effects of Co and Ni addition on reactive diffusion between Sn–3.5Ag solder and Cu during soldering and annealing

The thermal fatigue properties of Sn-xAg-0.5Cu (x=1, 2, 3, and 4 in mass%) flip-chip interconnects were investigated to study the effect of silver content on thermal fatigue endurance. The solder joints with lower silver context (x=1 and 2) had a greater failure rate compared to those with higher silver content (x=3 and 4) in thermal fatigue testing. Cracks developed in the solders near the solder/chip interface for all joints tested. This crack propagation may be mainly governed by the nature of the solders themselves because the strain-concentrated area was similar for tested alloys independent of the silver content. From the microstructural observation, the fracture was a mixed mode, transgranular and intergranular, independent of the silver content. Higher silver content alloys (x=3 and 4) had finer Sn grains before thermal cycling according to the dispersion of the Ag3Sn intermetallic compound, and even after the cycling, they suppressed microstructural coarsening, which degrades the fatigue resistance. The fatigue endurance of the solder joints was strongly correlated to the silver content, and solder joints with higher silver content had better fatigue resistance.

S.H. Huh

Papers

Effects of fourth alloying additive on microstructures and tensile properties of Sn–Ag–Cu alloy and joints with Cu