Solder is widely used to connect chips to their packaging substrates in flip chip technology as well as in surface mount technology. At present, the electronic packaging industry is actively searching for Pb-free solders due to environmental concern of Pb-based solders. Concerning the reliability of Pb-free solders, some electronic companies are reluctant to adopt them into their high-end products. Hence, a review of the reliability behavior of Pb-free solders is timely. We use the format of “case study” to review six reliability problems of Pb-free solders in electronic packaging technology. We conducted analysis of these cases on the basis of thermodynamic driving force, time-dependent kinetic processes, and morphology and microstructure changes. We made a direct comparison to the similar problem in SnPb solder whenever it is available. Specifically, we reviewed: (1) interfacial reactions between Pb-free solder and thick metalliztion of bond-pad on the substrate-side, (2) interfacial reactions between Pb-free solder and thin-film under-bump metallization on the chip-side, (3) the growth of a layered intermetallic compound (IMC) by ripening in solid state aging of solder joints, (4) a long range interaction between chip-side and substrate-side metallizations across a solder joint, (5) electromigration in flip chip solder joints, and finally (6) Sn whisker growth on Pb-free finish on Cu leadframe. Perhaps, these cases may serve as helpful references to the understanding of other reliability behaviors of Pb-free solders.

Six cases of reliability study of Pb-free solder joints in electronic packaging technology

We review the status of (Ti,Al)N based coatings obtained by various physical vapor deposition (PVD) techniques and compare their properties. PVD techniques based on sputtering and cathodic arc methods are widely used to deposit wear resistant (Ti,Al)N coatings. These techniques were further modified to improve the metal ionization rate and to eliminate macrodroplets from plasma streams. We summarize manufacture of target/cathode, substrate materials for deposition of coatings, deposition parameters, and the effect of deposition parameters on the physical and mechanical properties of (Ti,Al)N coatings. It is shown that (Ti,Al)N coatings by PVD enhance the wear, thermal, and oxidation resistance of a wide variety of tool materials. We discuss the wear resistant properties of (Ti,Al)N for various machining applications as compared with coatings such as TiN, Ti(C,N) and (Ti,Zr)N. High hardness (∼28–32 GPa), relatively low residual stress (∼5 GPa), superior oxidation resistance, high hot hardness, and low thermal conductivity make (Ti,Al)N coatings most desirable in dry machining and machining of abrasive alloys at high speeds. Multicomponent coatings based on different metallic and nonmetallic elements combine the benefit of individual components leading to a further refinement of coating properties. Alloying additions such as Cr and Y drastically improve the oxidation resistance, Zr and V improve the wear resistance, whereas, Si increases the hardness and resistance to chemical reactivity of the film. Addition of boron improves the abrasive wear behavior of Ti–Al based coatings due to the formation of TiB2 and BN phases depending on the deposition conditions. Hafnium based nitrides and carbides have potential for resistance to flank and crater wear. The presence of a large number of interfaces between individual layers of a multilayered structure results in a drastic increase in hardness and strength. (Ti,Al)N multilayer super lattice coatings with lattice periodicity of 5–10 nm allow creation of coatings with different properties than PVD deposited single layered thick coatings with columnar grain structure. A range of (Ti,Al)N based multilayers containing layers of (Ti,Al)CN, (Ti,Nb)N, TiN, AlN/TiN, CrN, Mo and WC are also reviewed. It is now possible to design new wear resistant or functional coatings based on a multilayer or a multicomponent system to meet the demanding applications of advanced materials.

Single layer and multilayer wear resistant coatings of (Ti,Al)N: a review

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

Damascene copper electroplating for on-chip interconnections, a process that we conceived and developed in the early 1990s, makes it possible to fill submicron trenches and vias with copper without creating a void or a seam and has thus proven superior to other technologies of copper deposition. We discuss here the relationship of additives in the plating bath to superfilling, the phenomenon that results in superconformal coverage, and we present a numerical model which accounts for the experimentally observed profile evolution of the plated metal.

Damascene copper electroplating for chip interconnections

Journal of Applied physics,Vol.33 : 1962年に発表されたレオロジー関連の論文

Three kinds of Sn-Ag-based lead-free solders, Sn-3.5Ag-0.7Cu, Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge, and Sn-3.5Ag-0.07Ni (in wt.%), were selected to explore the effect of microelements (Ni and Ge) on the interfacial reaction between the solder and the Cu substrate. The thickness of the interfacial intermetallics formed with the Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge and Sn-3.5Ag-0.07Ni solders is several times that of the Sn-3.5Ag-0.7Cu solder. The added microelements converted the feature of interfacial intermetallics from pebble shape to worm shape. However, the results of x-ray diffraction (XRD) analysis suggest that the interfacial intermetallics formed with both solders have the same crystal structure. The results of energy dispersive spectroscopy (EDS) analysis show that the major interfacial intermetallic formed with the Sn-3.5Ag-0.7Cu solder is Cu6Sn5, while it is (Cux,Ni1−x)6Sn5 with Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge. Ni influences the interfacial intermetallics and plays the influential role on the difference of interfacial reaction rate between liquid solder and solid Cu and the morphology of interfacial intermetallics. Additionally, the growth kinetics of the interfacial intermetallic compounds (IMCs) formed in the systems of Cu/Sn-3.5Ag-0.7Cu and Cu/Sn-3.5Ag-0.07Ni at high-temperature storage was also explored.

Effect of microelements addition on the interfacial reaction between Sn-Ag-Cu solders and the Cu substrate

The interaction kinetics and compound formation between electroless NiP and solder

The oxidation of 91Sn-9(95Zn-5Al) solder in theliquid state, 250°C, was studied by thermalgravimetric analysis (TGA). The oxidation behavior of63Sn-37Pb, 91Sn-9Zn, 99.4Sn-0.6Al, and Sn was alsoinvestigated for comparison. The weight gains per unitsurface area descend in the order: 63Sn-37Pb > Sn> 91Sn-9Zn > 91Sn-9(95Zn-5Al) > 99.4Sn-0.6Al.The initial weight gains of the materials investigated increase linearly with reaction time, whileparabolic behavior exists after the linear stage. Therate constants of the oxidation reaction for the tworeaction stages were determined. Activation energies for oxidation of the five materials weredetermined in the range of 250 to 400°C. Theactivation energies, derived from the linear rateconstants for the early stages of oxidation, are 27.7kJ/mole for 99.4Sn-0.6Al, 23.3 kJ/mole for 91Sn-9Zn, 21.4kJ/mole for 91Sn-9(95Zn-5Al), 20.5 kJ/mole for63Sn-37Pb, and 19.8 kJ/mole for Sn. Thesurface-oxidation behavior was investigated further withelectron spectroscopy for chemical analysis (ESCA) and Auger electronspectroscopy (AES). AES profiles showed that oxides ofZn and Al formed on 91Sn-9Zn and 91Sn-9(95Zn-5Al)solders, while tin oxide is formed on 63Sn-37Pbsolder.

High-Temperature Oxidation of a Sn-Zn-Al Solder

A process for manufacturing Cu/electroless Ni/Sn-Pb solder bump is discussed in this paper. An attempt to replace zincation with a Cu film as an active layer for the electroless Ni (EN) deposition on Al electrode on Si wafer is presented. Cu/electroless Ni is applied as under bump metallurgy (UBM) for solder bump. The Cu film required repeated etches with nitric acid along with activation to achieve a satisfactory EN deposit. Fluxes incorporating rosin and succinic acid were investigated for wetting kinetics and reflow effectiveness of the electroplated solder bump. The solder plating current density and the reflow condition for achieving solder bumps with uniform bump height were described. The Cu/EN/Sn-Pb solder system was found to be successfully produced on Al terminal in this study that avoids using zincating process.

Kwang-Lung Lin

Papers

Effect of microelements addition on the interfacial reaction between Sn-Ag-Cu solders and the Cu substrate

The interaction kinetics and compound formation between electroless NiP and solder

High-Temperature Oxidation of a Sn-Zn-Al Solder

Manufacturing of Cu/electroless nickel/Sn-Pb flip chip solder bumps

The microstructure and property variations of metals induced by electric current treatment: A review