The beneficial effect of Zn additions on the microstructure of SnCu and SnCuNi solder joints to Cu substrates
The commercial success as Pb-free solders of alloys based on a trace addition of Ni to Sn-0.7Cu and the academic recognition of the metallurgical effects that deliver the excellent performance in soldering processes and in service, means that Sn-Cu-Ni is now well established as one of the main alloy systems on which the electronics industry depends for the assembly of reliable circuitry. One important effect of the Ni addition is the stabilization of the hexagonal form of the Cu6Sn5 phase that forms at the interface between the solder and the Cu substrate. However, with the limited amount of Ni available in a solder joint, growth of the intermetallic layer by reaction with a copper substrate can result in the Ni level in the Cu6Sn5 falling below that required for stabilization. Increasing the Ni in the solder alloy beyond the level required for optimization of properties such as fluidity that are important in soldering processes can result in the appearance of undesirable high melting point Sn-Ni phases, It would therefore be useful if a second stabilizing element could be introduced to the system to support the effect of the Ni. Ni works as a stabilizer by partially substituting for Cu in the Cu6Sn5 so potential additives were considered on the basis of reports of their partially replacing either Cu or Ni in that crystal structure. Zn was selected for this study because it can partially substitute for Sn in the Cu6Sn5 crystal, potentially complementing the role of Ni. The effect of a Zn addition was studied in the basic Sn-0.7Cu and when there was also an addition of Ni. By itself a Zn addition did not promote a eutectic microstructure in the way that a Ni addition does so powerfully but alone or with Ni it substantially reduced undercooling and in the alloy with both Ni and Zn there was an overall refinement in the near completely eutectic microstructure. In combination with the Ni the Zn significantly refined the grain size of the Cu6Sn5 that formed at the solder/Cu interface. By itself the Zn did not suppress the formation of Cu3Sn at the interface between the Cu and the Cu6Sn5 in the way that Ni does but it does not interfere with that beneficial effect of the Ni. Diffraction studies with high energy synchrotron-generated X-rays confirm that as well as stabilizing the hexagonal form of the Cu6Sn5, Zn reduces the anisotropy of this phase and increases the randomness of the crystal orientation in the intermetallic layer. These effects should result in a stronger intermetallic layer that is less likely to degrade during thermal cycling. The combination of all of these effects mean that an addition of Zn to the widely used Sn-Cu-Ni lead free solders should result in an overall increase in reliability of the solder joint, particularly in harsh environments.
Dissolution in service of the copper substrate of solder joints
It is well known that during service the layer of Cu6Sn5 intermetallic at the interface between the solder and a Cu substrate grows but the usual concern has been that if this layer gets too thick it will be the brittleness of this intermetallic that will compromise the reliability of the joint, particularly in impact loading. There is another level of concern when the Cu-rich Cu3Sn phase starts to develop at the Cu6Sn5/Cu interface and an imbalance in the diffusion of atomic species, Sn and Cu, across that interface results in the formation at the Cu3Sn/Cu interface of Kirkendall voids, which can also compromise reliability in impact loading. However, when, as is the case in some microelectronics, the copper substrate is thin in relation to the volume of solder in the joint an overriding concern is that all of the Cu will be consumed by reaction with Sn to form these intermetallics. This paper reports an investigation into the kinetics of the growth of the interfacial intermetallic, and the consequent reduction in the thickness of the Cu substrate in solder joints made with three alloys, Sn-3.0Ag-0.5Cu, Sn-0.7Cu-0.05Ni and Sn-1.5Bi-0.7Cu-0.05Ni. A simple model developed for the reduction of the Cu thickness as a result of diffusion controlled reaction with Sn to form Cu6Sn5 was found to fit the experimental data well. The results reported in this paper provide an example of the way in which microstructural features that can affect joint reliability are affected by small alloying additions.
Test Procedures for Developing Solder Data
Certain commercial entities, equipment, or materials may be identified in this document in order to describe an experimental procedure or concept adequately. Such identification is not intended to imply recommendation or endorsement by the National Institute of Standards and Technology, nor is it intended to imply that the entities, materials, or equipment are necessarily the best available for the purpose. iii FOREWORD This publication documents standardized test procedures that can produce valid and reproducible mechanical-property data for lead-free solders. Such data speeds the application of lead-free solders in high-volume, automated production of electronic assemblies, especially when current production expectations combine high levels of quality with the lowest cost. Use of standardized procedures facilitates the comparison of data between laboratories and permits the combination of data from different sources into a single, comprehensive database. Most dimensions and temperatures are listed without tolerances. Unless otherwise specified, use ± 5% on dimensions, times, and pressures, and ± 3 °C for temperatures. Many of the procedures assume some skill in the arts of specimen production and testing. Various textbooks and industry brochures (some listed in the Bibliography) can provide background information on these skills and any hazards associated with these procedures.