Materials issues in the transition to lead-free solder alloys and joint miniaturization HuangZhiheng 2017 Within the context of the imminent implementation of the Pb-free soldering in Europe in 2006, this thesis addresses the gap in understanding that has emerged in the fundamental materials issues between well-understood and mature lead-containing solders and a plethora of new, Pb-free solders for which there are neither long term reliability data nor understanding of the materials behaviour and how these might be influenced by manufacture and in-service conditions. In addition, this thesis also addresses the question as to whether the solder joint size and geometry could become a reliability issue and therefore affect the implementation of the Pb-free solders in ultrafine micro joints. Thermodynamic calculations using MTDATA (developed by the National Physical Laboratory, NPL, UK) together with a thermodynamic database for solders under either equilibrium or Scheil conditions, have shown their usefulness in Pb-free solder design and processing, generating a wealth of information in respect of the temperature dependence of phase formation and composition. The predictions from MTDATA on a number of selected systems is generally in good agreement with the results from experimental work, and has assisted in the understanding of the microstructure and mechanical properties of the Pb-free solders and the implications of their interactions with a tin-lead solder. However, further critical assessment and the addition of new elements into the solder database, such as Ni and P, are required to make MTDA TA a more effective computational tool to assist the optimization of processing parameters and cost-effective production in using Pb-free solders. Molten solder can interact with the under bump metallizations (UBM) and/or board level metallizations on either side of the solder bump to form intermetallic compounds (IMCs) during solder reflow. In the modelling of the kinetics of the dissolution process of UBM into the liquid solder, the commonly used NernstBrunner (N-B) equation is found to have poor validity for these calculations for micro joints at 100 µm in diameter or less. Three bumping techniques, i.e. solder dipping (SD), solder paste stencil printing followed by reflow (SPR) and electroplating of solders and subsequent reflow (EPR), are used to investigate the interfacial interactions of molten Sn/Sn-rich solders, i.e. pure Sn, Sn-3.5Ag, and Sn-3.8AgO.7Cu, on electroless nickel immersion gold (ENIG) and copper pads at 240°C. The resultant bulk and interfacial microstructures from a variety of pad sizes, ranging from 1 mm down to 25 µm, suggest that in general the small bumps contain smaller β-Sn dendrites and Ag₃Sn IMC particles, nevertheless the interfacial IMC is thicker in the smalI bumps than in the large bumps. In addition, one and two-dimensional combined thermodynamic and kinetic models have been developed to assist the understanding of the kinetics of interdiffusion and the formation of interfacial intermetallic compounds during reflow. Both the experimental results and theoretical predictions suggest that the solder bump size and geometry can influence the as-soldered microstructure, and therefore this factor should be taken into consideration for the design of future reliable ultrafine Ph-free solder joints.