Electrodeposition of Pb-free, Sn-based Alloy Solder Films

  • Author / Creator
    Han, Chunfen
  • The dominant materials used for solders in electronic assemblies over the past 60 years have been Pb-Sn alloys. Increasing pressure from environmental and health authorities has stimulated the development of various Pb-free solders. Two of the most promising replacements are eutectic Sn-Cu and Sn-Ag-Cu alloys that are produced primarily by electrodeposition. During soldering and solid state aging (storage or in service of the electronic assemblies), interactions take place at the solder/substrate metal interface and form intermetallic compounds (IMCs) which are crucial for the reliability of the solder joints. Simple and "green" Sn-citrate and Sn-Cu-citrate solutions have been developed and optimized to electrodeposit eutectic and near eutectic Sn-Cu solder films. Sn-citrate suspensions with Cu particles and Sn-Cu-citrate suspensions with Ag nano-particles have also been developed and optimized to allow for electrochemical composite deposition of eutectic and near eutectic Sn-Cu and Sn-Ag-Cu solder films. Different plating and post-plating conditions, including solution concentration, current density, agitation, additives, and aging, have been investigated by evaluating their effects on plating rate, deposit composition and microstructure. Tri-ammonium citrate is used as the only complexing agent for Sn, Sn-Cu, and Sn-Ag-Cu deposition. Speciation diagram calculations, reduction potential calculations, and polarization studies are conducted to study Sn-citrate solution chemistry and the kinetics of Sn electrodeposition. X-ray photoelectron spectroscopy (XPS) analysis is used to identify the precipitates formed in Sn-citrate solutions at low pH. Current-controlled and potential-controlled electrochemical techniques, nucleation modeling, and surface morphology characterization techniques are applied to study the nucleation and film growth mechanism of Sn and Sn-Cu electrodeposition from Sn-citrate and Sn-Cu-citrate solutions. Reflow and aging tests for deposited Sn-Cu and Sn-Ag-Cu solder films on Cu and Ni substrates are performed to study the interactions between the solder and the substrate and the formation and growth of IMCs at the solder/substrate interface, by characterizing the microstructure of the IMCs and calculating diffusion coefficients.

  • Subjects / Keywords
  • Graduation date
  • Type of Item
  • Degree
    Doctor of Philosophy
  • DOI
  • License
    This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for non-commercial purposes. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.
  • Language
  • Institution
    University of Alberta
  • Degree level
  • Department
    • Department of Chemical and Materials Engineering
  • Supervisor / co-supervisor and their department(s)
    • Liu, Qi (Chemical and Materials Engineering)
    • Ivey, Douglas (Chemical and Materials Engineering)
  • Examining committee members and their departments
    • Sit, Jeremy (Electrical and Computer Engineering)
    • Nychka, John (Chemical and Materials Engineering)
    • Chen, Weixing (Chemical and Materials Engineering)
    • Barkey, Dale (Chemical Engineering, University of New Hampshire)