Abstract
The limited number of independent β-Sn grain orientations resulting from the difficulty in nucleating β-Sn during solidification of Sn-based solders has a large effect on the resulting β-Sn grain size and, hence, on overall solder joint performance and reliability. This study analyzes the efficacy of Ge as a heterogeneous nucleation agent for β-Sn by observing the morphologies and orientation relationships of as-deposited, solid-state annealed, and liquid-state annealed pure Sn films on single crystal Ge (100), (110), and (111) substrates. Results from scanning electron microscopy and electron backscatter diffraction showed that the as-deposited Sn films all deposited with a Sn (001)|| z-axis texture, regardless of the underlying Ge substrate orientation. Solid-state annealing at 150 °C for 5 min did not result in significant dewetting of the Sn films, and the films maintained their as-deposited texture of Sn (001)|| z-axis, regardless of the underlying Ge substrate orientation. Liquid-state annealing at 235 °C for 1 min resulted is large-scale dewetting of the Sn films and re-orientation of the Sn films on the various Ge substrates. After solidification, the Ge (100) and (110) single crystal substrates produced patches of dewetted grains of the same orientation but there were no consistent Sn grain textures after liquid-state annealing, suggesting no single orientation relationship. In contrast, solidification on Ge (111) single crystal substrates resulted in isolated grains with a single Sn film texture and an orientation relationship of \( \left( {100} \right)_{\rm{Sn}} \parallel \left( {111} \right)_{\rm{Ge}} {\hbox{and}} \left[ {100} \right]_{\rm{Sn}} \parallel \left[ {110} \right]_{\rm{Ge}} \). Density Functional Theory simulations of the experimentally observed Ge (111) sample orientation relationship and the Ge/Sn cube-on-cube orientation relationship suggest favorable relative interfacial binding energies for both interface orientations.
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Acknowledgments
The authors are grateful for Dan Josell and Maureen Williams at NIST for their assistance in performing the Sn film depositions, to Qingfeng Xing, Matt Lynn, Matt Besser, Mark Clarridge, Sarah Wiley, Emma White, Stephanie Choquette, and Iver Anderson of Ames Laboratory for their help in providing access and training on the EBSD system located at the Sensitive Instrument Facility in Ames, IA, USA, and to David Guzman, formerly at Purdue University and currently at Brookhaven National Laboratory, for his assistance in running the DFT simulations. This work was prepared by Lawrence Livermore National Laboratory (LLNL) under Contract DE-AC52-07NA27344. Ames Laboratory (US-DOE), Purdue University, and Nihon Superior supported this work through Ames Lab Contract No. DE-AC02-07CH11358. Additional funding was provided through government support under and awarded by the DoD Air Force Office of Scientific Research, National Defense Science and Engineering Graduate (NDSEG) Fellowship, 32 CFR 168a.
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Reeve, T.C., Reeve, S.T. & Handwerker, C.A. Orientation Relationships of Pure Tin on Single Crystal Germanium Substrates. J. Electron. Mater. 49, 140–151 (2020). https://doi.org/10.1007/s11664-019-07640-6
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DOI: https://doi.org/10.1007/s11664-019-07640-6