Zn4Sb3 is shown to be entropically stabilized versus decomposition to Zn and ZnSb though the effects of configurational disorder and phonon free energy. Single phase stability is predicted for a range of compositions and temperatures. Retrograde solubility of Zn is predicted on the two-phase boundary region between Zn4Sb3 and Zn. The complex temperature dependent solubility can be used to explain the variety of nanoparticle formation observed in the system: formation of ZnSb on the Sb rich side, Zn on the far Zn rich side and nano-void formation due to Zn precipitates being reabsorbed at lower temperatures.
@article{arxiv.1010.4795,
title = {Entropic Stabilization and Retrograde Solubility in Zn4Sb3},
author = {Gregory S. Pomrehn and Eric S. Toberer and G. Jeffrey Snyder and Axel van de Walle},
journal= {arXiv preprint arXiv:1010.4795},
year = {2011}
}