Ames Laboratory, Chemistry
Journal or Book Title
Chemistry of Materials
Composition, crystal structures, polymorphic transformations, and stability of the thermoelectric material known in the literature as “Zn4Sb3” have been studied on a polycrystalline sample and Bi-flux-grown single crystals using X-ray diffraction techniques, resistance, and Seebeck coefficient measurements at various temperatures ranging from 4 to 773 K. Microprobe analysis yields the composition of the flux-grown crystals to be close to Zn13Sb10, with minor Bi doping. High-temperature X-ray and Seebeck coefficient studies show that the phase is unstable at high temperatures in a vacuum because of Zn losses. Both X-ray diffraction and resistivity measurements indicate the presence of two consecutive symmetry-breaking transitions below room temperature, in agreement with our previous results on polycrystalline samples. Application of Landau theory suggests that the first R3̄c → C2/c symmetry breaking may be second-order in nature. The second, low-temperature symmetry breaking may proceed along two routes. One of these pathways, a first-order C2/c → C1 symmetry reduction, may lead to an incommensurate structure and is consistent with our experimental observations.
American Chemical Society
Mozharivskyj, Yurij; Janssen, Yuri; Harringa, Joel L.; Kracher, Alfred; Tsokol, Alexandra O.; and Miller, Gordon J., "Zn13Sb10: A Structural and Landau Theoretical Analysis of Its Phase Transitions" (2006). Chemistry Publications. 736.