Single crystal growth and characterization of new Zintl phase Ca9Zn3.1In0.9Sb9
Abstract
Complex Zintl phases have yielded a large variety of promising new thermoelectric materials. Here we report the discovery of the new Zintl phase Ca9(Zn1–xInx)4Sb9 (x ~ 0.9), needle-like crystals of which were serendipitously obtained from an In- and Sb-rich flux. Although its composition is reminiscent of Ca9Zn4+xSb9, an excellent thermoelectric material with zT > 1, the substitution of In on the Zn site leads to the formation of an entirely new structure type. Single crystal X-ray diffraction revealed a structure characterized by TSb4 tetrahedra (T = statistically disordered Zn and In atoms) and ZnSb3 triangular units, which share common corners to form [T4Sb9]18– polyanions. The average structure was found to have hexagonal symmetry. The valence electron count in this heavily-disordered structure appears to follows the Zintl-Klemm rules, suggesting semiconducting behavior. Single crystal electrical conductivity and Seebeck coefficient measurements support this conclusion, suggesting that the as-grown crystals are degenerate p-type semiconductors.
- Authors:
-
[1];
[2];
[1];
[2];
- Michigan State Univ., East Lansing, MI (United States). Dept. of Chemical Engineering and Materials Science
- Univ. of Delaware, Newark, DE (United States). Dept. of Chemistry and Biochemistry
- Publication Date:
- Research Org.:
- Univ. of Delaware, Newark, DE (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1851162
- Alternate Identifier(s):
- OSTI ID: 1776102
- Grant/Contract Number:
- SC0008885; 1709158
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Solid State Chemistry
- Additional Journal Information:
- Journal Volume: 296; Journal Issue: C; Journal ID: ISSN 0022-4596
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; zintl phases; crystal structure; electronic structure; single crystal x-ray diffraction; thermoelectrics; flux growth
Citation Formats
Smiadak, David M., Baranets, Sviatoslav, Rylko, Megan, Marshall, Mack, Calderón-Cueva, Mario, Bobev, Svilen, and Zevalkink, Alex. Single crystal growth and characterization of new Zintl phase Ca9Zn3.1In0.9Sb9. United States: N. p., 2021.
Web. doi:10.1016/j.jssc.2020.121947.
Smiadak, David M., Baranets, Sviatoslav, Rylko, Megan, Marshall, Mack, Calderón-Cueva, Mario, Bobev, Svilen, & Zevalkink, Alex. Single crystal growth and characterization of new Zintl phase Ca9Zn3.1In0.9Sb9. United States. https://doi.org/10.1016/j.jssc.2020.121947
Smiadak, David M., Baranets, Sviatoslav, Rylko, Megan, Marshall, Mack, Calderón-Cueva, Mario, Bobev, Svilen, and Zevalkink, Alex. Thu .
"Single crystal growth and characterization of new Zintl phase Ca9Zn3.1In0.9Sb9". United States. https://doi.org/10.1016/j.jssc.2020.121947. https://www.osti.gov/servlets/purl/1851162.
@article{osti_1851162,
title = {Single crystal growth and characterization of new Zintl phase Ca9Zn3.1In0.9Sb9},
author = {Smiadak, David M. and Baranets, Sviatoslav and Rylko, Megan and Marshall, Mack and Calderón-Cueva, Mario and Bobev, Svilen and Zevalkink, Alex},
abstractNote = {Complex Zintl phases have yielded a large variety of promising new thermoelectric materials. Here we report the discovery of the new Zintl phase Ca9(Zn1–xInx)4Sb9 (x ~ 0.9), needle-like crystals of which were serendipitously obtained from an In- and Sb-rich flux. Although its composition is reminiscent of Ca9Zn4+xSb9, an excellent thermoelectric material with zT > 1, the substitution of In on the Zn site leads to the formation of an entirely new structure type. Single crystal X-ray diffraction revealed a structure characterized by TSb4 tetrahedra (T = statistically disordered Zn and In atoms) and ZnSb3 triangular units, which share common corners to form [T4Sb9]18– polyanions. The average structure was found to have hexagonal symmetry. The valence electron count in this heavily-disordered structure appears to follows the Zintl-Klemm rules, suggesting semiconducting behavior. Single crystal electrical conductivity and Seebeck coefficient measurements support this conclusion, suggesting that the as-grown crystals are degenerate p-type semiconductors.},
doi = {10.1016/j.jssc.2020.121947},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 296,
place = {United States},
year = {Thu Apr 01 00:00:00 EDT 2021},
month = {Thu Apr 01 00:00:00 EDT 2021}
}
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