Title
Expanding the I-II-V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides
Publication Date
8-13-2018
Department
Ames Laboratory; Chemistry
Campus Units
Ames Laboratory, Chemistry
OSTI ID+
1477244
Report Number
IS-J 9738
DOI
10.1021/acs.chemmater.8b02910
Journal Title
Chemistry of Materials
Volume Number
30
Issue Number
17
First Page
6173
Last Page
6182
Abstract
Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that cannot be obtained through thermodynamically controlled, high-temperature reactions. A recent solution-phase exploration of Li–Zn–Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal LiGaGe-type LiZnSb and the cubic full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony-containing Zintl phases, required a thorough exploration of synthetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs h*-LiZnSb), binary (ZnSb vs Zn8Sb7), and metallic (Zn and Sb) products. Further, we find one of the ternary phases adopts a variant of the previously observed hexagonal LiZnSb structure. Our results demonstrate the utility of low-temperature solution-phase—soft synthesis—methods in accessing and mining a rich phase space. We anticipate that this work will motivate further exploration of multinary I–II–V compounds and encourage similarly thorough investigations of related Zintl systems by solution-phase methods
DOE Contract Number(s)
AC02-07CH11358
Language
en
Department of Energy Subject Categories
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Publisher
Iowa State University Digital Repository, Ames IA (United States)
