Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides
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 Zintlmore »
- Authors:
-
[2];
[2];
[2]
- Iowa State Univ., Ames, IA (United States)
- Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1477244
- Report Number(s):
- IS-J-9738
Journal ID: ISSN 0897-4756
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 17; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
White, Miles A., Baumler, Katelyn J., Chen, Yunhua, Venkatesh, Amrit, Medina-Gonzalez, Alan M., Rossini, Aaron J., Zaikina, Julia V., Chan, Emory M., and Vela, Javier. Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides. United States: N. p., 2018.
Web. doi:10.1021/acs.chemmater.8b02910.
White, Miles A., Baumler, Katelyn J., Chen, Yunhua, Venkatesh, Amrit, Medina-Gonzalez, Alan M., Rossini, Aaron J., Zaikina, Julia V., Chan, Emory M., & Vela, Javier. Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides. United States. https://doi.org/10.1021/acs.chemmater.8b02910
White, Miles A., Baumler, Katelyn J., Chen, Yunhua, Venkatesh, Amrit, Medina-Gonzalez, Alan M., Rossini, Aaron J., Zaikina, Julia V., Chan, Emory M., and Vela, Javier. Mon .
"Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides". United States. https://doi.org/10.1021/acs.chemmater.8b02910. https://www.osti.gov/servlets/purl/1477244.
@article{osti_1477244,
title = {Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides},
author = {White, Miles A. and Baumler, Katelyn J. and Chen, Yunhua and Venkatesh, Amrit and Medina-Gonzalez, Alan M. and Rossini, Aaron J. and Zaikina, Julia V. and Chan, Emory M. and Vela, Javier},
abstractNote = {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.},
doi = {10.1021/acs.chemmater.8b02910},
journal = {Chemistry of Materials},
number = 17,
volume = 30,
place = {United States},
year = {Mon Aug 13 00:00:00 EDT 2018},
month = {Mon Aug 13 00:00:00 EDT 2018}
}
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