Controlling thermoelectric transport via native defects in the diamond-like semiconductors Cu2HgGeTe4 and Hg2GeTe4
Abstract
Diamond like semiconductors (DLS) have emerged as candidates for thermoelectric energy conversion. Towards understanding and optimizing performance, we present a comprehensive investigation of the electronic properties of two DLS phases, quaternary Cu2HgGeTe4 and related ordered vacancy compound Hg2GeTe4, including thermodynamic stability, defect chemistry, and transport properties. To establish the thermodynamic link between the related but distinct phases, the stability region for both is visualized in chemical potential space. In spite of their similar structure and bonding, we show that the two materials exhibit reciprocal behaviors for dopability. Cu2HgGeTe4 is degenerately p-type in all environments despite its wide stability region, due to the presence of low-energy acceptor defects VCu and CuHg and is resistant to extrinsic n-type doping. Meanwhile Hg2GeTe4 has a narrow stability region and intrinsic behavior due to the relatively high formation energy of native defects, but presents an opportunity for bi-polar doping. While these two compounds have similar structure, bonding, and chemical constituents, the reciprocal nature of their dopability emerges from significant differences in band edge positions. A Brouwer band diagram approach is utilized to visualize the role of native defects on carrier concentrations, dopability, and transport properties. Here this study elucidates the doping asymmetry between two solid-solutionmore »
- Authors:
-
[1];
[4];
[2];
[1]
- University of Illinois at Urbana-Champaign, IL (United States)
- Colorado School of Mines, Golden, CO (United States)
- Northwestern University, Evanston, IL (United States)
- University of California, Santa Barbara, CA (United States)
- Publication Date:
- Research Org.:
- Krell Institute, Ames, IA (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1978840
- Alternate Identifier(s):
- OSTI ID: 1830861
- Grant/Contract Number:
- SC0020347; DMR-1729149; 1922758
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 46; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
Citation Formats
Qu, Jiaxing, Porter, Claire E., Gomes, Lídia C., Adamczyk, Jesse M., Toriyama, Michael Y., Ortiz, Brenden R., Toberer, Eric S., and Ertekin, Elif. Controlling thermoelectric transport via native defects in the diamond-like semiconductors Cu2HgGeTe4 and Hg2GeTe4. United States: N. p., 2021.
Web. doi:10.1039/d1ta07410e.
Qu, Jiaxing, Porter, Claire E., Gomes, Lídia C., Adamczyk, Jesse M., Toriyama, Michael Y., Ortiz, Brenden R., Toberer, Eric S., & Ertekin, Elif. Controlling thermoelectric transport via native defects in the diamond-like semiconductors Cu2HgGeTe4 and Hg2GeTe4. United States. https://doi.org/10.1039/d1ta07410e
Qu, Jiaxing, Porter, Claire E., Gomes, Lídia C., Adamczyk, Jesse M., Toriyama, Michael Y., Ortiz, Brenden R., Toberer, Eric S., and Ertekin, Elif. Fri .
"Controlling thermoelectric transport via native defects in the diamond-like semiconductors Cu2HgGeTe4 and Hg2GeTe4". United States. https://doi.org/10.1039/d1ta07410e. https://www.osti.gov/servlets/purl/1978840.
@article{osti_1978840,
title = {Controlling thermoelectric transport via native defects in the diamond-like semiconductors Cu2HgGeTe4 and Hg2GeTe4},
author = {Qu, Jiaxing and Porter, Claire E. and Gomes, Lídia C. and Adamczyk, Jesse M. and Toriyama, Michael Y. and Ortiz, Brenden R. and Toberer, Eric S. and Ertekin, Elif},
abstractNote = {Diamond like semiconductors (DLS) have emerged as candidates for thermoelectric energy conversion. Towards understanding and optimizing performance, we present a comprehensive investigation of the electronic properties of two DLS phases, quaternary Cu2HgGeTe4 and related ordered vacancy compound Hg2GeTe4, including thermodynamic stability, defect chemistry, and transport properties. To establish the thermodynamic link between the related but distinct phases, the stability region for both is visualized in chemical potential space. In spite of their similar structure and bonding, we show that the two materials exhibit reciprocal behaviors for dopability. Cu2HgGeTe4 is degenerately p-type in all environments despite its wide stability region, due to the presence of low-energy acceptor defects VCu and CuHg and is resistant to extrinsic n-type doping. Meanwhile Hg2GeTe4 has a narrow stability region and intrinsic behavior due to the relatively high formation energy of native defects, but presents an opportunity for bi-polar doping. While these two compounds have similar structure, bonding, and chemical constituents, the reciprocal nature of their dopability emerges from significant differences in band edge positions. A Brouwer band diagram approach is utilized to visualize the role of native defects on carrier concentrations, dopability, and transport properties. Here this study elucidates the doping asymmetry between two solid-solution forming DLS phases Cu2HgGeTe4 and Hg2GeTe4 by revealing the defect chemistry of each compound, and suggests design strategies for defect engineering of DLS phases.},
doi = {10.1039/d1ta07410e},
journal = {Journal of Materials Chemistry. A},
number = 46,
volume = 9,
place = {United States},
year = {Fri Nov 05 00:00:00 EDT 2021},
month = {Fri Nov 05 00:00:00 EDT 2021}
}
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Fig. 1 : Cu2HgGeTe4 crystallizes in the stannite structure, while Hg2GeTe4 adopts the defect chalcopyrite structure. Transitions from the quaternary to the ternary structure (which form a full solid solution) may be understood as the simultaneous substitution of one Hg atom onto a Cu site and the creation of amore »
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