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:
-
- 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}
}
Figures / Tables:
Works referenced in this record:
Band gap estimation from temperature dependent Seebeck measurement—Deviations from the 2e|S|maxTmax relation
journal, January 2015
- Gibbs, Zachary M.; Kim, Hyun-Sik; Wang, Heng
- Applied Physics Letters, Vol. 106, Issue 2
Phase Boundary Mapping to Obtain n-type Mg3Sb2-Based Thermoelectrics
journal, January 2018
- Ohno, Saneyuki; Imasato, Kazuki; Anand, Shashwat
- Joule, Vol. 2, Issue 1
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
First-Principle Study of the Electronic Structure and Stability of Reconstructed AgInSe2 (112) Polar Surfaces
journal, November 2017
- Kim, Namhoon; Martin, Pamela Pena; Rockett, Angus A.
- IEEE Journal of Photovoltaics, Vol. 7, Issue 6
Crystal and electronic band structure of Cu2ZnSnX4 (X=S and Se) photovoltaic absorbers: First-principles insights
journal, January 2009
- Chen, Shiyou; Gong, X. G.; Walsh, Aron
- Applied Physics Letters, Vol. 94, Issue 4
Theoretical study of defects Cu3SbSe4: Search for optimum dopants for enhancing thermoelectric properties
journal, March 2015
- Do, Dat T.; Mahanti, S. D.
- Journal of Alloys and Compounds, Vol. 625
Screened-exchange density functional theory description of the electronic structure and phase stability of the chalcopyrite materials and
journal, April 2016
- Kim, Namhoon; Martin, Pamela Peña; Rockett, Angus A.
- Physical Review B, Vol. 93, Issue 16
New technologies for CIGS photovoltaics
journal, December 2004
- Delahoy, Alan E.; Chen, Liangfan; Akhtar, Masud
- Solar Energy, Vol. 77, Issue 6
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Material descriptors for predicting thermoelectric performance
journal, January 2015
- Yan, Jun; Gorai, Prashun; Ortiz, Brenden
- Energy & Environmental Science, Vol. 8, Issue 3
-type doping of and
journal, July 2005
- Persson, Clas; Zhao, Yu-Jun; Lany, Stephan
- Physical Review B, Vol. 72, Issue 3
GaAs photovoltaics and optoelectronics using releasable multilayer epitaxial assemblies
journal, May 2010
- Yoon, Jongseung; Jo, Sungjin; Chun, Ik Su
- Nature, Vol. 465, Issue 7296
Measurement of the electrical resistivity and Hall coefficient at high temperatures
journal, December 2012
- Borup, Kasper A.; Toberer, Eric S.; Zoltan, Leslie D.
- Review of Scientific Instruments, Vol. 83, Issue 12
Bonds, bands, and band gaps in tetrahedrally bonded ternary compounds: The role of group V lone pairs
journal, April 2014
- Do, Dat T.; Mahanti, S. D.
- Journal of Physics and Chemistry of Solids, Vol. 75, Issue 4
Development of CZTS-based thin film solar cells
journal, February 2009
- Katagiri, Hironori; Jimbo, Kazuo; Maw, Win Shwe
- Thin Solid Films, Vol. 517, Issue 7, p. 2455-2460
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Native Defect Engineering in CuInTe 2
journal, December 2020
- Adamczyk, Jesse M.; Gomes, Lídia C.; Qu, Jiaxing
- Chemistry of Materials, Vol. 33, Issue 1
Synthesis of CuInS 2 , CuInSe 2 , and Cu(In x Ga 1- x )Se 2 (CIGS) Nanocrystal “Inks” for Printable Photovoltaics
journal, December 2008
- Panthani, Matthew G.; Akhavan, Vahid; Goodfellow, Brian
- Journal of the American Chemical Society, Vol. 130, Issue 49
Stretchable GaAs Photovoltaics with Designs That Enable High Areal Coverage
journal, January 2011
- Lee, Jongho; Wu, Jian; Shi, Mingxing
- Advanced Materials, Vol. 23, Issue 8
Solution-Based Synthesis and Characterization of Cu 2 ZnSnS 4 Nanocrystals
journal, September 2009
- Riha, Shannon C.; Parkinson, Bruce A.; Prieto, Amy L.
- Journal of the American Chemical Society, Vol. 131, Issue 34
Progressive Regulation of Electrical and Thermal Transport Properties to High-Performance CuInTe 2 Thermoelectric Materials
journal, April 2016
- Luo, Yubo; Yang, Junyou; Jiang, Qinghui
- Advanced Energy Materials, Vol. 6, Issue 12
Defect properties of CuInSe2 and CuGaSe2
journal, November 2005
- Wei, Su-Huai; Zhang, S. B.
- Journal of Physics and Chemistry of Solids, Vol. 66, Issue 11
Defect physics of the chalcopyrite semiconductor
journal, April 1998
- Zhang, S. B.; Wei, Su-Huai; Zunger, Alex
- Physical Review B, Vol. 57, Issue 16
Thermodynamics and kinetics of the copper vacancy in CuInSe2, CuGaSe2, CuInS2, and CuGaS2 from screened-exchange hybrid density functional theory
journal, July 2010
- Pohl, Johan; Albe, Karsten
- Journal of Applied Physics, Vol. 108, Issue 2
Role of Lone-Pair Electrons in Producing Minimum Thermal Conductivity in Nitrogen-Group Chalcogenide Compounds
journal, November 2011
- Skoug, Eric J.; Morelli, Donald T.
- Physical Review Letters, Vol. 107, Issue 23
Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs
journal, December 2008
- Lany, Stephan; Zunger, Alex
- Physical Review B, Vol. 78, Issue 23, Article No. 235104
Carrier density control in Cu 2 HgGeTe 4 and discovery of Hg 2 GeTe 4 via phase boundary mapping
journal, January 2019
- Ortiz, Brenden R.; Gordiz, Kiarash; Gomes, Lídia C.
- Journal of Materials Chemistry A, Vol. 7, Issue 2
New developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design
journal, May 2002
- Belsky, Alec; Hellenbrandt, Mariette; Karen, Vicky Lynn
- Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3
Understanding Cu incorporation in the structure using resonant x-ray diffraction
journal, January 2021
- Levy-Wendt, Ben L.; Ortiz, Brenden R.; Gomes, Lídia C.
- Physical Review Materials, Vol. 5, Issue 1
Ultralow Thermal Conductivity in Diamond-Like Semiconductors: Selective Scattering of Phonons from Antisite Defects
journal, May 2018
- Ortiz, Brenden R.; Peng, Wanyue; Gomes, Lídia C.
- Chemistry of Materials, Vol. 30, Issue 10
Chalcopyrite CuGaTe2: A High-Efficiency Bulk Thermoelectric Material
journal, June 2012
- Plirdpring, Theerayuth; Kurosaki, Ken; Kosuga, Atsuko
- Advanced Materials, Vol. 24, Issue 27
Wurtzite-derived polytypes of kesterite and stannite quaternary chalcogenide semiconductors
journal, November 2010
- Chen, Shiyou; Walsh, Aron; Luo, Ye
- Physical Review B, Vol. 82, Issue 19
Defect chemistry and doping of BiCuSeO
journal, January 2021
- Toriyama, Michael Y.; Qu, Jiaxing; Snyder, G. Jeffrey
- Journal of Materials Chemistry A, Vol. 9, Issue 36
Efficiency Enhancement of GaAs Photovoltaics Employing Antireflective Indium Tin Oxide Nanocolumns
journal, April 2009
- Yu, Peichen; Chang, Chia-Hua; Chiu, Ching-Hua
- Advanced Materials, Vol. 21, Issue 16
Empirical modeling of dopability in diamond-like semiconductors
journal, December 2018
- Miller, Samuel A.; Dylla, Maxwell; Anand, Shashwat
- npj Computational Materials, Vol. 4, Issue 1
Classification of Lattice Defects in the Kesterite Cu 2 ZnSnS 4 and Cu 2 ZnSnSe 4 Earth-Abundant Solar Cell Absorbers
journal, February 2013
- Chen, Shiyou; Walsh, Aron; Gong, Xin-Gao
- Advanced Materials, Vol. 25, Issue 11
Intrinsic point defects and complexes in the quaternary kesterite semiconductor
journal, June 2010
- Chen, Shiyou; Yang, Ji-Hui; Gong, X. G.
- Physical Review B, Vol. 81, Issue 24
Phase Stability and Electronic Structure of In-Free Photovoltaic Materials: Cu 2 ZnSiSe 4 , Cu 2 ZnGeSe 4 , and Cu 2 ZnSnSe 4
journal, December 2010
- Nakamura, Satoshi; Maeda, Tsuyoshi; Wada, Takahiro
- Japanese Journal of Applied Physics, Vol. 49, Issue 12
Ternary compound CuInTe2: a promising thermoelectric material with diamond-like structure
journal, January 2012
- Liu, Ruiheng; Xi, Lili; Liu, Huili
- Chemical Communications, Vol. 48, Issue 32
A high temperature apparatus for measurement of the Seebeck coefficient
journal, June 2011
- Iwanaga, Shiho; Toberer, Eric S.; LaLonde, Aaron
- Review of Scientific Instruments, Vol. 82, Issue 6
Efficient calculation of carrier scattering rates from first principles
journal, April 2021
- Ganose, Alex M.; Park, Junsoo; Faghaninia, Alireza
- Nature Communications, Vol. 12, Issue 1
Influence of doping and solid solution formation on the thermoelectric properties of chalcopyrite semiconductors
journal, May 2015
- Carr, Winston D.; Morelli, Donald T.
- Journal of Alloys and Compounds, Vol. 630
Thermoelectric Properties of the Compounds AgPb m LaTe m +2 †
journal, February 2010
- Ahn, Kyunghan; Li, Chang-Peng; Uher, Ctirad
- Chemistry of Materials, Vol. 22, Issue 3
Figures / Tables found in this record: