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Title: Valence Disproportionation of GeS in the PbS Matrix Forms Pb5Ge5S12 Inclusions with Conduction Band Alignment Leading to High n-Type Thermoelectric Performance

Abstract

Converting waste heat into useful electricity using solid-state thermoelectrics has a potential for enormous global energy savings. Lead chalcogenides are among the most prominent thermoelectric materials, whose performance decreases with an increase in chalcogen amounts (e.g., PbTe>PbSe>PbS). Herein, we demonstrate the simultaneous optimization of the electrical and thermal transport properties of PbS-based compounds by alloying with GeS. The addition of GeS triggers a complex cascade of beneficial events as follows: Ge2+ substitution in Pb2+ and discordant off-center behavior; formation of Pb5Ge5S12 as stable second phase inclusions through valence disproportionation of Ge2+ to Ge0 and Ge4+. PbS and Pb5Ge5S12 exhibit good conduction band energy alignment that preserves the high electron mobility; the formation of Pb5Ge5S12 increases the electron carrier concentration by introducing S vacancies. Sb doping as the electron donor produces a large power factor and low lattice thermal conductivity (κlat) of ~0.61 Wm-1K-1. The highest performance was obtained for the 14% GeS-alloyed samples, which exhibited an increased room temperature electron mobility of ~121 cm2V-1s-1 for 3 × 1019 cm-3 carrier density, and a ZT, of 1.32 at 923 K. This is ~ 55% greater that the corresponding Sb-doped PbS sample and is one of the highest reported for the n-typemore » PbS system. Moreover, the average ZT (ZTavg) of ~0.76 from 400 to 923 K is the highest for PbS-based systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [2];  [2];  [2];  [4];  [5]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [8];  [3]; ORCiD logo [2]; ORCiD logo [2];  [9]; ORCiD logo [10]; ORCiD logo [2]
  1. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian (China); Fuzhou Univ. (China); Nanyang Technological Univ. (Singapore); Northwestern Univ., Evanston, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Univ. of Michigan, Ann Arbor, MI (United States)
  4. Nanyang Technological Univ. (Singapore); Northwestern Univ., Evanston, IL (United States); Huazhong Univ. of Science and Technology, Wuhan (China)
  5. Fuzhou Univ. (China)
  6. Agency for Science, Technology and Research (A*STAR) (Singapore). Institute of Materials Research and Engineering
  7. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian (China); Nanjing Univ. (China)
  8. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian (China); Fuzhou Univ. (China)
  9. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian (China); Fuzhou Univ. (China); Nanjing Univ. (China)
  10. Nanyang Technological Univ. (Singapore)
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Natural Science Foundation of China (NSFC)
OSTI Identifier:
1867609
Grant/Contract Number:  
SC0014520; A19D9a0096; 2020YFA0710303; 2018-T2-1-010; ECCS-1542205; 52102218; 61728401; DMR-1720139; 2021ZZ127
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 144; Journal Issue: 16; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; 42 ENGINEERING; Waste heat harvesting; n-type PbS; Pb5Ge5S12; conduction band alignment; all-scale hierarchical architectures

Citation Formats

Luo, Zhong-Zhen, Cai, Songting, Hao, Shiqiang, Bailey, Trevor P., Xie, Hongyao, Slade, Tyler J., Liu, Yukun, Luo, Yubo, Chen, Zixuan, Xu, Jianwei, Luo, Wenjun, Yu, Yan, Uher, Ctirad, Wolverton, Christopher, Dravid, Vinayak P., Zou, Zhigang, Yan, Qingyu, and Kanatzidis, Mercouri G. Valence Disproportionation of GeS in the PbS Matrix Forms Pb5Ge5S12 Inclusions with Conduction Band Alignment Leading to High n-Type Thermoelectric Performance. United States: N. p., 2022. Web. doi:10.1021/jacs.2c01706.
Luo, Zhong-Zhen, Cai, Songting, Hao, Shiqiang, Bailey, Trevor P., Xie, Hongyao, Slade, Tyler J., Liu, Yukun, Luo, Yubo, Chen, Zixuan, Xu, Jianwei, Luo, Wenjun, Yu, Yan, Uher, Ctirad, Wolverton, Christopher, Dravid, Vinayak P., Zou, Zhigang, Yan, Qingyu, & Kanatzidis, Mercouri G. Valence Disproportionation of GeS in the PbS Matrix Forms Pb5Ge5S12 Inclusions with Conduction Band Alignment Leading to High n-Type Thermoelectric Performance. United States. https://doi.org/10.1021/jacs.2c01706
Luo, Zhong-Zhen, Cai, Songting, Hao, Shiqiang, Bailey, Trevor P., Xie, Hongyao, Slade, Tyler J., Liu, Yukun, Luo, Yubo, Chen, Zixuan, Xu, Jianwei, Luo, Wenjun, Yu, Yan, Uher, Ctirad, Wolverton, Christopher, Dravid, Vinayak P., Zou, Zhigang, Yan, Qingyu, and Kanatzidis, Mercouri G. Thu . "Valence Disproportionation of GeS in the PbS Matrix Forms Pb5Ge5S12 Inclusions with Conduction Band Alignment Leading to High n-Type Thermoelectric Performance". United States. https://doi.org/10.1021/jacs.2c01706. https://www.osti.gov/servlets/purl/1867609.
@article{osti_1867609,
title = {Valence Disproportionation of GeS in the PbS Matrix Forms Pb5Ge5S12 Inclusions with Conduction Band Alignment Leading to High n-Type Thermoelectric Performance},
author = {Luo, Zhong-Zhen and Cai, Songting and Hao, Shiqiang and Bailey, Trevor P. and Xie, Hongyao and Slade, Tyler J. and Liu, Yukun and Luo, Yubo and Chen, Zixuan and Xu, Jianwei and Luo, Wenjun and Yu, Yan and Uher, Ctirad and Wolverton, Christopher and Dravid, Vinayak P. and Zou, Zhigang and Yan, Qingyu and Kanatzidis, Mercouri G.},
abstractNote = {Converting waste heat into useful electricity using solid-state thermoelectrics has a potential for enormous global energy savings. Lead chalcogenides are among the most prominent thermoelectric materials, whose performance decreases with an increase in chalcogen amounts (e.g., PbTe>PbSe>PbS). Herein, we demonstrate the simultaneous optimization of the electrical and thermal transport properties of PbS-based compounds by alloying with GeS. The addition of GeS triggers a complex cascade of beneficial events as follows: Ge2+ substitution in Pb2+ and discordant off-center behavior; formation of Pb5Ge5S12 as stable second phase inclusions through valence disproportionation of Ge2+ to Ge0 and Ge4+. PbS and Pb5Ge5S12 exhibit good conduction band energy alignment that preserves the high electron mobility; the formation of Pb5Ge5S12 increases the electron carrier concentration by introducing S vacancies. Sb doping as the electron donor produces a large power factor and low lattice thermal conductivity (κlat) of ~0.61 Wm-1K-1. The highest performance was obtained for the 14% GeS-alloyed samples, which exhibited an increased room temperature electron mobility of ~121 cm2V-1s-1 for 3 × 1019 cm-3 carrier density, and a ZT, of 1.32 at 923 K. This is ~ 55% greater that the corresponding Sb-doped PbS sample and is one of the highest reported for the n-type PbS system. Moreover, the average ZT (ZTavg) of ~0.76 from 400 to 923 K is the highest for PbS-based systems.},
doi = {10.1021/jacs.2c01706},
journal = {Journal of the American Chemical Society},
number = 16,
volume = 144,
place = {United States},
year = {Thu Apr 14 00:00:00 EDT 2022},
month = {Thu Apr 14 00:00:00 EDT 2022}
}

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