High Thermoelectric Performance through Crystal Symmetry Enhancement in Triply Doped Diamondoid Compound Cu2SnSe3

Hu, Lei; Luo, Yubo; Fang, Yue‐Wen; Qin, Feiyu; Cao, Xun; Xie, Hongyao; Liu, Jiawei; Dong, Jinfeng; Sanson, Andrea; Giarola, Marco; Tan, Xianyi; Zheng, Yun; Suwardi, Ady; Huang, Yizhong; Hippalgaonkar, Kedar; He, Jiaqing; Zhang, Wenqing; Xu, Jianwei; Yan, Qingyu; Kanatzidis, Mercouri G.

doi:10.1002/aenm.202100661

Title: High Thermoelectric Performance through Crystal Symmetry Enhancement in Triply Doped Diamondoid Compound Cu₂SnSe₃

Journal Article · Sat Oct 09 00:00:00 EDT 2021 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202100661· OSTI ID:1834050

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Nanyang Technological Univ. (Singapore); Northwestern Univ., Evanston, IL (United States)
Tokyo Inst. of Technology, Yokohama (Japan)
Nanyang Technological Univ. (Singapore)
Northwestern Univ., Evanston, IL (United States)
Univ. of Padova (Italy)
Univ. of Verona (Italy)
Nanyang Technological Univ. (Singapore); A*STAR Agency for Science Technology and Research (Singapore)
A*STAR Agency for Science Technology and Research (Singapore)
Southern Univ. of Science and Technology, Shenzhen (China)

Abstract The presence of high crystallographic symmetry and nanoscale defects are favorable for thermoelectrics. With proper electronic structures, a highly symmetric crystal tends to possess multiple carrier channels and promote electrical conductivity without sacrificing Seebeck coefficient. In addition, nanoscale defects can effectively scatter acoustic phonons to suppress thermal conductivity. Here, it is reported that the triple doping of Cu ₂ SnSe ₃ leads to a high ZT value of 1.6 at 823 K for Cu _1.85 Ag _0.15 (Sn _0.88 Ga _0.1 Na _0.02 )Se ₃ , and a decent average ZT ( ZT _ave ) value of 0.7 is also achieved for Cu _1.85 Ag _0.15 (Sn _0.93 Mg _0.06 Na _0.01 )Se ₃ from 475 to 823 K. This study reveals: 1) Ag doping on Cu sites generates numerous point defects and greatly decreases lattice thermal conductivity. 2) Doping Mg or Ga converts the monoclinic Cu ₂ SnSe ₃ into a cubic structure. This symmetry enhancing leads to an increase in the effective mass from 0.8 m _e to 2.6 m _e ( m _e , free electron mass) and the power factor from 4.3 µW cm ⁻¹ K ⁻² for Cu ₂ SnSe ₃ to 11.6 µW cm ⁻¹ K ⁻² . 3) Na doping creates dense dislocation arrays and nanoprecipitates, which strengthens the phonon scattering. 4) Pair distribution function analysis shows localized symmetry breakdown in the cubic Cu _1.85 Ag _0.15 (Sn _0.88 Ga _0.1 Na _0.02 )Se ₃ . This work provides a standpoint to design promising thermoelectric materials by synergistically manipulating crystal symmetry and nanoscale defects.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0014520; AC02-06CH11357; AC02-05CH11231; DE‐AC02‐06CH11357; DE‐AC02‐05CH11231

OSTI ID:: 1834050

Alternate ID(s):: OSTI ID: 1825202

Journal Information:: Advanced Energy Materials, Vol. 11, Issue 42; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Realizing high figure of merit in heavy-band p-type half-Heusler thermoelectric materials Fu, Chenguang; Bai, Shengqiang; Liu, Yintu Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9144	journal	September 2015
Achieving high thermoelectric quality factor toward high figure of merit in GeTe Suwardi, A.; Cao, J.; Zhao, Y. Materials Today Physics, Vol. 14 https://doi.org/10.1016/j.mtphys.2020.100239	journal	August 2020
Investigations on electrical and thermal transport properties of Cu2SnSe3 with unusual coexisting nanophases Zhou, Y.; Wu, H.; Wang, D. Materials Today Physics, Vol. 7 https://doi.org/10.1016/j.mtphys.2018.11.001	journal	December 2018
Localized Symmetry Breaking for Tuning Thermal Expansion in ScF ₃ Nanoscale Frameworks Hu, Lei; Qin, Feiyu; Sanson, Andrea Journal of the American Chemical Society, Vol. 140, Issue 13 https://doi.org/10.1021/jacs.8b00885	journal	March 2018
Large Thermal Conductivity Drops in the Diamondoid Lattice of CuFeS ₂ by Discordant Atom Doping Xie, Hongyao; Su, Xianli; Hao, Shiqiang Journal of the American Chemical Society, Vol. 141, Issue 47 https://doi.org/10.1021/jacs.9b10983	journal	November 2019
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Origin of the High Performance in GeTe-Based Thermoelectric Materials upon Bi ₂ Te ₃ Doping Wu, Di; Zhao, Li-Dong; Hao, Shiqiang Journal of the American Chemical Society, Vol. 136, Issue 32 https://doi.org/10.1021/ja504896a	journal	August 2014
Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu _17.6 Fe _17.6 S ₃₂ Thermoelectric Material: Correlations between Lattice Dynamics and Thermal Transport Xie, Hongyao; Su, Xianli; Zhang, Xiaomi Journal of the American Chemical Society, Vol. 141, Issue 27 https://doi.org/10.1021/jacs.9b05072	journal	June 2019
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports Shi, Xun; Yang, Jiong; Salvador, James R. Journal of the American Chemical Society, Vol. 133, Issue 20 https://doi.org/10.1021/ja111199y	journal	May 2011
Low-Symmetry Rhombohedral GeTe Thermoelectrics Li, Juan; Zhang, Xinyue; Chen, Zhiwei Joule, Vol. 2, Issue 5 https://doi.org/10.1016/j.joule.2018.02.016	journal	May 2018
Exploring Resonance Levels and Nanostructuring in the PbTe−CdTe System and Enhancement of the Thermoelectric Figure of Merit Ahn, Kyunghan; Han, Mi-Kyung; He, Jiaqing Journal of the American Chemical Society, Vol. 132, Issue 14 https://doi.org/10.1021/ja910762q	journal	April 2010
Expression of interfacial Seebeck coefficient through grain boundary engineering with multi-layer graphene nanoplatelets Lin, Yue; Wood, Maxwell; Imasato, Kazuki Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/D0EE02490B	journal	January 2020
Convergence of multi-valley bands as the electronic origin of high thermoelectric performance in CoSb3 skutterudites Tang, Yinglu; Gibbs, Zachary M.; Agapito, Luis A. Nature Materials, Vol. 14, Issue 12 https://doi.org/10.1038/nmat4430	journal	October 2015
Convergence of electronic bands for high performance bulk thermoelectrics Pei, Yanzhong; Shi, Xiaoya; LaLonde, Aaron Nature, Vol. 473, Issue 7345, p. 66-69 https://doi.org/10.1038/nature09996	journal	May 2011
Band Engineering of Thermoelectric Materials Pei, Yanzhong; Wang, Heng; Snyder, G. J. Advanced Materials, Vol. 24, Issue 46 https://doi.org/10.1002/adma.201202919	journal	October 2012
New Monoclinic Phase at the Composition Cu ₂ SnSe ₃ and Its Thermoelectric Properties Fan, Jing; Carrillo-Cabrera, Wilder; Akselrud, Lev Inorganic Chemistry, Vol. 52, Issue 19 https://doi.org/10.1021/ic401317k	journal	October 2013
Lattice Dislocations Enhancing Thermoelectric PbTe in Addition to Band Convergence Chen, Zhiwei; Jian, Zhengzhong; Li, Wen Advanced Materials, Vol. 29, Issue 23 https://doi.org/10.1002/adma.201606768	journal	April 2017
High-performance bulk thermoelectrics with all-scale hierarchical architectures Biswas, Kanishka; He, Jiaqing; Blum, Ivan D. Nature, Vol. 489, Issue 7416, p. 414-418 https://doi.org/10.1038/nature11439	journal	September 2012
Zero Thermal Expansion and Ferromagnetism in Cubic Sc _{1– x} M _x F ₃ (M = Ga, Fe) over a Wide Temperature Range Hu, Lei; Chen, Jun; Fan, Longlong Journal of the American Chemical Society, Vol. 136, Issue 39 https://doi.org/10.1021/ja5077487	journal	September 2014
High Thermoelectric Performance in the Wide Band‐Gap AgGa _1‐ _x Te ₂ Compounds: Directional Negative Thermal Expansion and Intrinsically Low Thermal Conductivity Su, Xianli; Zhao, Na; Hao, Shiqiang Advanced Functional Materials, Vol. 29, Issue 6 https://doi.org/10.1002/adfm.201806534	journal	December 2018
Phonon engineering through crystal chemistry Toberer, Eric S.; Zevalkink, Alex; Snyder, G. Jeffrey Journal of Materials Chemistry, Vol. 21, Issue 40 https://doi.org/10.1039/c1jm11754h	journal	January 2011
Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals Zhao, Li-Dong; Lo, Shih-Han; Zhang, Yongsheng Nature, Vol. 508, Issue 7496, p. 373-377 https://doi.org/10.1038/nature13184	journal	April 2014
Electronic transport descriptors for the rapid screening of thermoelectric materials Deng, Tianqi; Recatala-Gomez, Jose; Ohnishi, Masato Materials Horizons, Vol. 8, Issue 9 https://doi.org/10.1039/D1MH00751C	journal	January 2021
SnSe: a remarkable new thermoelectric material Zhao, Li-Dong; Chang, Cheng; Tan, Gangjian Energy & Environmental Science, Vol. 9, Issue 10 https://doi.org/10.1039/C6EE01755J	journal	January 2016
The panoscopic approach to high performance thermoelectrics Zhao, Li-Dong; Dravid, Vinayak P.; Kanatzidis, Mercouri G. Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE43099E	journal	January 2014
Medium-temperature thermoelectric GeTe: vacancy suppression and band structure engineering leading to high performance Dong, Jinfeng; Sun, Fu-Hua; Tang, Huaichao Energy & Environmental Science, Vol. 12, Issue 4 https://doi.org/10.1039/C9EE00317G	journal	January 2019
Establishing the Golden Range of Seebeck Coefficient for Maximizing Thermoelectric Performance Hong, Min; Lyu, Wanyu; Wang, Yuan Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b13272	journal	January 2020
Skutterudite with graphene-modified grain-boundary complexion enhances zT enabling high-efficiency thermoelectric device Zong, Peng-an; Hanus, Riley; Dylla, Maxwell Energy & Environmental Science, Vol. 10, Issue 1 https://doi.org/10.1039/C6EE02467J	journal	January 2017
Constructing van der Waals gaps in cubic-structured SnTe-based thermoelectric materials Xu, Xiao; Cui, Juan; Yu, Yong Energy & Environmental Science, Vol. 13, Issue 12 https://doi.org/10.1039/D0EE02638G	journal	January 2020
Compromise and Synergy in High-Efficiency Thermoelectric Materials Zhu, Tiejun; Liu, Yintu; Fu, Chenguang Advanced Materials, Vol. 29, Issue 14 https://doi.org/10.1002/adma.201605884	journal	March 2017
Zintl Chemistry for Designing High Efficiency Thermoelectric Materials ^† ^‡ Toberer, Eric S.; May, Andrew F.; Snyder, G. Jeffrey Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm901956r	journal	February 2010
Thinking Like a Chemist: Intuition in Thermoelectric Materials Zeier, Wolfgang G.; Zevalkink, Alex; Gibbs, Zachary M. Angewandte Chemie International Edition, Vol. 55, Issue 24 https://doi.org/10.1002/anie.201508381	journal	April 2016
Correction: Computer-aided design of high-efficiency GeTe-based thermoelectric devices Hong, Min; Zheng, Kun; Lyv, Wanyu Energy & Environmental Science, Vol. 13, Issue 6 https://doi.org/10.1039/D0EE90029J	journal	January 2020
Rhombohedral to Cubic Conversion of GeTe via MnTe Alloying Leads to Ultralow Thermal Conductivity, Electronic Band Convergence, and High Thermoelectric Performance Zheng, Zheng; Su, Xianli; Deng, Rigui Journal of the American Chemical Society, Vol. 140, Issue 7 https://doi.org/10.1021/jacs.7b13611	journal	February 2018
Characterization of Lorenz number with Seebeck coefficient measurement Kim, Hyun-Sik; Gibbs, Zachary M.; Tang, Yinglu APL Materials, Vol. 3, Issue 4 https://doi.org/10.1063/1.4908244	journal	April 2015
Minimum thermal conductivity in the context of diffuson -mediated thermal transport Agne, Matthias T.; Hanus, Riley; Snyder, G. Jeffrey Energy & Environmental Science, Vol. 11, Issue 3 https://doi.org/10.1039/C7EE03256K	journal	January 2018
Low Thermal Conductivity and High Thermoelectric Performance in (GeTe) _{1–2 x} (GeSe) _x (GeS) _x : Competition between Solid Solution and Phase Separation Samanta, Manisha; Biswas, Kanishka Journal of the American Chemical Society, Vol. 139, Issue 27 https://doi.org/10.1021/jacs.7b05143	journal	June 2017
New and Old Concepts in Thermoelectric Materials Sootsman, Joseph R.; Chung, Duck Young; Kanatzidis, Mercouri G. Angewandte Chemie International Edition, Vol. 48, Issue 46, p. 8616-8639 https://doi.org/10.1002/anie.200900598	journal	November 2009
Codoping in SnTe: Enhancement of Thermoelectric Performance through Synergy of Resonance Levels and Band Convergence Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang Journal of the American Chemical Society, Vol. 137, Issue 15 https://doi.org/10.1021/jacs.5b00837	journal	April 2015
Enhanced Thermoelectric Properties of Cu ₂ SnSe ₃ by (Ag,In)-Co-Doping Li, Yuyang; Liu, Guanghua; Cao, Tengfei Advanced Functional Materials, Vol. 26, Issue 33 https://doi.org/10.1002/adfm.201601486	journal	June 2016
Thermoelectric properties of Zn doped Cu2SnSe3 Raju, Ch; Falmbigl, M.; Rogl, P. Materials Chemistry and Physics, Vol. 147, Issue 3 https://doi.org/10.1016/j.matchemphys.2014.06.054	journal	October 2014
Ultralow thermal conductivity in diamondoid lattices: high thermoelectric performance in chalcopyrite Cu _0.8+y Ag _0.2 In _1−y Te ₂ Xie, Hongyao; Hao, Shiqiang; Cai, Songting Energy & Environmental Science, Vol. 13, Issue 10 https://doi.org/10.1039/D0EE02323J	journal	January 2020
Strained endotaxial nanostructures with high thermoelectric figure of merit Biswas, Kanishka; He, Jiaqing; Zhang, Qichun Nature Chemistry, Vol. 3, Issue 2 https://doi.org/10.1038/nchem.955	journal	January 2011
Orbitally driven giant phonon anharmonicity in SnSe Li, C. W.; Hong, J.; May, A. F. Nature Physics, Vol. 11, Issue 12 https://doi.org/10.1038/nphys3492	journal	October 2015
Deep defect level engineering: a strategy of optimizing the carrier concentration for high thermoelectric performance Zhang, Qian; Song, Qichen; Wang, Xinyu Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C8EE00112J	journal	January 2018
Structural diversity and electronic properties of Cu $_{2}$ Sn $X_{3}$ ( $X = S$ , Se): A first-principles investigation Zhai, Ying-Teng; Chen, Shiyou; Yang, Ji-Hui Physical Review B, Vol. 84, Issue 7 https://doi.org/10.1103/PhysRevB.84.075213	journal	August 2011
Isotropic Conduction Network and Defect Chemistry in Mg ₃₊ _δ Sb ₂ -Based Layered Zintl Compounds with High Thermoelectric Performance Tamaki, Hiromasa; Sato, Hiroki K.; Kanno, Tsutomu Advanced Materials, Vol. 28, Issue 46 https://doi.org/10.1002/adma.201603955	journal	September 2016
Large thermoelectric power factor from crystal symmetry-protected non-bonding orbital in half-Heuslers Zhou, Jiawei; Zhu, Hangtian; Liu, Te-Huan Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03866-w	journal	April 2018
High thermoelectric performance enabled by convergence of nested conduction bands in Pb7Bi4Se13 with low thermal conductivity Hu, Lei; Fang, Yue-Wen; Qin, Feiyu Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25119-z	journal	August 2021
Enhanced thermoelectric performance of Pb doped Cu 2 SnSe 3 synthesized employing spark plasma sintering Shyam Prasad, K.; Rao, Ashok; Tyagi, Kriti Physica B: Condensed Matter, Vol. 512 https://doi.org/10.1016/j.physb.2017.02.021	journal	May 2017
Realizing high performance n-type PbTe by synergistically optimizing effective mass and carrier mobility and suppressing bipolar thermal conductivity Xiao, Yu; Wu, Haijun; Cui, Juan Energy & Environmental Science, Vol. 11, Issue 9 https://doi.org/10.1039/C8EE01151F	journal	January 2018
Non-equilibrium processing leads to record high thermoelectric figure of merit in PbTe–SrTe Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12167	journal	July 2016
A Unique Framework in BaGa ₂ Sb ₂ : A New Zintl Phase with Large Tunnels Kim, Sung-Jin; Kanatzidis, Mercouri G. Inorganic Chemistry, Vol. 40, Issue 15 https://doi.org/10.1021/ic010069n	journal	July 2001
High Thermoelectric Performance of p-Type SnTe via a Synergistic Band Engineering and Nanostructuring Approach Tan, Gangjian; Zhao, Li-Dong; Shi, Fengyuan Journal of the American Chemical Society, Vol. 136, Issue 19 https://doi.org/10.1021/ja500860m	journal	May 2014
Chemical bonding, conductive network, and thermoelectric performance of the ternary semiconductors Cu $_{2}$ Sn $X_{3}$ ( $X =$ Se, S) from first principles Xi, L.; Zhang, Y. B.; Shi, X. Y. Physical Review B, Vol. 86, Issue 15 https://doi.org/10.1103/PhysRevB.86.155201	journal	October 2012
Seeking new, highly effective thermoelectrics Xiao, Yu; Zhao, Li-Dong Science, Vol. 367, Issue 6483 https://doi.org/10.1126/science.aaz9426	journal	March 2020
Cu−Se Bond Network and Thermoelectric Compounds with Complex Diamondlike Structure Shi, Xiaoya; Xi, Lili; Fan, Jing Chemistry of Materials, Vol. 22, Issue 22 https://doi.org/10.1021/cm101589c	journal	November 2010
Heavily Doped p-Type PbSe with High Thermoelectric Performance: An Alternative for PbTe Wang, Heng; Pei, Yanzhong; LaLonde, Aaron D. Advanced Materials, Vol. 23, Issue 11, p. 1366-1370 https://doi.org/10.1002/adma.201004200	journal	February 2011
Grain boundary dominated charge transport in Mg ₃ Sb ₂ -based compounds Kuo, Jimmy Jiahong; Kang, Stephen Dongmin; Imasato, Kazuki Energy & Environmental Science, Vol. 11, Issue 2 https://doi.org/10.1039/C7EE03326E	journal	January 2018

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Title: High Thermoelectric Performance through Crystal Symmetry Enhancement in Triply Doped Diamondoid Compound Cu₂SnSe₃