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

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

doi:10.1002/aenm.202100661

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

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

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

64 Citations (Scopus)

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 Cu₂SnSe₃ leads to a high ZT value of 1.6 at 823 K for Cu_1.85Ag_0.15(Sn_0.88Ga_0.1Na_0.02)Se₃, and a decent average ZT (ZT_ave) value of 0.7 is also achieved for Cu_1.85Ag_0.15(Sn_0.93Mg_0.06Na_0.01)Se₃ 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 Cu₂SnSe₃ 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 Cu₂SnSe₃ 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_1.85Ag_0.15(Sn_0.88Ga_0.1Na_0.02)Se₃. This work provides a standpoint to design promising thermoelectric materials by synergistically manipulating crystal symmetry and nanoscale defects. © 2021 Wiley-VCH GmbH

Original language	English
Article number	2100661
Number of pages	11
Journal	Advanced Energy Materials
Volume	11
Issue number	42
Online published	9 Oct 2021
DOIs	https://doi.org/10.1002/aenm.202100661
Publication status	Published - 11 Nov 2021
Externally published	Yes

Funding

This work was supported by the U.S. Department of Energy, Office of Science Basic Energy Sciences under grant DE-SC0014520, DOE Office of Science (materials characterization, sample synthesis, transport properties). User Facilities were supported by the Office of Science of the U.S. Department of Energy under Contract Nos. DE-AC02-06CH11357 and DE-AC02-05CH11231. Access to facilities of high-performance computational resources at the Northwestern University is acknowledged. The authors also acknowledge Singapore MOE Tier 2 under Grant Nos. MOE2018-T2-1-010, Singapore A*STAR Pharos Program SERC 1527200022, and Singapore A*STAR project A19D9a0096. The electron microscopy and XRD work were performed at the Facility for Analysis, Characterization, Testing and Simulation (FACTS), Nanyang Technological University, Singapore. The synchrotron radiation experiments were performed at the BL02B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2021A1074). Use of the Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science, under Contract DE-AC02-06CH11357. Y.-W.F. acknowledges the computational resources provided by the New York University New York, Abu Dhabi and Shanghai. The authors acknowledge the SXRD and PDF data collection by Dr. Zhao Pan, Dr. Tianwei Li, and Senior Scientist Dr. Yang Ren.

Research Keywords

crystal symmetry
diamondoid structure
nanoscale defects
thermoelectrics

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Hu, L., Luo, Y., Fang, Y.-W., Qin, F., Cao, X., Xie, H., Liu, J., Dong, J., Sanson, A., Giarola, M., Tan, X., Zheng, Y., Suwardi, A., Huang, Y., Hippalgaonkar, K., He, J., Zhang, W., Xu, J., Yan, Q., & Kanatzidis, M. G. (2021). High Thermoelectric Performance through Crystal Symmetry Enhancement in Triply Doped Diamondoid Compound Cu₂SnSe₃. Advanced Energy Materials, 11(42), Article 2100661. https://doi.org/10.1002/aenm.202100661

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title = "High Thermoelectric Performance through Crystal Symmetry Enhancement in Triply Doped Diamondoid Compound Cu2SnSe3",

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 Cu2SnSe3 leads to a high ZT value of 1.6 at 823 K for Cu1.85Ag0.15(Sn0.88Ga0.1Na0.02)Se3, and a decent average ZT (ZTave) value of 0.7 is also achieved for Cu1.85Ag0.15(Sn0.93Mg0.06Na0.01)Se3 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 Cu2SnSe3 into a cubic structure. This symmetry enhancing leads to an increase in the effective mass from 0.8 me to 2.6 me (me, free electron mass) and the power factor from 4.3 µW cm−1 K−2 for Cu2SnSe3 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 Cu1.85Ag0.15(Sn0.88Ga0.1Na0.02)Se3. This work provides a standpoint to design promising thermoelectric materials by synergistically manipulating crystal symmetry and nanoscale defects. {\textcopyright} 2021 Wiley-VCH GmbH",

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

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Hu, L, Luo, Y, Fang, Y-W, Qin, F, Cao, X, Xie, H, Liu, J, Dong, J, Sanson, A, Giarola, M, Tan, X, Zheng, Y, Suwardi, A, Huang, Y, Hippalgaonkar, K, He, J, Zhang, W, Xu, J, Yan, Q & Kanatzidis, MG 2021, 'High Thermoelectric Performance through Crystal Symmetry Enhancement in Triply Doped Diamondoid Compound Cu₂SnSe₃', Advanced Energy Materials, vol. 11, no. 42, 2100661. https://doi.org/10.1002/aenm.202100661

TY - JOUR

T1 - High Thermoelectric Performance through Crystal Symmetry Enhancement in Triply Doped Diamondoid Compound Cu2SnSe3

AU - Hu, Lei

AU - Luo, Yubo

AU - Fang, Yue-Wen

AU - Qin, Feiyu

AU - Cao, Xun

AU - Xie, Hongyao

AU - Liu, Jiawei

AU - Dong, Jinfeng

AU - Sanson, Andrea

AU - Giarola, Marco

AU - Tan, Xianyi

AU - Zheng, Yun

AU - Suwardi, Ady

AU - Huang, Yizhong

AU - Hippalgaonkar, Kedar

AU - He, Jiaqing

AU - Zhang, Wenqing

AU - Xu, Jianwei

AU - Yan, Qingyu

AU - Kanatzidis, Mercouri G.

PY - 2021/11/11

Y1 - 2021/11/11

N2 - 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 Cu2SnSe3 leads to a high ZT value of 1.6 at 823 K for Cu1.85Ag0.15(Sn0.88Ga0.1Na0.02)Se3, and a decent average ZT (ZTave) value of 0.7 is also achieved for Cu1.85Ag0.15(Sn0.93Mg0.06Na0.01)Se3 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 Cu2SnSe3 into a cubic structure. This symmetry enhancing leads to an increase in the effective mass from 0.8 me to 2.6 me (me, free electron mass) and the power factor from 4.3 µW cm−1 K−2 for Cu2SnSe3 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 Cu1.85Ag0.15(Sn0.88Ga0.1Na0.02)Se3. This work provides a standpoint to design promising thermoelectric materials by synergistically manipulating crystal symmetry and nanoscale defects. © 2021 Wiley-VCH GmbH

AB - 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 Cu2SnSe3 leads to a high ZT value of 1.6 at 823 K for Cu1.85Ag0.15(Sn0.88Ga0.1Na0.02)Se3, and a decent average ZT (ZTave) value of 0.7 is also achieved for Cu1.85Ag0.15(Sn0.93Mg0.06Na0.01)Se3 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 Cu2SnSe3 into a cubic structure. This symmetry enhancing leads to an increase in the effective mass from 0.8 me to 2.6 me (me, free electron mass) and the power factor from 4.3 µW cm−1 K−2 for Cu2SnSe3 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 Cu1.85Ag0.15(Sn0.88Ga0.1Na0.02)Se3. This work provides a standpoint to design promising thermoelectric materials by synergistically manipulating crystal symmetry and nanoscale defects. © 2021 Wiley-VCH GmbH

KW - crystal symmetry

KW - diamondoid structure

KW - nanoscale defects

KW - thermoelectrics

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