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Title: High Thermoelectric Performance in p-type Polycrystalline Cd-doped SnSe Achieved by a Combination of Cation Vacancies and Localized Lattice Engineering

Abstract

In this paper, a high figure of merit (ZT) of ≈1.7 at 823 K is reported in p-type polycrystalline Cd-doped SnSe by combining cation vacancies and localized-lattice engineering. It is observed that the introduction of Cd atoms in SnSe lattice induce Sn vacancies, which act as p-type dopants. A combination of facile solvothermal synthesis and fast spark plasma sintering technique boosts the Sn vacancy to a high level of ≈2.9%, which results in an optimum hole concentration of ≈2.6 × 1019 cm-3 and an improved power factor of ≈6.9 µW cm-1 K-2. Simultaneously, a low thermal conductivity of ≈0.33 W m-1 K-1 is achieved by effective phonon scattering at localized crystal imperfections, as observed by detailed structural characterizations. Density functional theory calculations reveal that the role of Cd atoms in the SnSe lattice is to reduce the formation energy of Sn vacancies, which in turn lower the Fermi level down into the valence bands, generating holes. This work explores the fundamental Cd-doping mechanisms at the nanoscale in a SnSe matrix and demonstrates vacancy and localized-lattice engineering as an effective approach to boosting thermoelectric performance. The work provides an avenue in achieving high-performance thermoelectric properties of materials.

Authors:
 [1];  [1];  [2];  [3];  [1];  [1];  [4];  [2]; ORCiD logo [5];  [6]
  1. Univ. of Queensland, Brisbane, QLD (Australia). Materials Engineering
  2. Vanderbilt Univ., Nashville, TN (United States). Dept. of Physics and Astronomy, and Dept. of Electrical Engineering and Computer Science; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  3. Beijing Univ. of Technology (China). Inst. of Microstructure and Properties of Advanced Materials, Beijing Key Lab. of Microstructure and Property of Solids
  4. Univ. of Southern Queensland, Springfield Central, QLD (Australia). Centre for Future Materials
  5. Univ. of Queensland, Brisbane, QLD (Australia). Materials Engineering; Univ. of Southern Queensland, Springfield Central, QLD (Australia). Centre for Future Materials
  6. Univ. of Queensland, Brisbane, QLD (Australia). Materials Engineering, and Centre for Microscopy and Microanalysis
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Vanderbilt Univ., Nashville, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1530602
Alternate Identifier(s):
OSTI ID: 1492745; OSTI ID: 1597926
Grant/Contract Number:  
FG0209ER46554; AC02-05CH11231; FG02-09ER46554
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 9; Journal Issue: 11; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cd-doping; characterization; solvothermal; thermoelectric; tin selenide

Citation Formats

Shi, Xiaolei -L., Wu, Angyin -Y., Feng, Tianli, Zheng, Kun, Liu, Weidi -D., Sun, Qiang, Hong, Min, Pantelides, Sokrates T., Chen, Zhi-Gang, and Zou, Jin. High Thermoelectric Performance in p-type Polycrystalline Cd-doped SnSe Achieved by a Combination of Cation Vacancies and Localized Lattice Engineering. United States: N. p., 2019. Web. doi:10.1002/aenm.201803242.
Shi, Xiaolei -L., Wu, Angyin -Y., Feng, Tianli, Zheng, Kun, Liu, Weidi -D., Sun, Qiang, Hong, Min, Pantelides, Sokrates T., Chen, Zhi-Gang, & Zou, Jin. High Thermoelectric Performance in p-type Polycrystalline Cd-doped SnSe Achieved by a Combination of Cation Vacancies and Localized Lattice Engineering. United States. doi:https://doi.org/10.1002/aenm.201803242
Shi, Xiaolei -L., Wu, Angyin -Y., Feng, Tianli, Zheng, Kun, Liu, Weidi -D., Sun, Qiang, Hong, Min, Pantelides, Sokrates T., Chen, Zhi-Gang, and Zou, Jin. Tue . "High Thermoelectric Performance in p-type Polycrystalline Cd-doped SnSe Achieved by a Combination of Cation Vacancies and Localized Lattice Engineering". United States. doi:https://doi.org/10.1002/aenm.201803242. https://www.osti.gov/servlets/purl/1530602.
@article{osti_1530602,
title = {High Thermoelectric Performance in p-type Polycrystalline Cd-doped SnSe Achieved by a Combination of Cation Vacancies and Localized Lattice Engineering},
author = {Shi, Xiaolei -L. and Wu, Angyin -Y. and Feng, Tianli and Zheng, Kun and Liu, Weidi -D. and Sun, Qiang and Hong, Min and Pantelides, Sokrates T. and Chen, Zhi-Gang and Zou, Jin},
abstractNote = {In this paper, a high figure of merit (ZT) of ≈1.7 at 823 K is reported in p-type polycrystalline Cd-doped SnSe by combining cation vacancies and localized-lattice engineering. It is observed that the introduction of Cd atoms in SnSe lattice induce Sn vacancies, which act as p-type dopants. A combination of facile solvothermal synthesis and fast spark plasma sintering technique boosts the Sn vacancy to a high level of ≈2.9%, which results in an optimum hole concentration of ≈2.6 × 1019 cm-3 and an improved power factor of ≈6.9 µW cm-1 K-2. Simultaneously, a low thermal conductivity of ≈0.33 W m-1 K-1 is achieved by effective phonon scattering at localized crystal imperfections, as observed by detailed structural characterizations. Density functional theory calculations reveal that the role of Cd atoms in the SnSe lattice is to reduce the formation energy of Sn vacancies, which in turn lower the Fermi level down into the valence bands, generating holes. This work explores the fundamental Cd-doping mechanisms at the nanoscale in a SnSe matrix and demonstrates vacancy and localized-lattice engineering as an effective approach to boosting thermoelectric performance. The work provides an avenue in achieving high-performance thermoelectric properties of materials.},
doi = {10.1002/aenm.201803242},
journal = {Advanced Energy Materials},
number = 11,
volume = 9,
place = {United States},
year = {2019},
month = {1}
}

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Works referenced in this record:

Polycrystalline SnSe with Extraordinary Thermoelectric Property via Nanoporous Design
journal, October 2018


Incoherent imaging using dynamically scattered coherent electrons
journal, June 1999


Thermoelectric properties of p-type polycrystalline SnSe doped with Ag
journal, January 2014

  • Chen, Cheng-Lung; Wang, Heng; Chen, Yang-Yuan
  • Journal of Materials Chemistry A, Vol. 2, Issue 29, p. 11171-11176
  • DOI: 10.1039/C4TA01643B

Thermoelectric transport properties of pristine and Na-doped SnSe 1−x Te x polycrystals
journal, January 2015

  • Wei, Tian-Ran; Wu, Chao-Feng; Zhang, Xiaozhi
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 44
  • DOI: 10.1039/C5CP05510E

Thermoelectrics with earth abundant elements: low thermal conductivity and high thermopower in doped SnS
journal, January 2014

  • Tan, Qing; Zhao, Li-Dong; Li, Jing-Feng
  • J. Mater. Chem. A, Vol. 2, Issue 41
  • DOI: 10.1039/C4TA04462B

Studies on cadmium toxicity in plants: A review
journal, January 1997


Single parabolic band behavior of thermoelectric p-type CuGaTe 2
journal, January 2016

  • Shen, Jiawen; Chen, Zhiwei; lin, Siqi
  • Journal of Materials Chemistry C, Vol. 4, Issue 1
  • DOI: 10.1039/C5TC03325J

The intrinsic thermal conductivity of SnSe
journal, November 2016

  • Wei, Pai-Chun; Bhattacharya, S.; He, J.
  • Nature, Vol. 539, Issue 7627
  • DOI: 10.1038/nature19832

High-performance SnSe thermoelectric materials: Progress and future challenge
journal, August 2018


The effect of Sm doping on the transport and thermoelectric properties of SnSe
journal, September 2017


Enhancing p-Type Thermoelectric Performances of Polycrystalline SnSe via Tuning Phase Transition Temperature
journal, July 2017

  • Lee, Yong Kyu; Ahn, Kyunghan; Cha, Joonil
  • Journal of the American Chemical Society, Vol. 139, Issue 31
  • DOI: 10.1021/jacs.7b05881

New Directions for Low-Dimensional Thermoelectric Materials
journal, April 2007

  • Dresselhaus, M. S.; Chen, G.; Tang, M. Y.
  • Advanced Materials, Vol. 19, Issue 8, p. 1043-1053
  • DOI: 10.1002/adma.200600527

High Performance Thermoelectric Materials: Progress and Their Applications
journal, November 2017

  • Yang, Lei; Chen, Zhi-Gang; Dargusch, Matthew S.
  • Advanced Energy Materials, Vol. 8, Issue 6
  • DOI: 10.1002/aenm.201701797

Giant Seebeck effect in Ge-doped SnSe
journal, June 2016

  • Gharsallah, M.; Serrano-Sánchez, F.; Nemes, N. M.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep26774

Distinct Impact of Alkali-Ion Doping on Electrical Transport Properties of Thermoelectric p -Type Polycrystalline SnSe
journal, July 2016

  • Wei, Tian-Ran; Tan, Gangjian; Zhang, Xiaomi
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04181

Optimization of Thermoelectric Performance of Anisotropic Ag x Sn1−x Se Compounds
journal, October 2015


Detector geometry, thermal diffuse scattering and strain effects in ADF STEM imaging
journal, April 1995


Study on Thermoelectric Properties of Polycrystalline SnSe by Ge Doping
journal, March 2017


Realizing High Figure of Merit in Phase-Separated Polycrystalline Sn 1– x Pb x Se
journal, October 2016

  • Tang, Guodong; Wei, Wei; Zhang, Jian
  • Journal of the American Chemical Society, Vol. 138, Issue 41
  • DOI: 10.1021/jacs.6b07010

Thermoelectric transport properties of polycrystalline SnSe alloyed with PbSe
journal, January 2017

  • Wei, Tian-Ran; Tan, Gangjian; Wu, Chao-Feng
  • Applied Physics Letters, Vol. 110, Issue 5
  • DOI: 10.1063/1.4975603

Lower limit to the thermal conductivity of disordered crystals
journal, September 1992

  • Cahill, David G.; Watson, S. K.; Pohl, R. O.
  • Physical Review B, Vol. 46, Issue 10, p. 6131-6140
  • DOI: 10.1103/PhysRevB.46.6131

Indium substitution effect on thermoelectric and optical properties of Sn1−In Se compounds
journal, October 2016


Significant enhancement of figure-of-merit in carbon-reinforced Cu2Se nanocrystalline solids
journal, November 2017


Grain size optimization for high-performance polycrystalline SnSe thermoelectrics
journal, January 2017

  • Peng, Kunling; Wu, Hong; Yan, YanCi
  • Journal of Materials Chemistry A, Vol. 5, Issue 27
  • DOI: 10.1039/C7TA03390G

Solvothermal Route to Tin Monoselenide Bulk Single Crystal with Different Morphologies
journal, May 2000

  • Li, Bin; Xie, Yi; Huang, Jiaxing
  • Inorganic Chemistry, Vol. 39, Issue 10
  • DOI: 10.1021/ic990964v

Materials selection guidelines for low thermal conductivity thermal barrier coatings
journal, January 2003


Thermoelectric Properties of Tl-Doped SnSe: A Hint of Phononic Structure
journal, March 2016


Sodium doped polycrystalline SnSe: High pressure synthesis and thermoelectric properties
journal, December 2017


Achieving ZT=2.2 with Bi-doped n-type SnSe single crystals
journal, December 2016

  • Duong, Anh Tuan; Nguyen, Van Quang; Duvjir, Ganbat
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13713

Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals
journal, April 2014

  • Zhao, Li-Dong; Lo, Shih-Han; Zhang, Yongsheng
  • Nature, Vol. 508, Issue 7496, p. 373-377
  • DOI: 10.1038/nature13184

Facile chemical synthesis and enhanced thermoelectric properties of Ag doped SnSe nanocrystals
journal, January 2017

  • Chien, Chia-Hua; Chang, Chung-Chieh; Chen, Cheng-Lung
  • RSC Advances, Vol. 7, Issue 54
  • DOI: 10.1039/C7RA05819E

SnSe: a remarkable new thermoelectric material
journal, January 2016

  • Zhao, Li-Dong; Chang, Cheng; Tan, Gangjian
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE01755J

Three-Stage Inter-Orthorhombic Evolution and High Thermoelectric Performance in Ag-Doped Nanolaminar SnSe Polycrystals
journal, June 2017

  • Zhang, Lijuan; Wang, Jianli; Sun, Qiao
  • Advanced Energy Materials, Vol. 7, Issue 19
  • DOI: 10.1002/aenm.201700573

The panoscopic approach to high performance thermoelectrics
journal, January 2014

  • Zhao, Li-Dong; Dravid, Vinayak P.; Kanatzidis, Mercouri G.
  • Energy Environ. Sci., Vol. 7, Issue 1
  • DOI: 10.1039/C3EE43099E

Reinvestigation of the thermal properties of single-crystalline SnSe
journal, January 2017

  • Ibrahim, D.; Vaney, J. -B.; Sassi, S.
  • Applied Physics Letters, Vol. 110, Issue 3
  • DOI: 10.1063/1.4974348

The thermoelectric performance of anisotropic SnSe doped with Na
journal, January 2016

  • Leng, Hua-Qian; Zhou, Min; Zhao, Jie
  • RSC Advances, Vol. 6, Issue 11
  • DOI: 10.1039/C5RA19469E

A study of structural, optical and magnetic properties of Zn0.97−xCuxCr0.03O diluted magnetic semiconductors
journal, February 2011


Compromise and Synergy in High-Efficiency Thermoelectric Materials
journal, March 2017


Assessment of the thermoelectric performance of polycrystalline p-type SnSe
journal, May 2014

  • Sassi, S.; Candolfi, C.; Vaney, J.-B.
  • Applied Physics Letters, Vol. 104, Issue 21, Article No. 212105
  • DOI: 10.1063/1.4880817

Nanostructures in Te/Sb/Ge/Ag (TAGS) Thermoelectric Materials Induced by Phase Transitions Associated with Vacancy Ordering
journal, June 2014

  • Schröder, Thorsten; Rosenthal, Tobias; Giesbrecht, Nadja
  • Inorganic Chemistry, Vol. 53, Issue 14
  • DOI: 10.1021/ic5010243

Eco-Friendly Higher Manganese Silicide Thermoelectric Materials: Progress and Future Challenges
journal, April 2018

  • Liu, Wei-Di; Chen, Zhi-Gang; Zou, Jin
  • Advanced Energy Materials, Vol. 8, Issue 19
  • DOI: 10.1002/aenm.201800056

Enhanced mid-temperature thermoelectric performance of textured SnSe polycrystals made of solvothermally synthesized powders
journal, January 2016

  • Li, Yiwen; Li, Fu; Dong, Jinfeng
  • Journal of Materials Chemistry C, Vol. 4, Issue 10
  • DOI: 10.1039/C5TC04202J

The effect of doping on thermoelectric performance of p-type SnSe: Promising thermoelectric material
journal, May 2016


Performance optimization and single parabolic band behavior of thermoelectric MnTe
journal, January 2017

  • Xu, Yidong; Li, Wen; Wang, Chen
  • Journal of Materials Chemistry A, Vol. 5, Issue 36
  • DOI: 10.1039/C7TA04842D

Understanding of the Extremely Low Thermal Conductivity in High-Performance Polycrystalline SnSe through Potassium Doping
journal, August 2016

  • Chen, Yue-Xing; Ge, Zhen-Hua; Yin, Meijie
  • Advanced Functional Materials, Vol. 26, Issue 37
  • DOI: 10.1002/adfm.201602652

Eco-Friendly SnTe Thermoelectric Materials: Progress and Future Challenges
journal, September 2017

  • Moshwan, Raza; Yang, Lei; Zou, Jin
  • Advanced Functional Materials, Vol. 27, Issue 43
  • DOI: 10.1002/adfm.201703278

3D charge and 2D phonon transports leading to high out-of-plane ZT in n-type SnSe crystals
journal, May 2018


Thermoelectric performance of SnS and SnS–SnSe solid solution
journal, January 2015

  • Han, Ye-Mao; Zhao, Jie; Zhou, Min
  • Journal of Materials Chemistry A, Vol. 3, Issue 8
  • DOI: 10.1039/C4TA06955B

Achieving High Thermoelectric Figure of Merit in Polycrystalline SnSe via Introducing Sn Vacancies
journal, December 2017

  • Wei, Wei; Chang, Cheng; Yang, Teng
  • Journal of the American Chemical Society, Vol. 140, Issue 1
  • DOI: 10.1021/jacs.7b11875

High thermoelectric performance of higher manganese silicides prepared by ultra-fast thermal explosion
journal, January 2015

  • She, Xiaoyu; Su, Xianli; Du, Huizhen
  • Journal of Materials Chemistry C, Vol. 3, Issue 46
  • DOI: 10.1039/C5TC02837J

Studies on thermoelectric figure of merit of Na-doped p-type polycrystalline SnSe
journal, January 2016

  • Chere, Eyob K.; Zhang, Qian; Dahal, Keshab
  • Journal of Materials Chemistry A, Vol. 4, Issue 5
  • DOI: 10.1039/C5TA08847J

Enhancing the thermoelectric performance of SnSe 1−x Te x nanoplates through band engineering
journal, January 2017

  • Hong, Min; Chen, Zhi-Gang; Yang, Lei
  • Journal of Materials Chemistry A, Vol. 5, Issue 21
  • DOI: 10.1039/C7TA02677C

Enhanced Seebeck coefficient through energy-barrier scattering in PbTe nanocomposites
journal, March 2009


Promising Thermoelectric Bulk Materials with 2D Structures
journal, July 2017


Solid-State Explosive Reaction for Nanoporous Bulk Thermoelectric Materials
journal, September 2017

  • Zhao, Kunpeng; Duan, Haozhi; Raghavendra, Nunna
  • Advanced Materials, Vol. 29, Issue 42
  • DOI: 10.1002/adma.201701148

Enhanced thermoelectric performance of p-type SnSe doped with Zn
journal, January 2017


Raising thermoelectric performance of n-type SnSe via Br doping and Pb alloying
journal, January 2016

  • Chang, Cheng; Tan, Qing; Pei, Yanling
  • RSC Advances, Vol. 6, Issue 100
  • DOI: 10.1039/C6RA21884A

Boosting the Thermoelectric Performance of (Na,K)-Codoped Polycrystalline SnSe by Synergistic Tailoring of the Band Structure and Atomic-Scale Defect Phonon Scattering
journal, July 2017

  • Ge, Zhen-Hua; Song, Dongsheng; Chong, Xiaoyu
  • Journal of the American Chemical Society, Vol. 139, Issue 28
  • DOI: 10.1021/jacs.7b05339

Influence of Sodium Chloride Doping on Thermoelectric Properties of p-type SnSe
journal, August 2017

  • Yang, Shi Dan; Nutor, Raymond Kwesi; Chen, Zi Jie
  • Journal of Electronic Materials, Vol. 46, Issue 11
  • DOI: 10.1007/s11664-017-5715-2

Study on the thermoelectric performance of polycrystal SnSe with Se vacancies
journal, May 2018


Broad temperature plateau for high ZTs in heavily doped p-type SnSe single crystals
journal, January 2016

  • Peng, Kunling; Lu, Xu; Zhan, Heng
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/C5EE03366G

Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe
journal, November 2015


Achieving high Figure of Merit in p-type polycrystalline Sn0.98Se via self-doping and anisotropy-strengthening
journal, January 2018


Electronic structure and thermoelectric properties of n - and p -type SnSe from first-principles calculations
journal, May 2015


Low-cost and environmentally benign selenides as promising thermoelectric materials
journal, December 2018


    Works referencing / citing this record:

    High‐Performance Thermoelectric SnSe: Aqueous Synthesis, Innovations, and Challenges
    journal, February 2020


    Thermal Transport in 3D Nanostructures
    journal, August 2019

    • Zhan, Haifei; Nie, Yihan; Chen, Yongnan
    • Advanced Functional Materials, Vol. 30, Issue 8
    • DOI: 10.1002/adfm.201903841

    Promising and Eco‐Friendly Cu 2 X‐Based Thermoelectric Materials: Progress and Applications
    journal, January 2020


    Anisotropy Control–Induced Unique Anisotropic Thermoelectric Performance in the n‐Type Bi 2 Te 2.7 Se 0.3 Thin Films
    journal, May 2019


    Multifunctional inorganic nanomaterials for energy applications
    journal, January 2020

    • Wang, Huilin; Liang, Xitong; Wang, Jiutian
    • Nanoscale, Vol. 12, Issue 1
    • DOI: 10.1039/c9nr07008g

    Pressure-induced enhancement of thermoelectric power factor in pristine and hole-doped SnSe crystals
    journal, January 2019


    Facile in situ solution synthesis of SnSe/rGO nanocomposites with enhanced thermoelectric performance
    journal, January 2020

    • Huang, Lisi; Lu, Jianzhang; Ma, Duowen
    • Journal of Materials Chemistry A, Vol. 8, Issue 3
    • DOI: 10.1039/c9ta11737g

    Anion-exchange synthesis of thermoelectric layered SnS 0.1 Se 0.9−x Te x nano/microstructures in aqueous solution: complexity and carrier concentration
    journal, January 2019

    • Huang, Lisi; Han, Guang; Zhang, Bin
    • Journal of Materials Chemistry C, Vol. 7, Issue 25
    • DOI: 10.1039/c9tc01994d