Semiconducting Pavonites CdMBi4Se8 (M = Sn and Pb) and Their Thermoelectric Properties

Jing Zhao; Saiful M. Islam; Shiqiang Hao; Gangjian Tan; Xianli Su; Haijie Chen; Wenwen Lin; Rukang Li; Chris Wolverton; Mercouri G. Kanatzidis

doi:10.1021/acs.chemmater.7b03328

Semiconducting Pavonites CdMBi₄Se₈ (M = Sn and Pb) and Their Thermoelectric Properties

Jing Zhao, Saiful M. Islam, Shiqiang Hao, Gangjian Tan, Xianli Su, Haijie Chen, Wenwen Lin, Rukang Li, Chris Wolverton, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

20 Scopus citations

Abstract

Two new compounds CdPbBi₄Se₈ and CdSnBi₄Se₈ adopt the pavonite structure type and crystallize in the monoclinic space group C2/m with a = 13.713(3) Å, b = 4.1665(8) Å, c = 15.228(3) Å, β = 115.56(3)° for CdPbBi₄Se₈; a = 13.679 Å, b = 4.153 Å, c = 15.127 Å, β = 115.51° for CdSnBi₄Se₈. Their crystal structures are composed of two different types of polyhedral slabs, one containing a mixture of one octahedron [MSe₆] block and paired squared pyramids [MSe₅], while the other forms distorted galena-type (or NaCl-type) lattices with three [MSe₆] octahedral chains (M = Pb, Cd, Bi, Sn). Both CdPbBi₄Se₈ and CdSnBi₄Se₈ are stable up to -970 K. Density functional theory (DFT) calculations show that both CdPbBi₄Se₈ and CdSnBi₄Se₈ are indirect band gap semiconductors. DFT phonon dispersion calculations performed on CdSnBi₄Se₈ give valuable insights as to the origin of the observed low experimental lattice thermal conductivities of -0.58 W m^-1 K^-1 at 320 K. The title compounds exhibit n-type conduction, and they exhibit promising thermoelectric properties with a maximum thermoelectric figure of merit, ZT, reaching 0.63 for CdPbBi₄Se₈, and 0.40 for CdSnBi₄Se₈ at 850 K.

Original language	English (US)
Pages (from-to)	8494-8503
Number of pages	10
Journal	Chemistry of Materials
Volume	29
Issue number	19
DOIs	https://doi.org/10.1021/acs.chemmater.7b03328
State	Published - Oct 10 2017

Funding

This work was supported in part by the National Science Foundation (Grant DMR-1708254, exploratory synthesis of pavonites) and in part by by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award Number DE-SC0014520 (electronic structure calculations, sample measurements, thermoelectric characterization). This work made use of the EPIC facility (NUANCE Center-Northwestern University), which has received support under the State of Illinois, Northwestern University, and the National Science Foundation with Grants DMR-1121262 through the MRSEC program at the Materials Research Center, and EEC-0118025/003 through The Nanoscale Science and Engineering Center. S.H. and C.W. (DFT calculations) acknowledge support from the Department of Energy, Office of Science Basic Energy Sciences under Grant DE-SC0014520. This work was supported in part by a grant from the National Science Foundation of China (51702329).

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.7b03328

Cite this

@article{a96d629c59b645d68d00d0cbf03bccd5,

title = "Semiconducting Pavonites CdMBi4Se8 (M = Sn and Pb) and Their Thermoelectric Properties",

abstract = "Two new compounds CdPbBi4Se8 and CdSnBi4Se8 adopt the pavonite structure type and crystallize in the monoclinic space group C2/m with a = 13.713(3) {\AA}, b = 4.1665(8) {\AA}, c = 15.228(3) {\AA}, β = 115.56(3)° for CdPbBi4Se8; a = 13.679 {\AA}, b = 4.153 {\AA}, c = 15.127 {\AA}, β = 115.51° for CdSnBi4Se8. Their crystal structures are composed of two different types of polyhedral slabs, one containing a mixture of one octahedron [MSe6] block and paired squared pyramids [MSe5], while the other forms distorted galena-type (or NaCl-type) lattices with three [MSe6] octahedral chains (M = Pb, Cd, Bi, Sn). Both CdPbBi4Se8 and CdSnBi4Se8 are stable up to -970 K. Density functional theory (DFT) calculations show that both CdPbBi4Se8 and CdSnBi4Se8 are indirect band gap semiconductors. DFT phonon dispersion calculations performed on CdSnBi4Se8 give valuable insights as to the origin of the observed low experimental lattice thermal conductivities of -0.58 W m-1 K-1 at 320 K. The title compounds exhibit n-type conduction, and they exhibit promising thermoelectric properties with a maximum thermoelectric figure of merit, ZT, reaching 0.63 for CdPbBi4Se8, and 0.40 for CdSnBi4Se8 at 850 K.",

author = "Jing Zhao and Islam, {Saiful M.} and Shiqiang Hao and Gangjian Tan and Xianli Su and Haijie Chen and Wenwen Lin and Rukang Li and Chris Wolverton and Kanatzidis, {Mercouri G.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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doi = "10.1021/acs.chemmater.7b03328",

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T1 - Semiconducting Pavonites CdMBi4Se8 (M = Sn and Pb) and Their Thermoelectric Properties

AU - Zhao, Jing

AU - Islam, Saiful M.

AU - Hao, Shiqiang

AU - Tan, Gangjian

AU - Su, Xianli

AU - Chen, Haijie

AU - Lin, Wenwen

AU - Li, Rukang

AU - Wolverton, Chris

AU - Kanatzidis, Mercouri G.

PY - 2017/10/10

Y1 - 2017/10/10

N2 - Two new compounds CdPbBi4Se8 and CdSnBi4Se8 adopt the pavonite structure type and crystallize in the monoclinic space group C2/m with a = 13.713(3) Å, b = 4.1665(8) Å, c = 15.228(3) Å, β = 115.56(3)° for CdPbBi4Se8; a = 13.679 Å, b = 4.153 Å, c = 15.127 Å, β = 115.51° for CdSnBi4Se8. Their crystal structures are composed of two different types of polyhedral slabs, one containing a mixture of one octahedron [MSe6] block and paired squared pyramids [MSe5], while the other forms distorted galena-type (or NaCl-type) lattices with three [MSe6] octahedral chains (M = Pb, Cd, Bi, Sn). Both CdPbBi4Se8 and CdSnBi4Se8 are stable up to -970 K. Density functional theory (DFT) calculations show that both CdPbBi4Se8 and CdSnBi4Se8 are indirect band gap semiconductors. DFT phonon dispersion calculations performed on CdSnBi4Se8 give valuable insights as to the origin of the observed low experimental lattice thermal conductivities of -0.58 W m-1 K-1 at 320 K. The title compounds exhibit n-type conduction, and they exhibit promising thermoelectric properties with a maximum thermoelectric figure of merit, ZT, reaching 0.63 for CdPbBi4Se8, and 0.40 for CdSnBi4Se8 at 850 K.

AB - Two new compounds CdPbBi4Se8 and CdSnBi4Se8 adopt the pavonite structure type and crystallize in the monoclinic space group C2/m with a = 13.713(3) Å, b = 4.1665(8) Å, c = 15.228(3) Å, β = 115.56(3)° for CdPbBi4Se8; a = 13.679 Å, b = 4.153 Å, c = 15.127 Å, β = 115.51° for CdSnBi4Se8. Their crystal structures are composed of two different types of polyhedral slabs, one containing a mixture of one octahedron [MSe6] block and paired squared pyramids [MSe5], while the other forms distorted galena-type (or NaCl-type) lattices with three [MSe6] octahedral chains (M = Pb, Cd, Bi, Sn). Both CdPbBi4Se8 and CdSnBi4Se8 are stable up to -970 K. Density functional theory (DFT) calculations show that both CdPbBi4Se8 and CdSnBi4Se8 are indirect band gap semiconductors. DFT phonon dispersion calculations performed on CdSnBi4Se8 give valuable insights as to the origin of the observed low experimental lattice thermal conductivities of -0.58 W m-1 K-1 at 320 K. The title compounds exhibit n-type conduction, and they exhibit promising thermoelectric properties with a maximum thermoelectric figure of merit, ZT, reaching 0.63 for CdPbBi4Se8, and 0.40 for CdSnBi4Se8 at 850 K.

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