skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Thermoelectric properties of copper selenide with ordered selenium layer and disordered copper layer

Abstract

Thermoelectric figure-of-merit (ZT) of ~1.6 at 700 °C is achieved in β-phase copper selenide (Cu2Se) made by ball milling and hot pressing. The β-phase of such material possesses a natural superlattice-like structure that combines ordered selenium (Se) and disordered copper (Cu) layers in its unit cell, resulting in a low lattice thermal conductivity of 0.4–0.5 W m-1 K-1. A λ-shaped specific heat peak indicates a phase transition from cubic β-phase to tetragonal α-phase at around 140 °C upon cooling and vice versa. An abnormal decrease in specific heat with increasing temperature was also observed here due to the increased random motion of disordered Cu atoms. These features indicate that β-phase Cu2Se could be potentially an interesting thermoelectric material, competing with other conventional thermoelectric materials.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Boston College, Chestnut Hill, MA (United States). Dept. of Physics
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Mechanical Engineering
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1386802
Grant/Contract Number:  
SC0001299
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 1; Journal Issue: 3; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; copper selenide; thermoelectrics; ordered and disordered layers; natural superlattice; specific heat

Citation Formats

Yu, Bo, Liu, Weishu, Chen, Shuo, Wang, Hui, Wang, Hengzhi, Chen, Gang, and Ren, Zhifeng. Thermoelectric properties of copper selenide with ordered selenium layer and disordered copper layer. United States: N. p., 2012. Web. https://doi.org/10.1016/j.nanoen.2012.02.010.
Yu, Bo, Liu, Weishu, Chen, Shuo, Wang, Hui, Wang, Hengzhi, Chen, Gang, & Ren, Zhifeng. Thermoelectric properties of copper selenide with ordered selenium layer and disordered copper layer. United States. https://doi.org/10.1016/j.nanoen.2012.02.010
Yu, Bo, Liu, Weishu, Chen, Shuo, Wang, Hui, Wang, Hengzhi, Chen, Gang, and Ren, Zhifeng. Tue . "Thermoelectric properties of copper selenide with ordered selenium layer and disordered copper layer". United States. https://doi.org/10.1016/j.nanoen.2012.02.010. https://www.osti.gov/servlets/purl/1386802.
@article{osti_1386802,
title = {Thermoelectric properties of copper selenide with ordered selenium layer and disordered copper layer},
author = {Yu, Bo and Liu, Weishu and Chen, Shuo and Wang, Hui and Wang, Hengzhi and Chen, Gang and Ren, Zhifeng},
abstractNote = {Thermoelectric figure-of-merit (ZT) of ~1.6 at 700 °C is achieved in β-phase copper selenide (Cu2Se) made by ball milling and hot pressing. The β-phase of such material possesses a natural superlattice-like structure that combines ordered selenium (Se) and disordered copper (Cu) layers in its unit cell, resulting in a low lattice thermal conductivity of 0.4–0.5 W m-1 K-1. A λ-shaped specific heat peak indicates a phase transition from cubic β-phase to tetragonal α-phase at around 140 °C upon cooling and vice versa. An abnormal decrease in specific heat with increasing temperature was also observed here due to the increased random motion of disordered Cu atoms. These features indicate that β-phase Cu2Se could be potentially an interesting thermoelectric material, competing with other conventional thermoelectric materials.},
doi = {10.1016/j.nanoen.2012.02.010},
journal = {Nano Energy},
number = 3,
volume = 1,
place = {United States},
year = {2012},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 93 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys
journal, May 2008


Nanostructured Thermoelectrics: Big Efficiency Gains from Small Features
journal, July 2010

  • Vineis, Christopher J.; Shakouri, Ali; Majumdar, Arun
  • Advanced Materials, Vol. 22, Issue 36, p. 3970-3980
  • DOI: 10.1002/adma.201000839

Recent advances in thermoelectric nanocomposites
journal, January 2012


Filled Skutterudite Antimonides: A New Class of Thermoelectric Materials
journal, May 1996


Semiconducting Ge clathrates: Promising candidates for thermoelectric applications
journal, July 1998

  • Nolas, G. S.; Cohn, J. L.; Slack, G. A.
  • Applied Physics Letters, Vol. 73, Issue 2
  • DOI: 10.1063/1.121747

Complex thermoelectric materials
journal, February 2008

  • Snyder, G. Jeffrey; Toberer, Eric S.
  • Nature Materials, Vol. 7, Issue 2, p. 105-114
  • DOI: 10.1038/nmat2090

Thin-film thermoelectric devices with high room-temperature figures of merit
journal, October 2001

  • Venkatasubramanian, Rama; Siivola, Edward; Colpitts, Thomas
  • Nature, Vol. 413, Issue 6856, p. 597-602
  • DOI: 10.1038/35098012

Quantum Dot Superlattice Thermoelectric Materials and Devices
journal, September 2002


High-Temperature Thermoelectric Properties of Na x CoO 2-δ Single Crystals
journal, July 2001

  • Fujita, Kenjiro; Mochida, Tadashi; Nakamura, Kazuo
  • Japanese Journal of Applied Physics, Vol. 40, Issue Part 1, No. 7
  • DOI: 10.1143/JJAP.40.4644

Complex Oxide Materials for Potential Thermoelectric Applications
journal, March 2006

  • Koumoto, Kunihito; Terasaki, Ichiro; Funahashi, Ryoji
  • MRS Bulletin, Vol. 31, Issue 3
  • DOI: 10.1557/mrs2006.46

Size and Interface Effects on Thermal Conductivity of Superlattices and Periodic Thin-Film Structures
journal, May 1997


Thermal conductivity and ballistic-phonon transport in the cross-plane direction of superlattices
journal, June 1998


Peierls distortion as a route to high thermoelectric performance in In4Se3-δ crystals
journal, June 2009

  • Rhyee, Jong-Soo; Lee, Kyu Hyoung; Lee, Sang Mock
  • Nature, Vol. 459, Issue 7249
  • DOI: 10.1038/nature08088

X-ray study of the average structures of Cu2Se and Cu1.8S in the room temperature and the high temperature phases
journal, July 1991


Ionic conductivity and chemical diffusion in Ag2SeCu2Se mixed conductor compounds
journal, January 1989

  • Yakshibayev, R. A.; Almukhametov, R. F.; Balapanov, M. Kh.
  • Solid State Ionics, Vol. 31, Issue 4, p. 247-251
  • DOI: 10.1016/0167-2738(89)90464-5

Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports
journal, May 2011

  • Shi, Xun; Yang, Jiong; Salvador, James R.
  • Journal of the American Chemical Society, Vol. 133, Issue 20
  • DOI: 10.1021/ja111199y

Cubic AgPbmSbTe2+m: Bulk Thermoelectric Materials with High Figure of Merit
journal, February 2004


Enhancement of Thermoelectric Efficiency in PbTe by Distortion of the Electronic Density of States
journal, July 2008

  • Heremans, J. P.; Jovovic, V.; Toberer, E. S.
  • Science, Vol. 321, Issue 5888, p. 554-557
  • DOI: 10.1126/science.1159725

Convergence of electronic bands for high performance bulk thermoelectrics
journal, May 2011

  • Pei, Yanzhong; Shi, Xiaoya; LaLonde, Aaron
  • Nature, Vol. 473, Issue 7345, p. 66-69
  • DOI: 10.1038/nature09996

Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties
journal, June 2004

  • Snyder, G. Jeffrey; Christensen, Mogens; Nishibori, Eiji
  • Nature Materials, Vol. 3, Issue 7
  • DOI: 10.1038/nmat1154

Silver(I) sulfide: Ag2S Heat capacity from 5 to 1000 K, thermodynamic properties, and transitions
journal, April 1986

  • Grønvold, Fredrik; Westrum, Edgar F.
  • The Journal of Chemical Thermodynamics, Vol. 18, Issue 4, p. 381-401
  • DOI: 10.1016/0021-9614(86)90084-4

Order–Disorder Transition in AgCrSe 2 : a New Route to Efficient Thermoelectrics
journal, May 2011

  • Gascoin, Franck; Maignan, Antoine
  • Chemistry of Materials, Vol. 23, Issue 10
  • DOI: 10.1021/cm200581k

Anharmonic contributions to vibrational thermodynamic properties of solids
journal, September 1961


Anharmonic effects in the thermodynamic properties of solids II. Analysis of data for lead and aluminium
journal, December 1968


Temperature dependence of heat capacity and viscosity of non-associated liquids
journal, January 1968

  • Dexter, A. R.; Matheson, A. J.
  • Transactions of the Faraday Society, Vol. 64
  • DOI: 10.1039/tf9686402632

The Heat Capacity of Liquid Metals
journal, June 1975


Heat capacity of liquids: An approach from the solid phase
journal, September 2008


Superionics: crystal structures and conduction processes
journal, June 2004


Copper ion liquid-like thermoelectrics
journal, March 2012

  • Liu, Huili; Shi, Xun; Xu, Fangfang
  • Nature Materials, Vol. 11, Issue 5, p. 422-425
  • DOI: 10.1038/nmat3273

    Works referencing / citing this record:

    Recent advances in high-performance bulk thermoelectric materials
    journal, May 2016


    Mechanochemical synthesis of high thermoelectric performance bulk Cu 2 X (X = S, Se) materials
    journal, November 2016

    • Yang, Dongwang; Su, Xianli; Yan, Yonggao
    • APL Materials, Vol. 4, Issue 11
    • DOI: 10.1063/1.4968521

    A supercell approach to the doping effect on the thermoelectric properties of SnSe
    journal, January 2015

    • Suzuki, Yasumitsu; Nakamura, Hisao
    • Physical Chemistry Chemical Physics, Vol. 17, Issue 44
    • DOI: 10.1039/c5cp05151g

    High-performance and low thermal conductivity in nano-layered Cu 2 Se prepared by a NaCl-flux method
    journal, January 2019

    • Liu, Wenting; Shen, Lanxian; Shai, Xuxia
    • CrystEngComm, Vol. 21, Issue 44
    • DOI: 10.1039/c9ce01258c

    n-type thermoelectric material Mg 2 Sn 0.75 Ge 0.25 for high power generation
    journal, March 2015

    • Liu, Weishu; Kim, Hee Seok; Chen, Shuo
    • Proceedings of the National Academy of Sciences, Vol. 112, Issue 11
    • DOI: 10.1073/pnas.1424388112

    State-of-the-Art Reviews and Analyses of Emerging Research Findings and Achievements of Thermoelectric Materials over the Past Years
    journal, December 2018

    • Selvan, Krishna Veni; Hasan, Md Nazibul; Mohamed Ali, Mohamed Sultan
    • Journal of Electronic Materials, Vol. 48, Issue 2
    • DOI: 10.1007/s11664-018-06838-4

    High thermoelectric performance and low thermal conductivity in Cu2-xNaxSe bulk materials with micro-pores
    journal, July 2019


    High thermoelectric performance of Ba 3 Cu 16−x (S,Te) 11
    journal, January 2018

    • Jafarzadeh, Parisa; Oudah, Mohamed; Assoud, Abdeljalil
    • Journal of Materials Chemistry C, Vol. 6, Issue 47
    • DOI: 10.1039/c8tc05038d

    Epitaxial Growth of 1D Atomic Chain Based Se Nanoplates on Monolayer ReS 2 for High‐Performance Photodetectors
    journal, October 2018

    • Qin, Jing‐Kai; Qiu, Gang; He, Wen
    • Advanced Functional Materials, Vol. 28, Issue 48
    • DOI: 10.1002/adfm.201806254

    One-step ultra-rapid fabrication and thermoelectric properties of Cu 2 Se bulk thermoelectric material
    journal, January 2019

    • Hu, Tiezheng; Yan, Yonggao; Wang, Si
    • RSC Advances, Vol. 9, Issue 19
    • DOI: 10.1039/c9ra01008d

    High thermoelectric performance in copper telluride
    journal, August 2015

    • He, Ying; Zhang, Tiansong; Shi, Xun
    • NPG Asia Materials, Vol. 7, Issue 8
    • DOI: 10.1038/am.2015.91

    High thermoelectric and mechanical performance in highly dense Cu 2−x S bulks prepared by a melt-solidification technique
    journal, January 2015

    • Zhao, Lanling; Wang, Xiaolin; Fei, Frank Yun
    • Journal of Materials Chemistry A, Vol. 3, Issue 18
    • DOI: 10.1039/c5ta01667c

    Facile rapid synthesis of a nanocrystalline Cu 2 Te multi-phase transition material and its thermoelectric performance
    journal, January 2017

    • Qiu, Yuchong; Ye, Jinwen; Liu, Ying
    • RSC Advances, Vol. 7, Issue 36
    • DOI: 10.1039/c7ra02145c

    Obtaining Material Based on Copper Selenide by the Methods of Powder Metallurgy
    journal, December 2017


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


    Maximum Entropy Method Visualization of Disorder and Ion Migration in Thermoelectric Cu 2-δ Se
    journal, July 2018

    • Dalgaard, Kirstine J.; Eikeland, Espen Z.; Sist, Mattia
    • Advanced Theory and Simulations, Vol. 1, Issue 9
    • DOI: 10.1002/adts.201800068

    Achieving zT > 1 in Inexpensive Zintl Phase Ca 9 Zn 4+ x Sb 9 by Phase Boundary Mapping
    journal, March 2017

    • Ohno, Saneyuki; Aydemir, Umut; Amsler, Maximilian
    • Advanced Functional Materials, Vol. 27, Issue 20
    • DOI: 10.1002/adfm.201606361

    Ultrahigh Thermoelectric Performance by Electron and Phonon Critical Scattering in Cu 2 Se 1-x I x
    journal, September 2013


    Are Binary Copper Sulfides/Selenides Really New and Promising Thermoelectric Materials?
    journal, February 2014

    • Dennler, Gilles; Chmielowski, Radoslaw; Jacob, Stéphane
    • Advanced Energy Materials, Vol. 4, Issue 9
    • DOI: 10.1002/aenm.201301581

    Thermoelectric properties and stability of Ba 3 Cu 16 −  x Se 11 −  y Te y
    journal, July 2019

    • Jafarzadeh, Parisa; Assoud, Abdeljalil; Ramirez, Daniel
    • Journal of Applied Physics, Vol. 126, Issue 2
    • DOI: 10.1063/1.5110043

    Thermoelectric properties of Ag-doped Cu2Se and Cu2Te
    journal, January 2013

    • Ballikaya, Sedat; Chi, Hang; Salvador, James R.
    • Journal of Materials Chemistry A, Vol. 1, Issue 40
    • DOI: 10.1039/c3ta12508d

    Enhanced ZT and attempts to chemically stabilize Cu 2 Se via Sn doping
    journal, January 2016

    • Bailey, Trevor P.; Hui, Si; Xie, Hongyao
    • Journal of Materials Chemistry A, Vol. 4, Issue 43
    • DOI: 10.1039/c6ta06445k

    High thermoelectric performance in Cu 2 Se superionic conductor with enhanced liquid-like behaviour by dispersing SiC
    journal, January 2019

    • Lei, Jingdan; Ma, Zheng; Zhang, De
    • Journal of Materials Chemistry A, Vol. 7, Issue 12
    • DOI: 10.1039/c8ta12210e

    Chemical synthesis of nanostructured Cu2Se with high thermoelectric performance
    journal, January 2014

    • Li, Di; Qin, Xiao Ying; Liu, Yong Fei
    • RSC Advances, Vol. 4, Issue 17
    • DOI: 10.1039/c3ra47015f

    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

    Te-Doped Cu 2 Se nanoplates with a high average thermoelectric figure of merit
    journal, January 2016

    • Yang, Lei; Chen, Zhi-Gang; Han, Guang
    • Journal of Materials Chemistry A, Vol. 4, Issue 23
    • DOI: 10.1039/c6ta02998a

    High thermoelectric performance of superionic argyrodite compound Ag 8 SnSe 6
    journal, January 2016

    • Li, Lin; Liu, Yuan; Dai, Jiyan
    • Journal of Materials Chemistry C, Vol. 4, Issue 24
    • DOI: 10.1039/c6tc00810k

    Superior intrinsic thermoelectric performance with zT of 1.8 in single-crystal and melt-quenched highly dense Cu2-xSe bulks
    journal, January 2015

    • Zhao, Lan-ling; Wang, Xiao-lin; Wang, Ji-yang
    • Scientific Reports, Vol. 5, Issue 1
    • DOI: 10.1038/srep07671

    Recent Advances in Metal Chalcogenides (MX; X = S, Se) Nanostructures for Electrochemical Supercapacitor Applications: A Brief Review
    journal, April 2018

    • Theerthagiri, Jayaraman; Karuppasamy, K.; Durai, Govindarajan
    • Nanomaterials, Vol. 8, Issue 4
    • DOI: 10.3390/nano8040256

    Ultralow thermal conductivity of Tl 4 Ag 18 Te 11
    journal, January 2019

    • Shi, Yixuan; Mashmoushi, Nour; Wegner, Wojciech
    • Journal of Materials Chemistry C, Vol. 7, Issue 26
    • DOI: 10.1039/c9tc02029b

    Fracture structure and thermoelectric enhancement of Cu 2 Se with substitution of nanostructured Ag 2 Se
    journal, January 2019

    • Ballikaya, Sedat; Sertkol, Murat; Oner, Yildirhan
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 25
    • DOI: 10.1039/c9cp00793h

    Nanostructured binary copper chalcogenides: synthesis strategies and common applications
    journal, January 2018

    • Chen, Xinqi; Yang, Jianping; Wu, Tian
    • Nanoscale, Vol. 10, Issue 32
    • DOI: 10.1039/c8nr05558k

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


    Stretchable and dynamically stable promising two-dimensional thermoelectric materials: ScP and ScAs
    journal, January 2019

    • Kaur, Kulwinder; Murali, Devaraj; Nanda, B. R. K.
    • Journal of Materials Chemistry A, Vol. 7, Issue 20
    • DOI: 10.1039/c9ta01393h

    Apparent critical phenomena in the superionic phase transition of Cu 2- x Se
    journal, January 2016


    Are Cu 2 Te‐Based Compounds Excellent Thermoelectric Materials?
    journal, October 2019


    High superionic conduction arising from aligned large lamellae and large figure of merit in bulk Cu 1.94 Al 0.02 Se
    journal, September 2014

    • Zhong, Bin; Zhang, Yong; Li, Weiqian
    • Applied Physics Letters, Vol. 105, Issue 12
    • DOI: 10.1063/1.4896520

    Giant enhancement of the figure-of-merit over a broad temperature range in nano-boron incorporated Cu 2 Se
    journal, January 2018

    • Nazrul Islam, Sheik Md. Kazi; Li, Meng; Aydemir, Umut
    • Journal of Materials Chemistry A, Vol. 6, Issue 38
    • DOI: 10.1039/c8ta05455j

    Improvement of Thermoelectricity Through Magnetic Interactions in Layered Cr 2 Ge 2 Te 6
    journal, June 2018

    • Peng, Chengxiao; Zhang, Guangbiao; Wang, Chao
    • physica status solidi (RRL) - Rapid Research Letters, Vol. 12, Issue 9
    • DOI: 10.1002/pssr.201800172

    New evaluation parameter for wearable thermoelectric generators
    journal, April 2018

    • Wijethunge, Dimuthu; Kim, Woochul
    • Journal of Applied Physics, Vol. 123, Issue 14
    • DOI: 10.1063/1.5018762

    Recent Advances in Liquid‐Like Thermoelectric Materials
    journal, August 2019

    • Zhao, Kunpeng; Qiu, Pengfei; Shi, Xun
    • Advanced Functional Materials, Vol. 30, Issue 8
    • DOI: 10.1002/adfm.201903867

    The role of nanoscale defect features in enhancing the thermoelectric performance of p-type nanostructured SiGe alloys
    journal, January 2015

    • Bathula, Sivaiah; Jayasimhadri, M.; Gahtori, Bhasker
    • Nanoscale, Vol. 7, Issue 29
    • DOI: 10.1039/c5nr01786f

    Experimental and theoretical study of the thermoelectric properties of copper selenide
    journal, July 2017


    Enhancement of thermoelectric performance of Cu2Se by K doping
    journal, December 2018


    Solving the disordered structure of β-Cu 2− x Se using the three-dimensional difference pair distribution function
    journal, April 2019

    • Roth, Nikolaj; Iversen, Bo B.
    • Acta Crystallographica Section A Foundations and Advances, Vol. 75, Issue 3
    • DOI: 10.1107/s2053273319004820

    Remarkably high thermoelectric performance of Cu 2−x Li x Se bulks with nanopores
    journal, January 2018

    • Hu, Qiujun; Zhu, Zheng; Zhang, Yuewen
    • Journal of Materials Chemistry A, Vol. 6, Issue 46
    • DOI: 10.1039/c8ta06912c