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Title: Crystal structure across the β to α phase transition in thermoelectric Cu 2–xSe

Abstract

Here, the crystal structure uniquely imparts the specific properties of a material, and thus provides the starting point for any quantitative understanding of thermoelectric properties. Cu 2–xSe is an intensely studied high performing, non-toxic and cheap thermoelectric material, and here for the first time, the average structure of β-Cu 2–xSe is reported based on analysis of multi-temperature single-crystal X-ray diffraction data. It consists of Se–Cu layers with additional copper between every alternate layer. The structural changes during the peculiar zT enhancing phase transition mainly consist of changes in the inter-layer distance coupled with subtle Cu migration. Just prior to the transition the structure exhibits strong negative thermal expansion due to the reordering of Cu atoms, when approached from low temperatures. The phase transition is fully reversible and group–subgroup symmetry relations are derived that relate the low-temperature β-phase to the high-temperature α-phase. Weak superstructure reflections are observed and a possible Cu ordering is proposed. The structural rearrangement may have a significant impact on the band structure and the Cu rearrangement may also be linked to an entropy increase. Both factors potentially contribute to the extraordinary zT enhancement across the phase transition.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [1];  [3];  [3];  [1]
+ Show Author Affiliations
  1. Aarhus Univ., Aarhus (Denmark)
  2. Aarhus Univ., Aarhus (Denmark); National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Chinese Academy of Sciences, Shanghai (People's Republic of China)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
Danish National Research Foundation; USDOE
OSTI Identifier:
1373682
Report Number(s):
NREL/JA-5J00-68972
Journal ID: ISSN 2052-2525; IUCRAJ
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
IUCrJ
Additional Journal Information:
Journal Volume: 4; Journal Issue: 4; Journal ID: ISSN 2052-2525
Publisher:
International Union of Crystallography
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; thermoelectrics; negative thermal expansion; properties of solids; inorganic materials

Citation Formats

Eikeland, Espen, Blichfeld, Anders B., Borup, Kasper A., Zhao, Kunpeng, Overgaard, Jacob, Shi, Xun, Chen, Lidong, and Iversen, Bo B. Crystal structure across the β to α phase transition in thermoelectric Cu2–xSe. United States: N. p., 2017. Web. doi:10.1107/S2052252517005553.
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Eikeland, Espen, Blichfeld, Anders B., Borup, Kasper A., Zhao, Kunpeng, Overgaard, Jacob, Shi, Xun, Chen, Lidong, & Iversen, Bo B. Crystal structure across the β to α phase transition in thermoelectric Cu2–xSe. United States. doi:10.1107/S2052252517005553.
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Eikeland, Espen, Blichfeld, Anders B., Borup, Kasper A., Zhao, Kunpeng, Overgaard, Jacob, Shi, Xun, Chen, Lidong, and Iversen, Bo B. Tue . "Crystal structure across the β to α phase transition in thermoelectric Cu2–xSe". United States. doi:10.1107/S2052252517005553. https://www.osti.gov/servlets/purl/1373682.
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@article{osti_1373682,
title = {Crystal structure across the β to α phase transition in thermoelectric Cu2–xSe},
author = {Eikeland, Espen and Blichfeld, Anders B. and Borup, Kasper A. and Zhao, Kunpeng and Overgaard, Jacob and Shi, Xun and Chen, Lidong and Iversen, Bo B.},
abstractNote = {Here, the crystal structure uniquely imparts the specific properties of a material, and thus provides the starting point for any quantitative understanding of thermoelectric properties. Cu2–xSe is an intensely studied high performing, non-toxic and cheap thermoelectric material, and here for the first time, the average structure of β-Cu2–xSe is reported based on analysis of multi-temperature single-crystal X-ray diffraction data. It consists of Se–Cu layers with additional copper between every alternate layer. The structural changes during the peculiar zT enhancing phase transition mainly consist of changes in the inter-layer distance coupled with subtle Cu migration. Just prior to the transition the structure exhibits strong negative thermal expansion due to the reordering of Cu atoms, when approached from low temperatures. The phase transition is fully reversible and group–subgroup symmetry relations are derived that relate the low-temperature β-phase to the high-temperature α-phase. Weak superstructure reflections are observed and a possible Cu ordering is proposed. The structural rearrangement may have a significant impact on the band structure and the Cu rearrangement may also be linked to an entropy increase. Both factors potentially contribute to the extraordinary zT enhancement across the phase transition.},
doi = {10.1107/S2052252517005553},
journal = {IUCrJ},
number = 4,
volume = 4,
place = {United States},
year = {2017},
month = {6}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  10.1107/S2052252517005553
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Citation Metrics:
Cited by: 11 works
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Figures / Tables:

Figure 1 Figure 1: Published thermoelectric data for Cu2–xSe. (a) Seebeck coefficient (S), (b) resistivity (p) and (c) hall mobility (μHall) from selected publications to illustrate the trend in the TE properties for Cu2Se. The references used are Liu et al. (2012), Yu et al. (2012), Ballikaya et al. (2013), Zhao etmore » al. (2015b), Chi et al. (2014), Liu et al. (2013b) and Brown et al. (2013a).« less
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Works referencing / citing this record:

CCDC 1543669: Experimental Crystal Structure Determination: JAYGIC : Non-CSD Structure
dataset, April 2017

CCDC 1543670: Experimental Crystal Structure Determination: JAYGOI : Non-CSD Structure
dataset, April 2017

CCDC 1543671: Experimental Crystal Structure Determination: JAYGUO : Non-CSD Structure
dataset, April 2017

CCDC 1543672: Experimental Crystal Structure Determination: JAYHAV : Non-CSD Structure
dataset, April 2017

CCDC 1543673: Experimental Crystal Structure Determination: JAYHEZ : Non-CSD Structure
dataset, April 2017

CCDC 1543674: Experimental Crystal Structure Determination: JAYHID : Non-CSD Structure
dataset, April 2017

CCDC 1543675: Experimental Crystal Structure Determination: JAYHOJ : Non-CSD Structure
dataset, April 2017

CCDC 1543676: Experimental Crystal Structure Determination: JAYHUP : Non-CSD Structure
dataset, April 2017

CCDC 1543677: Experimental Crystal Structure Determination: JAYJAX : Non-CSD Structure
dataset, April 2017

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    Table 1(p. 5)table
    Figure 3(p. 6)figure
    Figure 4(p. 7)figure
    Figure 5(p. 8)figure
    Figure 6(p. 8)figure
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