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Defect-Controlled Electronic Structure and Phase Stability in Thermoelectric Skutterudite CoSb_3

Li, Guodong and Aydemir, Umut and Wood, Max and Goddard III, William A. and Zhai, Pengcheng and Zhang, Qingjie and Snyder, G. Jeffrey (2017) Defect-Controlled Electronic Structure and Phase Stability in Thermoelectric Skutterudite CoSb_3. Chemistry of Materials, 29 (9). pp. 3999-4007. ISSN 0897-4756. doi:10.1021/acs.chemmater.7b00559.

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Controlling extrinsic defects to tune the carrier concentration of electrons or holes is a crucial point concerning the engineering application of thermoelectric semiconductors. To understand the defect-controlled electronic structure in thermoelectric materials, we apply density functional theory (DFT) to investigate the defect chemistry of dopants M (M = O, S, Se, Te) in CoSb_3. DFT predicts that the breakage of Sb_4-rings induced by these dopants produces the unexpected (n- or p-type) conductivity behavior in CoSb_3. For example, energetically dominant O interstitials (Oi) chemically break Sb_4-rings and form O-4Sb five-membered rings, leading to the charge neutral behavior of O_i. While S interstitials (S_i) collapse Te-3Sb four-membered rings within Te doped CoSb_3 leading to a p-type conduction behavior, Se substitution on Sb (Se_(Sb)) breaks the Se-Te-2Sb four-membered ring resulting in a charge neutral behavior of the complex defect Se_(Sb)+Te_(Sb). Furthermore, the solubility limits of M dopants (M = S, Se, Te) are also calculated to provide essential information on single-phase material design. This study provides a new insight to understand the complicated chemical structure in doped CoSb_3, which is beneficial for devising effective doping strategies to develop high-performance bulk thermoelectric materials.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Li, Guodong0000-0002-4761-6991
Aydemir, Umut0000-0003-1164-1973
Wood, Max0000-0003-2758-6155
Goddard III, William A.0000-0003-0097-5716
Zhai, Pengcheng0000-0002-5737-5220
Snyder, G. Jeffrey0000-0003-1414-8682
Additional Information:© 2017 American Chemical Society. Received 9 February 2017. Published online 17 April 2017. This work is partially supported by National Basic Research Program of China (973-program) under Project No. 2013CB632505, the 111 Project of China under Project No. B07040, Materials Project by Department of Energy Basic Energy Sciences Program under Grant No. EDCBEE, DOE Contract DE-AC02-05CH11231, and China Postdoctoral Science Foundation (408-32200031). We would like to acknowledge the Jet Propulsion Laboratory, California Institute of Technology, as a funding source under a contract with the National Aeronautics and Space Administration, which was supported by the NASA Science Missions Directorate's Radioisotope Power Systems Technology Advancement Program.
Funding AgencyGrant Number
National Basic Research Program of China 973 Program2013CB632505
111 Project of ChinaB07040
Department of Energy (DOE)EDCBEE
Department of Energy (DOE)DE-AC02-05CH11231
China Postdoctoral Science Foundation408-32200031
Issue or Number:9
Record Number:CaltechAUTHORS:20170418-115115037
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Official Citation:Defect-Controlled Electronic Structure and Phase Stability in Thermoelectric Skutterudite CoSb3 Guodong Li, Umut Aydemir, Max Wood, William A. Goddard, III, Pengcheng Zhai, Qingjie Zhang, and G. Jeffrey Snyder Chemistry of Materials 2017 29 (9), 3999-4007 DOI: 10.1021/acs.chemmater.7b00559
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76638
Deposited By: Ruth Sustaita
Deposited On:18 Apr 2017 20:53
Last Modified:15 Nov 2021 17:01

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