P-Type Co Interstitial Defects in Thermoelectric Skutterudite CoSb3 Due to the Breakage of Sb4-Rings

Guodong Li, Saurabh Bajaj, Umut Aydemir, Shiqiang Hao, Hai Xiao, William A. Goddard*, Pengcheng Zhai, Qingjie Zhang, G. Jeffrey Snyder

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

27 Scopus citations


Skutterudite CoSb3 based thermoelectric devices have high potential for engineering applications because both n- and p-type doped CoSb3 demonstrate excellent thermoelectric performance. A crucial point concerning the application of CoSb3 is to understand and control its defect chemistry. To reveal the native conductivity behavior of nonstoichiometric CoSb3, we investigated the intrinsic point defects in CoSb3 using density functional theory. We found CoSb3 is p-type in either Co or Sb rich regions of phase stability. Interstitial Co (Coi) and interstitial Co-pair (Coi-p) are the dominant point defects in the Co rich region. However, Coi-p will be difficult to form because the formation temperature of Coi-p is much lower than the synthesis temperature of CoSb3. The unexpected acceptor nature of the Coi or Coi-p defects is explained by the breakage of multiple Sb4-rings. Co vacancy (Cov) is found to be the p-type defect in the Sb rich region. Furthermore, the solubility of excess Co in CoSb3 is expected to be larger than that of Sb because of the lower formation energy and higher carrier concentration of Coi compared with those of Cov.

Original languageEnglish (US)
Pages (from-to)2172-2179
Number of pages8
JournalChemistry of Materials
Issue number7
StatePublished - Apr 26 2016

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry


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