Skutterudite CoSb_3 based thermoelectric devices have high potential for engineering applications because both n- and p-type doped CoSb_3 demonstrate excellent thermoelectric performance. A crucial point concerning the application of CoSb_3 is to understand and control its defect chemistry. To reveal the native conductivity behavior of nonstoichiometric CoSb_3, we investigated the intrinsic point defects in CoSb_3 using density functional theory. We found CoSb_3 is p-type in either Co or Sb rich regions of phase stability. Interstitial Co (Co_i) and interstitial Co-pair (Co_(i-p)) are the dominant point defects in the Co rich region. However, Co_(i-p) will be difficult to form because the formation temperature of Co_(i-p) is much lower than the synthesis temperature of CoSb_3. The unexpected acceptor nature of the Co_i or Co_(i-p) defects is explained by the breakage of multiple Sb_4-rings. Co vacancy (Co_v) is found to be the p-type defect in the Sb rich region. Furthermore, the solubility of excess Co in CoSb_3 is expected to be larger than that of Sb because of the lower formation energy and higher carrier concentration of Co_i compared with those of Co_v
