Complex doping of group 13 elements In and Ga in caged skutterudite CoSb3

Xi, Lili; Qiu, Yting; Zheng, Shang; Shi, Xun; Yang, Jiong; Chen, Lidong; Singh, David J.; Yang, Jihui; Zhang, Wenqing

doi:10.1016/j.actamat.2014.11.022

Title: Complex doping of group 13 elements In and Ga in caged skutterudite CoSb₃

Journal Article · Fri Dec 12 00:00:00 EST 2014 · Acta Materialia

DOI:https://doi.org/10.1016/j.actamat.2014.11.022· OSTI ID:1185658

Xi, Lili ^[1]; Qiu, Yting ^[1]; Zheng, Shang ^[1]; Shi, Xun ^[1]; Yang, Jiong ^[2]; Chen, Lidong ^[1]; Singh, David J. ^[3]; Yang, Jihui ^[2]; Zhang, Wenqing ^[1]

Chinese Academy of Sciences, Shanghai (China)
Univ. of Washington, Seattle, WA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The complex doping behavior of Ga and In in CoSb₃ has been investigated using ab initio total-energy calculations and thermodynamics. The formation energies of void filling, Sb substitution and complex dual-site occupancy defects with different charge states, and their dependence on chemical potentials of species, were studied. Results show that Ga predominantly forms dual-site 2Ga_VF–Ga_Sb defects and substitutes for Sb only at very high Fermi levels or electron concentrations. In, on the other hand, can play multiple roles in skutterudites, including filling in the crystalline voids, substituting for Sb atoms or forming dual-site occupancy, among which the fully charge-compensated dual-site defects (2In_VF–In_Sb and 4In_VF–2In_Sb) are dominant. The equilibrium concentration ratio of impurities at void-filling sites to those at Sb-substitution sites for Ga-doped CoSb₃ is very close to be 2:1, while this value markedly deviates from 2:1 for In-doped CoSb₃. Furthermore, the 2:1 ratio of Ga doping in CoSb₃ leads to low electron concentration (~2 × 10¹⁹ cm^–3) and makes the doped system a semiconductor.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Solid-State Solar-Thermal Energy Conversion Center (S3TEC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; SC0001299; FG02-09ER46577

OSTI ID:: 1185658

Alternate ID(s):: OSTI ID: 1259924

Journal Information:: Acta Materialia, Vol. 85; ISSN 1359-6454

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 24 works

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Enhancement of thermoelectric properties of p -type single-filled skutterudites Ce _x Fe _y Co _{4- y} Sb ₁₂ by tuning the Ce and Fe content Kim, Jungmin; Ohishi, Yuji; Muta, Hiroaki AIP Advances, Vol. 8, Issue 10 https://doi.org/10.1063/1.5044222	journal	October 2018

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Title: Complex doping of group 13 elements In and Ga in caged skutterudite CoSb3

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Title: Complex doping of group 13 elements In and Ga in caged skutterudite CoSb₃