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Title: Local structure investigation of Ga and Yb dopants in Co 4 Sb 12 skutterudites

Abstract

We report our x-ray absorption spectroscopy studies at both Ga K-edge and Yb L2-edge to elucidate the local structure of Ga and Yb dopants in YbxGayCo4Sb12. Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24g site replacing Sb, and the other is the 2a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2a on-center site. At low concentrations of Yb, Ga24g and Ga2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga24g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24g site for the highest Yb concentration (x = 0.4). In addition to the local crystal structure evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K-edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga2a to Ga24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-dopedmore » Co4Sb12 skutterudites is due to the increased Ga24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.« less

Authors:
 [1];  [2];  [1];  [3];  [2];  [4];  [4];  [1]
  1. Univ. of Toronto, ON (Canada). Dept. of Physics
  2. Canadian Light Source, Saskatoon (Canada)
  3. General Motors, Warren, MI (United States). Chemical and Materials Systems Lab, R&D Center
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1433993
Alternate Identifier(s):
OSTI ID: 1416449
Report Number(s):
BNL-203537-2018-JAAM
Journal ID: ISSN 2469-9950; PRBMDO; TRN: US1802814
Grant/Contract Number:  
SC0012704; EE0005432; RGPIN-2014-06071
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 96; Journal Issue: 22; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Hu, Yanyun, Chen, Ning, Clancy, J. P., Salvador, James R., Kim, Chang-Yong, Shi, Xiaoya, Li, Qiang, and Kim, Young-June. Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites. United States: N. p., 2017. Web. doi:10.1103/PhysRevB.96.224107.
Hu, Yanyun, Chen, Ning, Clancy, J. P., Salvador, James R., Kim, Chang-Yong, Shi, Xiaoya, Li, Qiang, & Kim, Young-June. Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites. United States. doi:10.1103/PhysRevB.96.224107.
Hu, Yanyun, Chen, Ning, Clancy, J. P., Salvador, James R., Kim, Chang-Yong, Shi, Xiaoya, Li, Qiang, and Kim, Young-June. Fri . "Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites". United States. doi:10.1103/PhysRevB.96.224107. https://www.osti.gov/servlets/purl/1433993.
@article{osti_1433993,
title = {Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites},
author = {Hu, Yanyun and Chen, Ning and Clancy, J. P. and Salvador, James R. and Kim, Chang-Yong and Shi, Xiaoya and Li, Qiang and Kim, Young-June},
abstractNote = {We report our x-ray absorption spectroscopy studies at both Ga K-edge and Yb L2-edge to elucidate the local structure of Ga and Yb dopants in YbxGayCo4Sb12. Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24g site replacing Sb, and the other is the 2a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2a on-center site. At low concentrations of Yb, Ga24g and Ga2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga24g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24g site for the highest Yb concentration (x = 0.4). In addition to the local crystal structure evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K-edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga2a to Ga24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co4Sb12 skutterudites is due to the increased Ga24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.},
doi = {10.1103/PhysRevB.96.224107},
journal = {Physical Review B},
number = 22,
volume = 96,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

FIG. 1. FIG. 1.: (Color online) Ga K-edge data in r-space for YbxGa0.2Co4Sb12 (x = 0.05, 0.10, 0.15, 0.20) and YbxGa0.15Co4Sb12 (x = 0, 0.25, 0.30, 0.35, 0.40) compounds. Vertical dark yellow dashed lines are guides to the eye for the similarities and differences between these compounds. The FT ranges are 3−14more » ̊A−1.« less

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