Local structure investigation of Ga and Yb dopants in 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 »
- Authors:
-
- Univ. of Toronto, ON (Canada). Dept. of Physics
- Canadian Light Source, Saskatoon (Canada)
- General Motors, Warren, MI (United States). Chemical and Materials Systems Lab, R&D Center
- Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (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. https://doi.org/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. https://doi.org/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 = {Fri Dec 29 00:00:00 EST 2017},
month = {Fri Dec 29 00:00:00 EST 2017}
}
Web of Science
Figures / Tables:
Works referenced in this record:
High figure of merit in partially filled ytterbium skutterudite materials
journal, January 2000
- Nolas, G. S.; Kaeser, M.; Littleton, R. T.
- Applied Physics Letters, Vol. 77, Issue 12
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
Lattice dynamics and reduced thermal conductivity of filled skutterudites
journal, April 2000
- Feldman, J. L.; Singh, D. J.; Mazin, I. I.
- Physical Review B, Vol. 61, Issue 14
Localized vibrational modes in metallic solids
journal, October 1998
- Keppens, V.; Mandrus, D.; Sales, B. C.
- Nature, Vol. 395, Issue 6705
Synthesis and thermoelectric properties of KyCo4Sb12
journal, November 2006
- Pei, Y. Z.; Chen, L. D.; Zhang, W.
- Applied Physics Letters, Vol. 89, Issue 22
Complex thermoelectric materials
journal, February 2008
- Snyder, G. Jeffrey; Toberer, Eric S.
- Nature Materials, Vol. 7, Issue 2, p. 105-114
Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports
journal, May 2011
- Shi, Xun; Yang, Jiong; Salvador, James R.
- Journal of the American Chemical Society, Vol. 133, Issue 20
Effect of partial void filling on the transport properties of Nd x Co 4 Sb 12 skutterudites
journal, July 2003
- Kuznetsov, V. L.; Kuznetsova, L. A.; Rowe, D. M.
- Journal of Physics: Condensed Matter, Vol. 15, Issue 29
Filled skutterudite antimonides: Electron crystals and phonon glasses
journal, December 1997
- Sales, B. C.; Mandrus, D.; Chakoumakos, B. C.
- Physical Review B, Vol. 56, Issue 23
Cerium filling and doping of cobalt triantimonide
journal, September 1997
- Morelli, Donald T.; Meisner, Gregory P.; Chen, Baoxing
- Physical Review B, Vol. 56, Issue 12
EXAFS study of - and -type
journal, July 2008
- Jiang, Y.; Bridges, F.; Avila, M. A.
- Physical Review B, Vol. 78, Issue 1
Solubility design leading to high figure of merit in low-cost Ce-CoSb3 skutterudites
journal, July 2015
- Tang, Yinglu; Hanus, Riley; Chen, Sinn-wen
- Nature Communications, Vol. 6, Issue 1
Thermoelectric properties of Ga-added CoSb 3 based skutterudites
journal, July 2011
- Harnwunggmoung, Adul; Kurosaki, Ken; Plirdpring, Theerayuth
- Journal of Applied Physics, Vol. 110, Issue 1
Physical properties of skutterudites , M = Fe, Co, Rh, Ir
journal, March 2000
- Bauer, E.; Galatanu, A.; Michor, H.
- The European Physical Journal B, Vol. 14, Issue 3
Parameter-free calculations of X-ray spectra with FEFF9
journal, January 2010
- Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 21
Charge-Compensated Compound Defects in Ga-containing Thermoelectric Skutterudites
journal, February 2013
- Qiu, Yuting; Xi, Lili; Shi, Xun
- Advanced Functional Materials, Vol. 23, Issue 25
X-ray-absorption fine-structure standards: A comparison of experiment and theory
journal, September 1995
- Li, G. G.; Bridges, F.; Booth, C. H.
- Physical Review B, Vol. 52, Issue 9
Thermoelectric properties of chemically substituted skutterudites YbyCo4SnxSb12−x
journal, August 2000
- Dilley, N. R.; Bauer, E. D.; Maple, M. B.
- Journal of Applied Physics, Vol. 88, Issue 4
Study on lattice dynamics of filled skutterudites In x Yb y Co 4 Sb 12
journal, July 2012
- Peng, Jiangying; Xu, Wei; Yan, Yonggao
- Journal of Applied Physics, Vol. 112, Issue 2
Electrical properties and microcosmic study on compound defects in Ga-containing thermoelectric skutterudites
journal, January 2014
- Qiu, Yuting; Xing, Juanjuan; Gao, Xiang
- Journal of Materials Chemistry A, Vol. 2, Issue 28
Extended x-ray-absorption fine-structure amplitudes—Wave-function relaxation and chemical effects
journal, January 1978
- Rehr, J. J.; Stern, E. A.; Martin, R. L.
- Physical Review B, Vol. 17, Issue 2
High performance InxCeyCo4Sb12 thermoelectric materials with in situ forming nanostructured InSb phase
journal, March 2009
- Li, Han; Tang, Xinfeng; Zhang, Qingjie
- Applied Physics Letters, Vol. 94, Issue 10
Number of relevant independent points in x-ray-absorption fine-structure spectra
journal, October 1993
- Stern, Edward A.
- Physical Review B, Vol. 48, Issue 13
SKUTTERUDITES: A Phonon-Glass-Electron Crystal Approach to Advanced Thermoelectric Energy Conversion Applications
journal, August 1999
- Nolas, G. S.; Morelli, D. T.; Tritt, Terry M.
- Annual Review of Materials Science, Vol. 29, Issue 1
Filled Skutterudite Antimonides: A New Class of Thermoelectric Materials
journal, May 1996
- Sales, B. C.; Mandrus, D.; Williams, R. K.
- Science, Vol. 272, Issue 5266
Experimental resource pulses influence social-network dynamics and the potential for information flow in tool-using crows
journal, November 2015
- St Clair, James J. H.; Burns, Zackory T.; Bettaney, Elaine M.
- Nature Communications, Vol. 6, Issue 1
The local structure of skutterudites: A view from inside the unit cell
journal, February 2016
- Bridges, Frank
- Modern Physics Letters B, Vol. 30, Issue 05
Lead Is Not Off Center in PbTe: The Importance of -Space Phase Information in Extended X-Ray Absorption Fine Structure Spectroscopy
journal, August 2013
- Keiber, T.; Bridges, F.; Sales, B. C.
- Physical Review Letters, Vol. 111, Issue 9
Thermoelectric properties of indium filled and germanium doped Co 4 Sb 12 skutterudites
journal, January 2012
- Chandra Mallik, Ramesh; Mueller, Eckhard; Kim, Il-Ho
- Journal of Applied Physics, Vol. 111, Issue 2
High thermoelectric performance of triple-filled n -type skutterudites (Sr,Ba,Yb) y Co 4 Sb 12
journal, October 2009
- Zhang, L.; Grytsiv, A.; Rogl, P.
- Journal of Physics D: Applied Physics, Vol. 42, Issue 22
Enhanced Thermoelectric Performance in Barium and Indium Double-Filled Skutterudite Bulk Materials via Orbital Hybridization Induced by Indium Filler
journal, March 2009
- Zhao, Wenyu; Wei, Ping; Zhang, Qingjie
- Journal of the American Chemical Society, Vol. 131, Issue 10
Complex doping of group 13 elements In and Ga in caged skutterudite CoSb3
journal, February 2015
- Xi, Lili; Qiu, Yuting; Zheng, Shan
- Acta Materialia, Vol. 85
Band Structure Engineering and Thermoelectric Properties of Charge-Compensated Filled Skutterudites
journal, October 2015
- Shi, Xiaoya; Yang, Jiong; Wu, Lijun
- Scientific Reports, Vol. 5, Issue 1
Off-center phonon scattering sites in and
journal, January 2005
- Baumbach, R.; Bridges, F.; Downward, L.
- Physical Review B, Vol. 71, Issue 2
Realization of high thermoelectric performance in n-type partially filled skutterudites
journal, May 2011
- Shi, Xun; Bai, Shengqiang; Xi, Lili
- Journal of Materials Research, Vol. 26, Issue 15
Anomalous barium filling fraction and n -type thermoelectric performance of BayCo4Sb12
journal, August 2001
- Chen, L. D.; Kawahara, T.; Tang, X. F.
- Journal of Applied Physics, Vol. 90, Issue 4
Effect of partial void filling on the lattice thermal conductivity of skutterudites
journal, July 1998
- Nolas, G. S.; Cohn, J. L.; Slack, G. A.
- Physical Review B, Vol. 58, Issue 1
High temperature transport properties of partially filled CaxCo4Sb12 skutterudites
journal, May 2004
- Puyet, M.; Lenoir, B.; Dauscher, A.
- Journal of Applied Physics, Vol. 95, Issue 9
Avoided crossing of rattler modes in thermoelectric materials
journal, August 2008
- Christensen, Mogens; Abrahamsen, Asger B.; Christensen, Niels B.
- Nature Materials, Vol. 7, Issue 10
Skutterudites as thermoelectric materials: revisited
journal, January 2015
- Rull-Bravo, M.; Moure, A.; Fernández, J. F.
- RSC Advances, Vol. 5, Issue 52
A comparison of the local structure in ball-milled and hand ground skutterudite samples using EXAFS
journal, August 2015
- Short, M.; Bridges, F.; Keiber, T.
- Intermetallics, Vol. 63
Filling fraction limits for rare-earth atoms in : An ab initio approach
journal, October 2006
- Mei, Z. G.; Zhang, W.; Chen, L. D.
- Physical Review B, Vol. 74, Issue 15
Unusual local disorder in NdOs Sb and PrOs Sb skutterudites
journal, November 2012
- Keiber, T.; Bridges, F.; Baumbach, R. E.
- Physical Review B, Vol. 86, Issue 17
Einstein modes in the phonon density of states of the single-filled skutterudite
journal, November 2010
- Dimitrov, I. K.; Manley, M. E.; Shapiro, S. M.
- Physical Review B, Vol. 82, Issue 17
Anomalous Dual-Element Filling in Partially Filled Skutterudites
journal, April 2009
- Xi, Lili; Yang, Jiong; Zhang, Wenqing
- Journal of the American Chemical Society, Vol. 131, Issue 15
Double-filled skutterudites of the type YbxCayCo4Sb12: Synthesis and properties
journal, February 2010
- Salvador, J. R.; Yang, J.; Wang, H.
- Journal of Applied Physics, Vol. 107, Issue 4
Thermoelectric Properties of Indium-Filled Skutterudites
journal, February 2006
- He, Tao; Chen, Jiazhong; Rosenfeld, H. David
- Chemistry of Materials, Vol. 18, Issue 3
First-principles study of filled and unfilled antimony skutterudites
journal, February 2007
- Ghosez, Philippe; Veithen, Marek
- Journal of Physics: Condensed Matter, Vol. 19, Issue 9
Ab initio calculations of structural and electronic properties of gallium solid-state phases
journal, October 1995
- Bernasconi, M.; Chiarotti, Guido L.; Tosatti, E.
- Physical Review B, Vol. 52, Issue 14
Einstein Oscillators in Thallium Filled Antimony Skutterudites
journal, April 2003
- Hermann, Raphaël P.; Jin, Rongying; Schweika, Werner
- Physical Review Letters, Vol. 90, Issue 13
Eu7Ga6Sb8: A Zintl phase with Ga–Ga bonds and polymeric gallium antimonide chains
journal, August 2004
- Park, Seon-Mi; Kim, Sung-Jin; Kanatzidis, Mercouri G.
- Journal of Solid State Chemistry, Vol. 177, Issue 8
High figure of merit in Eu-filled CoSb 3 -based skutterudites
journal, January 2002
- Lamberton, G. A.; Bhattacharya, S.; Littleton, R. T.
- Applied Physics Letters, Vol. 80, Issue 4
Filling Fraction Limit for Intrinsic Voids in Crystals: Doping in Skutterudites
journal, October 2005
- Shi, X.; Zhang, W.; Chen, L. D.
- Physical Review Letters, Vol. 95, Issue 18
Breakdown of phonon glass paradigm in La- and Ce-filled Fe4Sb12 skutterudites
journal, August 2008
- Koza, Michael Marek; Johnson, Mark Robert; Viennois, Romain
- Nature Materials, Vol. 7, Issue 10
Evidence for rattling behavior of the filler atom in the filled skutterudites from EXAFS studies
journal, September 2004
- Cao, D.; Bridges, F.; Chesler, P.
- Physical Review B, Vol. 70, Issue 9
Figures / Tables found in this record: