Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites

Hu, Yanyun; Chen, Ning; Clancy, J. P.; Salvador, James R.; Kim, Chang-Yong; Shi, Xiaoya; Li, Qiang; Kim, Young-June

doi:10.1103/PhysRevB.96.224107

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

Journal Article · Fri Dec 29 00:00:00 EST 2017 · Physical Review B

DOI:https://doi.org/10.1103/PhysRevB.96.224107· OSTI ID:1433993

Hu, Yanyun ^[1]; Chen, Ning ^[2]; Clancy, J. P. ^[1]; Salvador, James R. ^[3]; Kim, Chang-Yong ^[2]; Shi, Xiaoya ^[4]; Li, Qiang ^[4]; Kim, Young-June ^[1]

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.

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 Yb_xGa_yCo₄Sb₁₂. 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, Ga_24g and Ga_2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga_24g 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 Ga_2a to Ga_24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co₄Sb₁₂ skutterudites is due to the increased Ga_24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: SC0012704; EE0005432; RGPIN-2014-06071

OSTI ID:: 1433993

Alternate ID(s):: OSTI ID: 1416449

Report Number(s):: BNL-203537-2018-JAAM; PRBMDO; TRN: US1802814

Journal Information:: Physical Review B, Vol. 96, Issue 22; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 5 works

Citation information provided by
Web of Science

References (55)

High figure of merit in partially filled ytterbium skutterudite materials Nolas, G. S.; Kaeser, M.; Littleton, R. T. Applied Physics Letters, Vol. 77, Issue 12 https://doi.org/10.1063/1.1311597	journal	January 2000
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Lattice dynamics and reduced thermal conductivity of filled skutterudites Feldman, J. L.; Singh, D. J.; Mazin, I. I. Physical Review B, Vol. 61, Issue 14 https://doi.org/10.1103/PhysRevB.61.R9209	journal	April 2000
Localized vibrational modes in metallic solids Keppens, V.; Mandrus, D.; Sales, B. C. Nature, Vol. 395, Issue 6705 https://doi.org/10.1038/27625	journal	October 1998
Synthesis and thermoelectric properties of KyCo4Sb12 Pei, Y. Z.; Chen, L. D.; Zhang, W. Applied Physics Letters, Vol. 89, Issue 22 https://doi.org/10.1063/1.2397538	journal	November 2006
Complex thermoelectric materials Snyder, G. Jeffrey; Toberer, Eric S. Nature Materials, Vol. 7, Issue 2, p. 105-114 https://doi.org/10.1038/nmat2090	journal	February 2008
Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports Shi, Xun; Yang, Jiong; Salvador, James R. Journal of the American Chemical Society, Vol. 133, Issue 20 https://doi.org/10.1021/ja111199y	journal	May 2011
Effect of partial void filling on the transport properties of Nd _x Co ₄ Sb ₁₂ skutterudites Kuznetsov, V. L.; Kuznetsova, L. A.; Rowe, D. M. Journal of Physics: Condensed Matter, Vol. 15, Issue 29 https://doi.org/10.1088/0953-8984/15/29/315	journal	July 2003
Filled skutterudite antimonides: Electron crystals and phonon glasses Sales, B. C.; Mandrus, D.; Chakoumakos, B. C. Physical Review B, Vol. 56, Issue 23 https://doi.org/10.1103/PhysRevB.56.15081	journal	December 1997
Cerium filling and doping of cobalt triantimonide Morelli, Donald T.; Meisner, Gregory P.; Chen, Baoxing Physical Review B, Vol. 56, Issue 12 https://doi.org/10.1103/PhysRevB.56.7376	journal	September 1997
EXAFS study of $n$ - and $p$ -type ${Ba}_{8} {Ga}_{16} {Ge}_{30}$ Jiang, Y.; Bridges, F.; Avila, M. A. Physical Review B, Vol. 78, Issue 1 https://doi.org/10.1103/PhysRevB.78.014111	journal	July 2008
Solubility design leading to high figure of merit in low-cost Ce-CoSb3 skutterudites Tang, Yinglu; Hanus, Riley; Chen, Sinn-wen Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8584	journal	July 2015
Thermoelectric properties of Ga-added CoSb ₃ based skutterudites Harnwunggmoung, Adul; Kurosaki, Ken; Plirdpring, Theerayuth Journal of Applied Physics, Vol. 110, Issue 1 https://doi.org/10.1063/1.3606417	journal	July 2011
Physical properties of skutterudites , M = Fe, Co, Rh, Ir Bauer, E.; Galatanu, A.; Michor, H. The European Physical Journal B, Vol. 14, Issue 3 https://doi.org/10.1007/s100510051057	journal	March 2000
Parameter-free calculations of X-ray spectra with FEFF9 Rehr, John J.; Kas, Joshua J.; Vila, Fernando D. Physical Chemistry Chemical Physics, Vol. 12, Issue 21 https://doi.org/10.1039/b926434e	journal	January 2010
Charge-Compensated Compound Defects in Ga-containing Thermoelectric Skutterudites Qiu, Yuting; Xi, Lili; Shi, Xun Advanced Functional Materials, Vol. 23, Issue 25 https://doi.org/10.1002/adfm.201202571	journal	February 2013
X-ray-absorption fine-structure standards: A comparison of experiment and theory Li, G. G.; Bridges, F.; Booth, C. H. Physical Review B, Vol. 52, Issue 9 https://doi.org/10.1103/PhysRevB.52.6332	journal	September 1995
Thermoelectric properties of chemically substituted skutterudites YbyCo4SnxSb12−x Dilley, N. R.; Bauer, E. D.; Maple, M. B. Journal of Applied Physics, Vol. 88, Issue 4 https://doi.org/10.1063/1.1305837	journal	August 2000
Study on lattice dynamics of filled skutterudites In _x Yb _y Co ₄ Sb ₁₂ Peng, Jiangying; Xu, Wei; Yan, Yonggao Journal of Applied Physics, Vol. 112, Issue 2 https://doi.org/10.1063/1.4739762	journal	July 2012
Electrical properties and microcosmic study on compound defects in Ga-containing thermoelectric skutterudites Qiu, Yuting; Xing, Juanjuan; Gao, Xiang Journal of Materials Chemistry A, Vol. 2, Issue 28 https://doi.org/10.1039/c4ta00487f	journal	January 2014
Extended x-ray-absorption fine-structure amplitudes—Wave-function relaxation and chemical effects Rehr, J. J.; Stern, E. A.; Martin, R. L. Physical Review B, Vol. 17, Issue 2 https://doi.org/10.1103/PhysRevB.17.560	journal	January 1978
High performance InxCeyCo4Sb12 thermoelectric materials with in situ forming nanostructured InSb phase Li, Han; Tang, Xinfeng; Zhang, Qingjie Applied Physics Letters, Vol. 94, Issue 10 https://doi.org/10.1063/1.3099804	journal	March 2009
Number of relevant independent points in x-ray-absorption fine-structure spectra Stern, Edward A. Physical Review B, Vol. 48, Issue 13 https://doi.org/10.1103/PhysRevB.48.9825	journal	October 1993
SKUTTERUDITES: A Phonon-Glass-Electron Crystal Approach to Advanced Thermoelectric Energy Conversion Applications Nolas, G. S.; Morelli, D. T.; Tritt, Terry M. Annual Review of Materials Science, Vol. 29, Issue 1 https://doi.org/10.1146/annurev.matsci.29.1.89	journal	August 1999
Filled Skutterudite Antimonides: A New Class of Thermoelectric Materials Sales, B. C.; Mandrus, D.; Williams, R. K. Science, Vol. 272, Issue 5266 https://doi.org/10.1126/science.272.5266.1325	journal	May 1996
Experimental resource pulses influence social-network dynamics and the potential for information flow in tool-using crows St Clair, James J. H.; Burns, Zackory T.; Bettaney, Elaine M. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8197	journal	November 2015
The local structure of skutterudites: A view from inside the unit cell Bridges, Frank Modern Physics Letters B, Vol. 30, Issue 05 https://doi.org/10.1142/S0217984916300015	journal	February 2016
Lead Is Not Off Center in PbTe: The Importance of $r$ -Space Phase Information in Extended X-Ray Absorption Fine Structure Spectroscopy Keiber, T.; Bridges, F.; Sales, B. C. Physical Review Letters, Vol. 111, Issue 9 https://doi.org/10.1103/PhysRevLett.111.095504	journal	August 2013
Thermoelectric properties of indium filled and germanium doped Co ₄ Sb ₁₂ skutterudites Chandra Mallik, Ramesh; Mueller, Eckhard; Kim, Il-Ho Journal of Applied Physics, Vol. 111, Issue 2 https://doi.org/10.1063/1.3677982	journal	January 2012
High thermoelectric performance of triple-filled n -type skutterudites (Sr,Ba,Yb) _y Co ₄ Sb ₁₂ Zhang, L.; Grytsiv, A.; Rogl, P. Journal of Physics D: Applied Physics, Vol. 42, Issue 22 https://doi.org/10.1088/0022-3727/42/22/225405	journal	October 2009
Enhanced Thermoelectric Performance in Barium and Indium Double-Filled Skutterudite Bulk Materials via Orbital Hybridization Induced by Indium Filler Zhao, Wenyu; Wei, Ping; Zhang, Qingjie Journal of the American Chemical Society, Vol. 131, Issue 10 https://doi.org/10.1021/ja8089334	journal	March 2009
Complex doping of group 13 elements In and Ga in caged skutterudite CoSb3 Xi, Lili; Qiu, Yuting; Zheng, Shan Acta Materialia, Vol. 85 https://doi.org/10.1016/j.actamat.2014.11.022	journal	February 2015
Band Structure Engineering and Thermoelectric Properties of Charge-Compensated Filled Skutterudites Shi, Xiaoya; Yang, Jiong; Wu, Lijun Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep14641	journal	October 2015
Off-center phonon scattering sites in ${Eu}_{8} {Ga}_{16} {Ge}_{30}$ and ${Sr}_{8} {Ga}_{16} {Ge}_{30}$ Baumbach, R.; Bridges, F.; Downward, L. Physical Review B, Vol. 71, Issue 2 https://doi.org/10.1103/PhysRevB.71.024202	journal	January 2005
Realization of high thermoelectric performance in n-type partially filled skutterudites Shi, Xun; Bai, Shengqiang; Xi, Lili Journal of Materials Research, Vol. 26, Issue 15 https://doi.org/10.1557/jmr.2011.84	journal	May 2011
Anomalous barium filling fraction and n -type thermoelectric performance of BayCo4Sb12 Chen, L. D.; Kawahara, T.; Tang, X. F. Journal of Applied Physics, Vol. 90, Issue 4 https://doi.org/10.1063/1.1388162	journal	August 2001
Effect of partial void filling on the lattice thermal conductivity of skutterudites Nolas, G. S.; Cohn, J. L.; Slack, G. A. Physical Review B, Vol. 58, Issue 1 https://doi.org/10.1103/PhysRevB.58.164	journal	July 1998
High temperature transport properties of partially filled CaxCo4Sb12 skutterudites Puyet, M.; Lenoir, B.; Dauscher, A. Journal of Applied Physics, Vol. 95, Issue 9 https://doi.org/10.1063/1.1688463	journal	May 2004
Avoided crossing of rattler modes in thermoelectric materials Christensen, Mogens; Abrahamsen, Asger B.; Christensen, Niels B. Nature Materials, Vol. 7, Issue 10 https://doi.org/10.1038/nmat2273	journal	August 2008
Skutterudites as thermoelectric materials: revisited Rull-Bravo, M.; Moure, A.; Fernández, J. F. RSC Advances, Vol. 5, Issue 52 https://doi.org/10.1039/C5RA03942H	journal	January 2015
A comparison of the local structure in ball-milled and hand ground skutterudite samples using EXAFS Short, M.; Bridges, F.; Keiber, T. Intermetallics, Vol. 63 https://doi.org/10.1016/j.intermet.2015.04.001	journal	August 2015
Filling fraction limits for rare-earth atoms in $Co {Sb}_{3}$ : An ab initio approach Mei, Z. G.; Zhang, W.; Chen, L. D. Physical Review B, Vol. 74, Issue 15 https://doi.org/10.1103/PhysRevB.74.153202	journal	October 2006
Unusual local disorder in NdOs $_{4}$ Sb $_{12}$ and PrOs $_{4}$ Sb $_{12}$ skutterudites Keiber, T.; Bridges, F.; Baumbach, R. E. Physical Review B, Vol. 86, Issue 17 https://doi.org/10.1103/PhysRevB.86.174106	journal	November 2012
Einstein modes in the phonon density of states of the single-filled skutterudite ${Yb}_{0.2} {Co}_{4} {Sb}_{12}$ Dimitrov, I. K.; Manley, M. E.; Shapiro, S. M. Physical Review B, Vol. 82, Issue 17 https://doi.org/10.1103/PhysRevB.82.174301	journal	November 2010
Anomalous Dual-Element Filling in Partially Filled Skutterudites Xi, Lili; Yang, Jiong; Zhang, Wenqing Journal of the American Chemical Society, Vol. 131, Issue 15 https://doi.org/10.1021/ja8093845	journal	April 2009
Double-filled skutterudites of the type YbxCayCo4Sb12: Synthesis and properties Salvador, J. R.; Yang, J.; Wang, H. Journal of Applied Physics, Vol. 107, Issue 4 https://doi.org/10.1063/1.3296186	journal	February 2010
Thermoelectric Properties of Indium-Filled Skutterudites He, Tao; Chen, Jiazhong; Rosenfeld, H. David Chemistry of Materials, Vol. 18, Issue 3 https://doi.org/10.1021/cm052055b	journal	February 2006
First-principles study of filled and unfilled antimony skutterudites Ghosez, Philippe; Veithen, Marek Journal of Physics: Condensed Matter, Vol. 19, Issue 9 https://doi.org/10.1088/0953-8984/19/9/096002	journal	February 2007
Ab initio calculations of structural and electronic properties of gallium solid-state phases Bernasconi, M.; Chiarotti, Guido L.; Tosatti, E. Physical Review B, Vol. 52, Issue 14 https://doi.org/10.1103/PhysRevB.52.9988	journal	October 1995
Einstein Oscillators in Thallium Filled Antimony Skutterudites Hermann, Raphaël P.; Jin, Rongying; Schweika, Werner Physical Review Letters, Vol. 90, Issue 13 https://doi.org/10.1103/PhysRevLett.90.135505	journal	April 2003
Eu7Ga6Sb8: A Zintl phase with Ga–Ga bonds and polymeric gallium antimonide chains Park, Seon-Mi; Kim, Sung-Jin; Kanatzidis, Mercouri G. Journal of Solid State Chemistry, Vol. 177, Issue 8 https://doi.org/10.1016/j.jssc.2004.04.025	journal	August 2004
High figure of merit in Eu-filled CoSb ₃ -based skutterudites Lamberton, G. A.; Bhattacharya, S.; Littleton, R. T. Applied Physics Letters, Vol. 80, Issue 4 https://doi.org/10.1063/1.1433911	journal	January 2002
Filling Fraction Limit for Intrinsic Voids in Crystals: Doping in Skutterudites Shi, X.; Zhang, W.; Chen, L. D. Physical Review Letters, Vol. 95, Issue 18 https://doi.org/10.1103/PhysRevLett.95.185503	journal	October 2005
Breakdown of phonon glass paradigm in La- and Ce-filled Fe4Sb12 skutterudites Koza, Michael Marek; Johnson, Mark Robert; Viennois, Romain Nature Materials, Vol. 7, Issue 10 https://doi.org/10.1038/nmat2260	journal	August 2008
Evidence for rattling behavior of the filler atom $(L)$ in the filled skutterudites $L T_{4} X_{12}$ $(L = Ce, Eu, Yb; T = Fe, Ru; X = P, Sb)$ from EXAFS studies Cao, D.; Bridges, F.; Chesler, P. Physical Review B, Vol. 70, Issue 9 https://doi.org/10.1103/PhysRevB.70.094109	journal	September 2004