skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 L 2-edge to elucidate the local structure of Ga and Yb dopants in Yb xGa yCo 4Sb 12. 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 resultmore » suggests that the increased solubility of Yb in Yb-Ga co-doped Co 4Sb 12 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.« 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) (SC-22); 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:
Journal Article: 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},
issn = {2469-9950},
number = 22,
volume = 96,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

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

Save / Share:

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
  • DOI: 10.1063/1.1311597

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Lattice dynamics and reduced thermal conductivity of filled skutterudites
journal, April 2000


Localized vibrational modes in metallic solids
journal, October 1998

  • Keppens, V.; Mandrus, D.; Sales, B. C.
  • Nature, Vol. 395, Issue 6705
  • DOI: 10.1038/27625

Synthesis and thermoelectric properties of KyCo4Sb12
journal, November 2006

  • Pei, Y. Z.; Chen, L. D.; Zhang, W.
  • Applied Physics Letters, Vol. 89, Issue 22
  • DOI: 10.1063/1.2397538

Complex thermoelectric materials
journal, February 2008

  • Snyder, G. Jeffrey; Toberer, Eric S.
  • Nature Materials, Vol. 7, Issue 2, p. 105-114
  • DOI: 10.1038/nmat2090

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
  • DOI: 10.1021/ja111199y

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
  • DOI: 10.1088/0953-8984/15/29/315

Filled skutterudite antimonides: Electron crystals and phonon glasses
journal, December 1997


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
  • DOI: 10.1103/PhysRevB.56.7376

EXAFS study of n - and p -type Ba 8 Ga 16 Ge 30
journal, July 2008


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
  • DOI: 10.1038/ncomms8584

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
  • DOI: 10.1063/1.3606417

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
  • DOI: 10.1007/s100510051057

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
  • DOI: 10.1039/b926434e

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
  • DOI: 10.1002/adfm.201202571

X-ray-absorption fine-structure standards: A comparison of experiment and theory
journal, September 1995


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
  • DOI: 10.1063/1.1305837

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
  • DOI: 10.1063/1.4739762

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
  • DOI: 10.1039/c4ta00487f

Extended x-ray-absorption fine-structure amplitudes—Wave-function relaxation and chemical effects
journal, January 1978


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
  • DOI: 10.1063/1.3099804

Number of relevant independent points in x-ray-absorption fine-structure spectra
journal, October 1993


SKUTTERUDITES: A Phonon-Glass-Electron Crystal Approach to Advanced Thermoelectric Energy Conversion Applications
journal, August 1999


Filled Skutterudite Antimonides: A New Class of Thermoelectric Materials
journal, May 1996


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
  • DOI: 10.1038/ncomms8197

The local structure of skutterudites: A view from inside the unit cell
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
journal, August 2013


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
  • DOI: 10.1063/1.3677982

High thermoelectric performance of triple-filled n -type skutterudites (Sr,Ba,Yb) y Co 4 Sb 12
journal, October 2009


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
  • DOI: 10.1021/ja8089334

Complex doping of group 13 elements In and Ga in caged skutterudite CoSb3
journal, February 2015


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
  • DOI: 10.1038/srep14641

Off-center phonon scattering sites in Eu 8 Ga 16 Ge 30 and Sr 8 Ga 16 Ge 30
journal, January 2005


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
  • DOI: 10.1557/jmr.2011.84

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
  • DOI: 10.1063/1.1388162

Effect of partial void filling on the lattice thermal conductivity of skutterudites
journal, July 1998


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
  • DOI: 10.1063/1.1688463

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
  • DOI: 10.1038/nmat2273

Skutterudites as thermoelectric materials: revisited
journal, January 2015

  • Rull-Bravo, M.; Moure, A.; Fernández, J. F.
  • RSC Advances, Vol. 5, Issue 52
  • DOI: 10.1039/C5RA03942H

A comparison of the local structure in ball-milled and hand ground skutterudite samples using EXAFS
journal, August 2015


Filling fraction limits for rare-earth atoms in Co Sb 3 : An ab initio approach
journal, October 2006


Unusual local disorder in NdOs 4 Sb 12 and PrOs 4 Sb 12 skutterudites
journal, November 2012


Einstein modes in the phonon density of states of the single-filled skutterudite Yb 0.2 Co 4 Sb 12
journal, November 2010


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
  • DOI: 10.1021/ja8093845

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
  • DOI: 10.1063/1.3296186

Thermoelectric Properties of Indium-Filled Skutterudites
journal, February 2006

  • He, Tao; Chen, Jiazhong; Rosenfeld, H. David
  • Chemistry of Materials, Vol. 18, Issue 3
  • DOI: 10.1021/cm052055b

First-principles study of filled and unfilled antimony skutterudites
journal, February 2007


Ab initio calculations of structural and electronic properties of gallium solid-state phases
journal, October 1995


Einstein Oscillators in Thallium Filled Antimony Skutterudites
journal, April 2003


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
  • DOI: 10.1016/j.jssc.2004.04.025

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
  • DOI: 10.1063/1.1433911

Filling Fraction Limit for Intrinsic Voids in Crystals: Doping in Skutterudites
journal, October 2005


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
  • DOI: 10.1038/nmat2260

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.