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

Title: Effects of partial La filling and Sb vacancy defects on CoS b 3 skutterudites

Abstract

Over the past decade, the open frame ("cagey") structure of CoSb3 skutterudite has invited intensive filling studies with various rare-earth elements for delivering state-of-the-art mid-temperature thermoelectric performance. In order to rationalize previously reported experimental results and provide new insight into the underexplored roles of La fillers and Sb vacancies, ab initio density functional theory studies, along with semi-classical Boltzmann transport theory calculations, are performed for pristine CoSb3 of different lattice settings and La-filled CoSb3 with and without Sb s mono- and di-vacancy defects. We examine the effects of van der Waals (vdW) interactions, spin-orbit coupling (SOC), spin polarization, partial La-filling, and Sb vacancy defects on the structural, electronic, and thermoelectric properties. The vdW interactions profoundly affect the lattice constant, which in turn affects the band gap. The SOC shows minor effects on the electronic and thermoelectric properties. The peculiar quasi-Dirac band in the pristine CoSb3 largely survives La filling but not Sb vacancies, which instead introduce dispersive bands in the band gap region. Importantly, the band structure, density of states, and Fermi surface of La-filled CoSb3 are significantly spin polarized, giving rise to spin-dependent thermoelectric properties. Seebeck coefficients directly calculated as a function of chemical potential are interpreted in connectionmore » with the electronic structures. Temperature-dependent Seebeck coefficients derived for the experimentally studied materials agree well with available experimental data. Seebeck coefficients obtained as a function of charge carrier concentration corroborate a thermoelectrically favorable role at high filling fractions played by the electron/hole pockets on the Fermi surface associated with the degenerate valleys/hills in the conduction/valence bands, respectively. Our results serve to advance the understanding of CoSb3 skutterudite, a class of materials with important fundamental and application implications for thermoelectrics and spintronics.« less

Authors:
 [1];  [2];  [2];  [2];  [3];  [2];  [2];  [4];  [4];  [4];  [4]
  1. Clemson Univ., SC (United States). Dept. of Mechanical Engineering; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Mechanical Engineering
  2. Clemson Univ., SC (United States). Dept. of Physics and Astronomy
  3. Clemson Univ., SC (United States). Dept. of Mechanical Engineering
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences and Computational Sciences and Engineering Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1354662
Alternate Identifier(s):
OSTI ID: 1353134
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 95; Journal Issue: 16; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Hu, Chongze, Zeng, Xiaoyu, Liu, Yufei, Zhou, Menghan, Zhao, Huijuan, Tritt, Terry M., He, Jian, Jakowski, Jacek, Kent, Paul R. C., Huang, Jingsong, and Sumpter, Bobby G. Effects of partial La filling and Sb vacancy defects on CoSb3 skutterudites. United States: N. p., 2017. Web. doi:10.1103/PhysRevB.95.165204.
Hu, Chongze, Zeng, Xiaoyu, Liu, Yufei, Zhou, Menghan, Zhao, Huijuan, Tritt, Terry M., He, Jian, Jakowski, Jacek, Kent, Paul R. C., Huang, Jingsong, & Sumpter, Bobby G. Effects of partial La filling and Sb vacancy defects on CoSb3 skutterudites. United States. doi:10.1103/PhysRevB.95.165204.
Hu, Chongze, Zeng, Xiaoyu, Liu, Yufei, Zhou, Menghan, Zhao, Huijuan, Tritt, Terry M., He, Jian, Jakowski, Jacek, Kent, Paul R. C., Huang, Jingsong, and Sumpter, Bobby G. Tue . "Effects of partial La filling and Sb vacancy defects on CoSb3 skutterudites". United States. doi:10.1103/PhysRevB.95.165204. https://www.osti.gov/servlets/purl/1354662.
@article{osti_1354662,
title = {Effects of partial La filling and Sb vacancy defects on CoSb3 skutterudites},
author = {Hu, Chongze and Zeng, Xiaoyu and Liu, Yufei and Zhou, Menghan and Zhao, Huijuan and Tritt, Terry M. and He, Jian and Jakowski, Jacek and Kent, Paul R. C. and Huang, Jingsong and Sumpter, Bobby G.},
abstractNote = {Over the past decade, the open frame ("cagey") structure of CoSb3 skutterudite has invited intensive filling studies with various rare-earth elements for delivering state-of-the-art mid-temperature thermoelectric performance. In order to rationalize previously reported experimental results and provide new insight into the underexplored roles of La fillers and Sb vacancies, ab initio density functional theory studies, along with semi-classical Boltzmann transport theory calculations, are performed for pristine CoSb3 of different lattice settings and La-filled CoSb3 with and without Sb s mono- and di-vacancy defects. We examine the effects of van der Waals (vdW) interactions, spin-orbit coupling (SOC), spin polarization, partial La-filling, and Sb vacancy defects on the structural, electronic, and thermoelectric properties. The vdW interactions profoundly affect the lattice constant, which in turn affects the band gap. The SOC shows minor effects on the electronic and thermoelectric properties. The peculiar quasi-Dirac band in the pristine CoSb3 largely survives La filling but not Sb vacancies, which instead introduce dispersive bands in the band gap region. Importantly, the band structure, density of states, and Fermi surface of La-filled CoSb3 are significantly spin polarized, giving rise to spin-dependent thermoelectric properties. Seebeck coefficients directly calculated as a function of chemical potential are interpreted in connection with the electronic structures. Temperature-dependent Seebeck coefficients derived for the experimentally studied materials agree well with available experimental data. Seebeck coefficients obtained as a function of charge carrier concentration corroborate a thermoelectrically favorable role at high filling fractions played by the electron/hole pockets on the Fermi surface associated with the degenerate valleys/hills in the conduction/valence bands, respectively. Our results serve to advance the understanding of CoSb3 skutterudite, a class of materials with important fundamental and application implications for thermoelectrics and spintronics.},
doi = {10.1103/PhysRevB.95.165204},
journal = {Physical Review B},
number = 16,
volume = 95,
place = {United States},
year = {2017},
month = {4}
}

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

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

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

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Cohesive Properties and Asymptotics of the Dispersion Interaction in Graphite by the Random Phase Approximation
journal, November 2010


Projector augmented-wave method
journal, December 1994


Computer graphics and graphical user interfaces as tools in simulations of matter at the atomic scale
journal, October 2003


Magnetism in Na-filled Fe-based skutterudites
journal, June 2015

  • Xing, Guangzong; Fan, Xiaofeng; Zheng, Weitao
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep10782

Structures, Energetics, and Electronic Properties of Layered Materials and Nanotubes of Cadmium Chalcogenides
journal, November 2013

  • Zhou, Jia; Huang, Jingsong; Sumpter, Bobby G.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 48
  • DOI: 10.1021/jp409772r

Electronic structure and the ground-state properties of cobalt antimonide skutterudites: Revisited with different theoretical methods
journal, September 2012

  • Hammerschmidt, Lukas; Schlecht, Sabine; Paulus, Beate
  • physica status solidi (a), Vol. 210, Issue 1
  • DOI: 10.1002/pssa.201228453

Thermoelectric properties of Yb-filled Ge-compensated CoSb3 skutterudite materials
journal, June 2005

  • Lamberton, G. A.; Tedstrom, R. H.; Tritt, T. M.
  • Journal of Applied Physics, Vol. 97, Issue 11
  • DOI: 10.1063/1.1927702

Alkali-metal-filled Co Sb 3 skutterudites as thermoelectric materials: Theoretical study
journal, January 2008


Low-index surfaces of CoSb3 skutterudites from first principles
journal, July 2015


Spin-polarized positron annihilation spectroscopy for spintronics applications
journal, June 2013


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

wannier90: A tool for obtaining maximally-localised Wannier functions
journal, May 2008

  • Mostofi, Arash A.; Yates, Jonathan R.; Lee, Young-Su
  • Computer Physics Communications, Vol. 178, Issue 9
  • DOI: 10.1016/j.cpc.2007.11.016

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


Properties of single crystalline semiconducting CoSb 3
journal, October 1996

  • Caillat, T.; Borshchevsky, A.; Fleurial, J. ‐P.
  • Journal of Applied Physics, Vol. 80, Issue 8
  • DOI: 10.1063/1.363405

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Phase diagram of In–Co–Sb system and thermoelectric properties of In-containing skutterudites
journal, January 2014

  • Tang, Yinglu; Qiu, Yuting; Xi, Lili
  • Energy Environ. Sci., Vol. 7, Issue 2
  • DOI: 10.1039/C3EE43240H

Structural phase transition accompanied by metal-insulator transition in PrRu 4 P 12
journal, December 2000


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

Convergence of multi-valley bands as the electronic origin of high thermoelectric performance in CoSb3 skutterudites
journal, October 2015

  • Tang, Yinglu; Gibbs, Zachary M.; Agapito, Luis A.
  • Nature Materials, Vol. 14, Issue 12
  • DOI: 10.1038/nmat4430

Chemical accuracy for the van der Waals density functional
journal, December 2009

  • Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
  • Journal of Physics: Condensed Matter, Vol. 22, Issue 2
  • DOI: 10.1088/0953-8984/22/2/022201

n-Type skutterudites (R,Ba,Yb)yCo4Sb12 (R=Sr, La, Mm, DD, SrMm, SrDD) approaching ZT≈2.0
journal, January 2014


Properties of alkaline-earth-filled skutterudite antimonides: A ( Fe , Ni ) 4 Sb 12 ( A = Ca , Sr, and Ba)
journal, August 2010


Convergence of electronic bands for high performance bulk thermoelectrics
journal, May 2011

  • Pei, Yanzhong; Shi, Xiaoya; LaLonde, Aaron
  • Nature, Vol. 473, Issue 7345, p. 66-69
  • DOI: 10.1038/nature09996

Multi-localization transport behaviour in bulk thermoelectric materials
journal, February 2015

  • Zhao, Wenyu; Wei, Ping; Zhang, Qingjie
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7197

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

Dynamics of a Disordered Diatomic Chain
journal, May 1969


Thermoelectric properties and Kondo behavior in indium incorporated p-type Ce 0.9 Fe 3.5 Ni 0.5 Sb 12 skutterudites
journal, August 2012

  • Puneet, Pooja; He, Jian; Zhu, Song
  • Journal of Applied Physics, Vol. 112, Issue 3
  • DOI: 10.1063/1.4740072

Ab initiomolecular dynamics for liquid metals
journal, January 1993


BoltzWann: A code for the evaluation of thermoelectric and electronic transport properties with a maximally-localized Wannier functions basis
journal, January 2014

  • Pizzi, Giovanni; Volja, Dmitri; Kozinsky, Boris
  • Computer Physics Communications, Vol. 185, Issue 1
  • DOI: 10.1016/j.cpc.2013.09.015

Opportunities and challenges for a sustainable energy future
journal, August 2012

  • Chu, Steven; Majumdar, Arun
  • Nature, Vol. 488, Issue 7411, p. 294-303
  • DOI: 10.1038/nature11475

Thermoelectric properties of La-filled CoSb3 skutterudites
journal, April 2014

  • Park, Kwan-Ho; Lee, Soonil; Seo, Won-Seon
  • Journal of the Korean Physical Society, Vol. 64, Issue 7
  • DOI: 10.3938/jkps.64.1004

The electronic properties of graphene
journal, January 2009

  • Castro Neto, A. H.; Guinea, F.; Peres, N. M. R.
  • Reviews of Modern Physics, Vol. 81, Issue 1, p. 109-162
  • DOI: 10.1103/RevModPhys.81.109

Accurate Band Gaps of Semiconductors and Insulators with a Semilocal Exchange-Correlation Potential
journal, June 2009


Superconductivity and heavy fermion behavior in PrOs 4 Sb 12
journal, February 2002


Electronic structure of CoSb 3 : A narrow-band-gap semiconductor
journal, December 1998


The filled skutterudite CeOs4As12: A hybridization gap semiconductor
journal, November 2008

  • Baumbach, R. E.; Ho, P. C.; Sayles, T. A.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 45
  • DOI: 10.1073/pnas.0808991105

Thermoelectric properties of CoSb 3 and related alloys
journal, July 1995

  • Sharp, J. W.; Jones, E. C.; Williams, R. K.
  • Journal of Applied Physics, Vol. 78, Issue 2
  • DOI: 10.1063/1.360402

Thermodynamic analysis of the filling fraction limits for impurities in CoSb3 based on ab initio calculations
journal, May 2008


Enhanced thermoelectric performance in rare-earth filled-skutterudites
journal, January 2016

  • Li, Yulong; Qiu, Pengfei; Duan, Haozhi
  • Journal of Materials Chemistry C, Vol. 4, Issue 20
  • DOI: 10.1039/C6TC01000H

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


Nitrogen Doping Enables Covalent-Like π–π Bonding between Graphenes
journal, July 2015


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


Raman scattering study of antimony‐based skutterudites
journal, March 1996

  • Nolas, G. S.; Slack, G. A.; Caillat, T.
  • Journal of Applied Physics, Vol. 79, Issue 5
  • DOI: 10.1063/1.361132

Electronic transport in lightly doped CoSb 3
journal, August 1995


Skutterudite antimonides: Quasilinear bands and unusual transport
journal, October 1994


High-performance n-type YbxCo4Sb12: from partially filled skutterudites towards composite thermoelectrics
journal, July 2016

  • Wang, Shanyu; Salvador, James R.; Yang, Jiong
  • NPG Asia Materials, Vol. 8, Issue 7
  • DOI: 10.1038/am.2016.77

Syntheses, Structures, and Theoretical Studies of New Ternary Antimonides β- RE CoSb 3 ( RE = La-Nd, Sm)
journal, January 2009

  • Cai, Wei-Zhao; Wu, Li-Ming; Li, Long-Hua
  • European Journal of Inorganic Chemistry, Vol. 2009, Issue 2
  • DOI: 10.1002/ejic.200800836

Effects of filling in CoSb 3 : Local structure, band gap, and phonons from first principles
journal, January 2010


Evidence for Unconventional Strong-Coupling Superconductivity in P r O s 4 S b 12 : An Sb Nuclear Quadrupole Resonance Study
journal, January 2003


Anomalous heavy-fermion and ordered states in the filled skutterudite PrFe 4 P 12
journal, January 2002


Metal-Insulator Transition in PrRu 4 P 12 with Skutterudite Structure
journal, October 1997


Dirac Point Degenerate with Massive Bands at a Topological Quantum Critical Point
journal, February 2011


Spin-polarized photoemission
journal, November 1997


High thermoelectric performance of nonequilibrium synthesized CeFe 4 Sb 12 composite with multi-scaled nanostructures
journal, October 2013

  • Tan, Gangjian; Zheng, Yun; Tang, Xinfeng
  • Applied Physics Letters, Vol. 103, Issue 18
  • DOI: 10.1063/1.4827555

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

Multitemperature synchrotron powder diffraction and thermoelectric properties of the skutterudite La0.1Co4Sb12
journal, June 2010

  • Mi, Jian-Li; Christensen, Mogens; Nishibori, Eiji
  • Journal of Applied Physics, Vol. 107, Issue 11
  • DOI: 10.1063/1.3428435

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Observation of a three-dimensional topological Dirac semimetal phase in high-mobility Cd3As2
journal, May 2014

  • Neupane, Madhab; Xu, Su-Yang; Sankar, Raman
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4786

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


Discovery of a Three-Dimensional Topological Dirac Semimetal, Na3Bi
journal, January 2014


Charge-Doping-Driven Evolution of Magnetism and Non-Fermi-Liquid Behavior in the Filled Skutterudite CePt 4 Ge 12 x Sb x
journal, December 2012


Bonding in skutterudites: Combined experimental and theoretical characterization of CoSb 3
journal, March 2001


Discovery of a Weyl fermion semimetal and topological Fermi arcs
journal, July 2015


Thermoelectric properties of the skutterudite Co1−xFexSb3 system
journal, December 1998

  • Katsuyama, S.; Shichijo, Y.; Ito, M.
  • Journal of Applied Physics, Vol. 84, Issue 12
  • DOI: 10.1063/1.369048

Electronic band structures of binary skutterudites
journal, October 2015


Molecular dynamics simulation on mechanical properties of crystalline CoSb3 with vacancy defect
journal, June 2012


Temperature dependent solubility of Yb in Yb–CoSb3 skutterudite and its effect on preparation, optimization and lifetime of thermoelectrics
journal, March 2015


Evidence for magnetic ordering associated with metal-insulator transition in Sm Ru 4 P 12 studied by muon spin relaxation
journal, February 2006


Electronic Structures and Transport Properties of Single-Filled CoSb3
journal, February 2010


Electron tunneling experiments on skutterudite Co1−xFexSb3 semiconductors
journal, June 2000

  • Nagao, Jiro; Ferhat, Marhoun; Anno, Hiroaki
  • Applied Physics Letters, Vol. 76, Issue 23
  • DOI: 10.1063/1.126670

The effect of rare-earth filling on the lattice thermal conductivity of skutterudites
journal, January 1996

  • Nolas, G. S.; Slack, G. A.; Morelli, D. T.
  • Journal of Applied Physics, Vol. 79, Issue 8
  • DOI: 10.1063/1.361828

Thermopower analysis of the electronic structure around the metal-insulator transition in V 1 x W x O 2
journal, October 2014


Tkatchenko-Scheffler van der Waals correction method with and without self-consistent screening applied to solids
journal, February 2013


Evidence for Magnetic-Field-Induced Quadrupolar Ordering in the Heavy-Fermion Superconductor PrOs 4 Sb 12
journal, May 2003

  • Kohgi, Masahumi; Iwasa, Kazuaki; Nakajima, Motoki
  • Journal of the Physical Society of Japan, Vol. 72, Issue 5
  • DOI: 10.1143/JPSJ.72.1002

Investigation of skutterudite Mg y Co 4 Sb 12 : High pressure synthesis and thermoelectric properties
journal, March 2013

  • Yang, Jianqing; Zhang, Long; Liu, Yadi
  • Journal of Applied Physics, Vol. 113, Issue 11
  • DOI: 10.1063/1.4795599

A large family of filled skutterudites stabilized by electron count
journal, March 2015

  • Luo, Huixia; Krizan, Jason W.; Muechler, Lukas
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7489

Spin-dependent Seebeck coefficients of Ni 80 Fe 20 and Co in nanopillar spin valves
journal, July 2012


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


Skutterudites under pressure: An ab initio study
journal, March 2014

  • Ram, Swetarekha; Kanchana, V.; Valsakumar, M. C.
  • Journal of Applied Physics, Vol. 115, Issue 9
  • DOI: 10.1063/1.4867041

Shubnikov–de Haas oscillations in CoSb 3 single crystals
journal, February 2000


Improving the modified Becke-Johnson exchange potential
journal, April 2012