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Resonant bonding, multiband thermoelectric transport and native defects in n-type BaBiTe_(3-x)Se_x (x = 0, 0.05 and 0.1)

Maier, S. and Ohno, S. and Yu, G. and Kang, S. D. and Chasapis, T. C. and Ha, V. A. and Miller, S. A. and Berthebaud, D. and Kanatzidis, M. G. and Rignanese, G.-M. and Hautier, G. and Snyder, G. J. and Gascoin, F. (2018) Resonant bonding, multiband thermoelectric transport and native defects in n-type BaBiTe_(3-x)Se_x (x = 0, 0.05 and 0.1). Chemistry of Materials, 30 (1). pp. 174-184. ISSN 0897-4756.

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The unique crystal structure of BaBiTe_3 containing Te···Te resonant bonds and its narrow band gap motivated the systematic study of the thermoelectric transport properties of BaBiTe_(3–x)Se_x (x = 0, 0.05, and 0.1) presented here. This study gives insight in the chemical bonding and thermoelectric transport properties of BaBiTe_3. The study shows that the presence of Te···Te resonant bonds in BaBiTe_3 is best described as a linear combination of interdigitating (Te^(1–))_2 side groups and infinite Te_n chains. Rietveld X-ray structure refinements and extrinsic defect calculations reveal that the substitution of Te by Se occurs preferentially on the Te4 and Te5 sites, which are not involved in Te···Te bonding. This work strongly suggests that both multiband effects and native defects play an important role in the transport properties of BaBiTe_(3–x)Se_x (x = 0, 0.05, and 0.1). The carrier concentration of BaBiTe_3 can be tuned via Se substitution (BaBiTe_(3–x)Se_x with x = 0, 0.05, and 0.1) to values near those needed to optimize the thermoelectric performance. The thermal conductivity of BaBiTe_(3–x)Se_x (x = 0, 0.05, and 0.1) is found to be remarkably low (ca. 0.4 Wm^(–1)K^(–1) at 600 K), reaching values close to the glass limit of BaBiSe_3 (0.34 W m^(–1) K^(–1)) and BaBiTe_3 (0.28 W m^(–1) K^(–1)). Calculations of the defect formation energies in BaBiTe_3 suggest the presence of native Bi_(Ba)^(+1) and Te_(Bi)^(+1) antisite defects, which are low in energy and likely responsible for the native n-type conduction and the high carrier concentration (ca. 10^(20) cm^(–3)) found for all samples. The analyses of the electronic structure of BaBiTe_3 and of the optical absorption spectra of BaBiTe_(3–x)Se_x (x = 0, 0.05, 0.1, and 3) strongly suggest the presence of multiple electron pockets in the conduction band (CB) in all samples. These analyses also provide a possible explanation for the two optical transitions observed for BaBiTe_3. High-temperature optical absorption measurements and thermoelectric transport analyses indicate that bands higher in the conduction band converge with the conduction band minimum (CBM) with increasing temperature and contribute to the thermoelectric transport properties of BaBiTe_3 and BaBiTe_(2.95)Se_(0.05). This multiband contribution can account for the ∼50% higher zT_(max) of BaBiTe_3 and BaBiTe_(2.95)Se_(0.05) (∼0.4 at 617 K) compared to BaBiTe_(2.9)Se_(0.1) (∼0.2 at 617 K), for which no such contribution was found. The increase in the band offset between the CBM and bands higher in the conduction band with respect to the selenium content is one possible explanation for the absence of multiband effects in the thermoelectric transport properties of BaBiTe_(2.9)Se_(0.1).

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Maier, S.0000-0002-2210-6290
Ohno, S.0000-0001-8192-996X
Kang, S. D.0000-0002-7491-7933
Miller, S. A.0000-0002-3181-1426
Kanatzidis, M. G.0000-0003-2037-4168
Rignanese, G.-M.0000-0002-1422-1205
Hautier, G.0000-0003-1754-2220
Snyder, G. J.0000-0003-1414-8682
Gascoin, F.0000-0002-9791-1358
Alternate Title:Resonant bonding, multiband thermoelectric transport and native defects in n-type BaBiTe3-xSex (x = 0, 0.05 and 0.1)
Additional Information:© 2017 American Chemical Society. Received: September 28, 2017; Revised: December 4, 2017; Published: December 4, 2017. The authors thank Riley Hanus for his support concerning the measurement and evaluation of the speed of sound. Financial support from the 2016 ITS Summer Fellowship awarded by the International Thermoelectric Society is gratefully acknowledged. The authors acknowledge financial support from the french “Agence Nationale de la Recherche” (ANR) through the program “Investissements d’Avenir”(ANR-10-LABX-09-01), LabEx EMC3. This work made use of the EPIC facility of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. M.G.K. is supported by a grant by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under the Award Number DE-SC0014520 (electronic structure calculations, sample measurements, characterization). G.Y., G.H., and G.-M.R. acknowledge financial support from the F.R.S.-FNRS project HTBaSE (Contract No. PDR-T.1071.15). V.A.H. was funded through a grant from the FRIA. Computational resources were provided by the supercomputing facilities of the Université catholique de Louvain (CISM/UCL), the Consortium des Equipements de Calcul Intensif en Fédération Wallonie Bruxelles (CECI), funded by the F.R.S.-FNRS. The authors declare no competing financial interest.
Funding AgencyGrant Number
International Thermoelectric SocietyUNSPECIFIED
Agence Nationale pour la Recherche (ANR)ANR-10-LABX-09-01
International Institute for Nanotechnology (IIN)UNSPECIFIED
W. M. Keck FoundationUNSPECIFIED
State of IllinoisUNSPECIFIED
Department of Energy (DOE)DE-SC0014520
Fonds de la Recherche Scientifique (FNRS)PDRT.1071.15
Fonds pour la Formation à la Recherche dans l’índustrie et dans l’Ágriculture (FRIA-Belgium)UNSPECIFIED
Issue or Number:1
Record Number:CaltechAUTHORS:20171204-153825443
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Official Citation:Resonant Bonding, Multiband Thermoelectric Transport, and Native Defects in n-Type BaBiTe3–xSex (x = 0, 0.05, and 0.1). S. Maier, S. Ohno, G. Yu, S. D. Kang, T. C. Chasapis, V. A. Ha, S. A. Miller, D. Berthebaud, M. G. Kanatzidis, G.-M. Rignanese, G. Hautier, G. J. Snyder, and F. Gascoin Chemistry of Materials 2018 30 (1), 174-184. DOI: 10.1021/acs.chemmater.7b04123
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:83674
Deposited By: Tony Diaz
Deposited On:07 Dec 2017 00:11
Last Modified:09 Mar 2020 13:19

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