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Discovery of highly polarizable semiconductors BaZrS₃ and Ba₃Zr₂S₇

Filippone, Stephen and Zhao, Boyang and Niu, Shanyuan and Koocher, Nathan Z. and Silevitch, Daniel and Fina, Ignasi and Rondinelli, James M. and Ravichandran, Jayakanth and Jaramillo, R. (2020) Discovery of highly polarizable semiconductors BaZrS₃ and Ba₃Zr₂S₇. Physical Review Materials, 4 (9). Art. No. 091601. ISSN 2475-9953. doi:10.1103/physrevmaterials.4.091601.

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There are few known semiconductors exhibiting both strong optical response and large dielectric polarizability. Inorganic materials with large dielectric polarizability tend to be wide-band gap complex oxides. Semiconductors with a strong photoresponse to visible and infrared light tend to be weakly polarizable. Interesting exceptions to these trends are halide perovskites and phase-change chalcogenides. Here we introduce complex chalcogenides in the Ba-Zr-S system in perovskite and Ruddlesden-Popper structures as a family of highly polarizable semiconductors. We report the results of impedance spectroscopy on single crystals that establish BaZrS₃ and Ba₃Zr₂S₇ as semiconductors with a low-frequency relative dielectric constant ɛ0 in the range 50–100 and band gap in the range 1.3–1.8 eV. Our electronic structure calculations indicate that the enhanced dielectric response in perovskite BaZrS₃ versus Ruddlesden-Popper Ba₃Zr₂S₇ is primarily due to enhanced IR mode-effective charges and variations in phonon frequencies along 〈001〉; differences in the Born effective charges and the lattice stiffness are of secondary importance. This combination of covalent bonding in crystal structures more common to complex oxides, but comprising sulfur, results in a sizable Fröhlich coupling constant, which suggests that charge carriers are large polarons.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper
Filippone, Stephen0000-0002-6182-8341
Silevitch, Daniel0000-0002-6347-3513
Fina, Ignasi0000-0003-4182-6194
Rondinelli, James M.0000-0003-0508-2175
Ravichandran, Jayakanth0000-0001-5030-9143
Jaramillo, R.0000-0003-3116-6719
Additional Information:© 2020 American Physical Society. Received 18 June 2020; accepted 20 July 2020; published 8 September 2020. We acknowledge support from the National Science Foundation (NSF) under Grant No. 1751736, “CAREER: Fundamentals of Complex Chalcogenide Electronic Materials,” from the MIT Skoltech Program, and from “la Caixa” Foundation MISTI Global Seed Funds. Financial support from the Spanish Ministry of Economy, Competitiveness and Universities, through the “Severo Ochoa” Programme for Centres of Excellence in R&D (Grant No. SEV-2015-0496) and Projects No. MAT2015-73839-JIN (MINECO/FEDER, EU) and No. PID2019-107727RB-I00, and from Generalitat de Catalunya (Grant No. 2017 SGR 1377) is acknowledged. I.F. acknowledges Ramón y Cajal Contract No. RYC-2017-22531. S.F. acknowledges support from the NSF Graduate Research Fellowship under Grant No. 1122374. The work at Caltech was supported by National Science Foundation Grant No. DMR-1606858. J.R., B.Z., and S.N. acknowledge support from Army Research Office under Award No. W911NF-19-1-0137 and Air Force Office of Scientific Research under Award No. FA9550-16-1-0335. N.Z.K. and J.M.R. acknowledge support from the U.S. Department of Energy under Grant No. DE-SC0012375 and the DOD-HPCMP for computational resources. N.Z.K. thanks Dr. Michael Waters and Dr. Xuezeng Lu for helpful discussions. S.F. and R.J. acknowledge David Bono and Brian Neltner for helpful discussions and technical assistance.
Funding AgencyGrant Number
Massachusetts Institute of Technology (MIT)UNSPECIFIED
La Caixa FoundationUNSPECIFIED
Severo OchoaSEV-2015-0496
Ministerio de Economía, Industria y Competitividad (MINECO)MAT2015-73839-JIN
Fondo Europeo de Desarrollo Regional (FEDER)UNSPECIFIED
Ministerio de Economía, Industria y Competitividad (MINECO)PID2019-107727RB-I00
Generalitat de Catalunya2017 SGR 1377
Ramón y Cajal ProgrammeRYC-2017-22531
NSF Graduate Research FellowshipDGE-1122374
Army Research Office (ARO)W911NF-19-1-0137
Air Force Office of Scientific Research (AFOSR)FA9550-16-1-0335
Department of Energy (DOE)DE-SC0012375
Issue or Number:9
Record Number:CaltechAUTHORS:20200910-105646089
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105311
Deposited By: Tony Diaz
Deposited On:10 Sep 2020 18:15
Last Modified:16 Nov 2021 18:41

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