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Title: Synthesis, crystal structure and physical properties of the solid solutions Ca14–x RExCdSb11 (RE = La–Nd, Sm, Gd–Yb,x ≈ 0.85±0.15)

Abstract

This article presents new antimonides represented with the general formula Ca14–xRExCdSb11 (RE=La–Nd, Sm, Gd–Yb, x ≈ 0.85±0.15). The 12 studied compounds constitute a nearly complete series of rare-earth metal substituted variants of the ternary Ca14CdSb11 phase. All have been synthesized from the respective elements, employing high-temperature reactions under molten flux conditions. The structures have been fully characterized by single-crystal X-ray diffraction methods. All materials crystallize in the tetragonal Ca14AlSb11 structure type (space group I41/acd, No. 142, Z=8). Rare-earth element atoms randomly substitute Ca atoms on the four available crystallographic sites, with a noted preference for the Ca2 site in case of the light (La–Nd) rare-earth elements and the Ca1 site in case of the heavier (Sm, Gd–Yb) ones. The electronic structure calculations and resistivity measurements indicate title compounds as degenerated semiconductors. Magnetization measurements at varied temperature show Curie-Weiss paramagnetic behavior consistent with local-moment magnetism due to the 3+ ground state for the rare-earth metal ions. In the case of the Yb-containing sample, a mixed-valence Yb2+/3+ state is apparent. Furthermore, the measured charge transport properties suggest small bandgap degenerate semiconductor-like behavior and suitability for thermoelectrics.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
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  1. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
OSTI Identifier:
1595071
Alternate Identifier(s):
OSTI ID: 1529033
Grant/Contract Number:  
SC0008885
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Applied Physics
Additional Journal Information:
Journal Volume: 125; Journal Issue: 24; Journal ID: ISSN 0021-8979
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; antimonides; crystal structure; electronic structure; thermoelectrics; Zintl phases

Citation Formats

Baranets, Sviatoslav, Voss, Leonard, Stoyko, Stanislav, and Bobev, Svilen. Synthesis, crystal structure and physical properties of the solid solutions Ca14–x RExCdSb11 (RE = La–Nd, Sm, Gd–Yb,x ≈ 0.85±0.15). United States: N. p., 2019. Web. doi:10.1063/1.5099632.
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Baranets, Sviatoslav, Voss, Leonard, Stoyko, Stanislav, & Bobev, Svilen. Synthesis, crystal structure and physical properties of the solid solutions Ca14–x RExCdSb11 (RE = La–Nd, Sm, Gd–Yb,x ≈ 0.85±0.15). United States. https://doi.org/10.1063/1.5099632
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Baranets, Sviatoslav, Voss, Leonard, Stoyko, Stanislav, and Bobev, Svilen. Mon . "Synthesis, crystal structure and physical properties of the solid solutions Ca14–x RExCdSb11 (RE = La–Nd, Sm, Gd–Yb,x ≈ 0.85±0.15)". United States. https://doi.org/10.1063/1.5099632. https://www.osti.gov/servlets/purl/1595071.
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@article{osti_1595071,
title = {Synthesis, crystal structure and physical properties of the solid solutions Ca14–x RExCdSb11 (RE = La–Nd, Sm, Gd–Yb,x ≈ 0.85±0.15)},
author = {Baranets, Sviatoslav and Voss, Leonard and Stoyko, Stanislav and Bobev, Svilen},
abstractNote = {This article presents new antimonides represented with the general formula Ca14–xRExCdSb11 (RE=La–Nd, Sm, Gd–Yb, x ≈ 0.85±0.15). The 12 studied compounds constitute a nearly complete series of rare-earth metal substituted variants of the ternary Ca14CdSb11 phase. All have been synthesized from the respective elements, employing high-temperature reactions under molten flux conditions. The structures have been fully characterized by single-crystal X-ray diffraction methods. All materials crystallize in the tetragonal Ca14AlSb11 structure type (space group I41/acd, No. 142, Z=8). Rare-earth element atoms randomly substitute Ca atoms on the four available crystallographic sites, with a noted preference for the Ca2 site in case of the light (La–Nd) rare-earth elements and the Ca1 site in case of the heavier (Sm, Gd–Yb) ones. The electronic structure calculations and resistivity measurements indicate title compounds as degenerated semiconductors. Magnetization measurements at varied temperature show Curie-Weiss paramagnetic behavior consistent with local-moment magnetism due to the 3+ ground state for the rare-earth metal ions. In the case of the Yb-containing sample, a mixed-valence Yb2+/3+ state is apparent. Furthermore, the measured charge transport properties suggest small bandgap degenerate semiconductor-like behavior and suitability for thermoelectrics.},
doi = {10.1063/1.5099632},
journal = {Journal of Applied Physics},
number = 24,
volume = 125,
place = {United States},
year = {Mon Jun 24 00:00:00 EDT 2019},
month = {Mon Jun 24 00:00:00 EDT 2019}
}
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Publisher's Version of Record
https://doi.org/10.1063/1.5099632
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Cited by: 18 works
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Figures / Tables:

Figure 1 Figure 1: Schematic view of the tetragonal Ca14AlSb11 structure. The aluminum atoms centering the Sb tetrahedra are shown in blue; the Ca atoms are light-grey, and the Sb atoms are drawn as yellow spheres, respectively. The hypervalent Sb37– trimers, which are the hallmark of this structure type are also depictedmore » in yellow; unit cell is outlined.« less
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    Works referencing / citing this record:

    Exploration of Multi-Component Vanadium and Titanium Pnictides Using Flux Growth and Conventional High-Temperature Methods
    journal, January 2020

    On the New Oxyarsenides Eu5Zn2As5O and Eu5Cd2As5O
    journal, June 2020

    • Darone, Gregory M.; Baranets, Sviatoslav A.; Bobev, Svilen
    • Crystals, Vol. 10, Issue 6
    • DOI: 10.3390/cryst10060475
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      Figure S1 (p. 48)figure
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