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

This content will become publicly available on June 24, 2020

Title: Synthesis, crystal structure and physical properties of the solid solutions Ca 14–x REx CdSb 11 ( RE =La–Nd, Sm, Gd–Yb, x ≈0.85±0.15)

Abstract

This article presents new antimonides represented with the general formula Ca 14–x RExCdSb 11 ( 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 Ca 14CdSb 11 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 Ca 14AlSb 11 structure type (space group I4 1/ 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 Yb 2+/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]
  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 Ca 14–x REx CdSb 11 ( RE =La–Nd, Sm, Gd–Yb, x ≈0.85±0.15). United States: N. p., 2019. Web. doi:10.1063/1.5099632.
Baranets, Sviatoslav, Voss, Leonard, Stoyko, Stanislav, & Bobev, Svilen. Synthesis, crystal structure and physical properties of the solid solutions Ca 14–x REx CdSb 11 ( RE =La–Nd, Sm, Gd–Yb, x ≈0.85±0.15). United States. doi:10.1063/1.5099632.
Baranets, Sviatoslav, Voss, Leonard, Stoyko, Stanislav, and Bobev, Svilen. Mon . "Synthesis, crystal structure and physical properties of the solid solutions Ca 14–x REx CdSb 11 ( RE =La–Nd, Sm, Gd–Yb, x ≈0.85±0.15)". United States. doi:10.1063/1.5099632.
@article{osti_1595071,
title = {Synthesis, crystal structure and physical properties of the solid solutions Ca 14–x REx CdSb 11 ( 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 = {2019},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 24, 2020
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:

Yb 14 ZnSb 11 : Charge Balance in Zintl Compounds as a Route to Intermediate Yb Valence
journal, July 2000


The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties
journal, March 2019

  • Hu, Yufei; Cerretti, Giacomo; Kunz Wille, Elizabeth L.
  • Journal of Solid State Chemistry, Vol. 271
  • DOI: 10.1016/j.jssc.2018.12.037

Tuning Magnetism of [MnSb 4 ] 9– Cluster in Yb 14 MnSb 11 through Chemical Substitutions on Yb Sites: Appearance and Disappearance of Spin Reorientation
journal, September 2016

  • Hu, Yufei; Chen, Chih-Wei; Cao, Huibo
  • Journal of the American Chemical Society, Vol. 138, Issue 38
  • DOI: 10.1021/jacs.6b05636

Zintl Chemistry for Designing High Efficiency Thermoelectric Materials
journal, February 2010

  • Toberer, Eric S.; May, Andrew F.; Snyder, G. Jeffrey
  • Chemistry of Materials, Vol. 22, Issue 3
  • DOI: 10.1021/cm901956r

Exploring the Limits of the Zintl Concept for the A14MPn11 Structure Type with M = Zn, Cd
journal, January 1995

  • Young, Dianna M.; Torardi, Charles C.; Olmstead, Marilyn M.
  • Chemistry of Materials, Vol. 7, Issue 1
  • DOI: 10.1021/cm00049a015

Zintl phases with group 15 elements and the transition metals: A brief overview of pnictides with diverse and complex structures
journal, February 2019


Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


X-ray photoelectron spectroscopy studies of Yb14MnSb11 and Yb14ZnSb11
journal, January 2005

  • Holm, Aaron P.; Ozawa, Tadashi C.; Kauzlarich, Susan M.
  • Journal of Solid State Chemistry, Vol. 178, Issue 1
  • DOI: 10.1016/j.jssc.2004.07.009

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

Darstellung und Struktur der Verbindung Ca14AlSb11
journal, December 1984

  • Cordier, Gerhard; Sch�fer, Herbert; Stelter, Michael
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 519, Issue 12
  • DOI: 10.1002/zaac.19845191219

Crystal chemistry and magnetic properties of the solid solutions Ca 14−x RE x MnBi 11 (RE = La–Nd, Sm, and Gd–Ho; x ≈ 0.6–0.8)
journal, January 2017

  • Ovchinnikov, Alexander; Prakash, Jai; Bobev, Svilen
  • Dalton Transactions, Vol. 46, Issue 46
  • DOI: 10.1039/C7DT03715E

Traversing the Metal-Insulator Transition in a Zintl Phase: Rational Enhancement of Thermoelectric Efficiency in Yb 14 Mn 1− x Al x Sb 11
journal, September 2008

  • Toberer, Eric S.; Cox, Catherine A.; Brown, Shawna R.
  • Advanced Functional Materials, Vol. 18, Issue 18
  • DOI: 10.1002/adfm.200800298

Effective Field Theories of Magnetism
journal, August 1966

  • Smart, J. Samuel; Van Vleck, J. H.
  • Physics Today, Vol. 19, Issue 8
  • DOI: 10.1063/1.3048415

Atomic Radii and Interatomic Distances in Metals
journal, March 1947

  • Pauling, Linus
  • Journal of the American Chemical Society, Vol. 69, Issue 3
  • DOI: 10.1021/ja01195a024

Zintl phases for thermoelectric devices
journal, January 2007

  • Kauzlarich, Susan M.; Brown, Shawna R.; Jeffrey Snyder, G.
  • Dalton Transactions, Issue 21
  • DOI: 10.1039/b702266b

Van Arkel—Ketelaar triangles
journal, December 1993


Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

Single crystal growth and magnetic properties of the mixed valent Yb containing Zintl phase, Yb 14 MgSb 11
journal, January 2018

  • Kunz Wille, Elizabeth L.; Jo, Na Hyun; Fettinger, James C.
  • Chemical Communications, Vol. 54, Issue 92
  • DOI: 10.1039/C8CC05471A

Enhanced High-Temperature Thermoelectric Performance of Yb 14– x Ca x MnSb 11
journal, April 2012

  • Uvarov, Catherine A.; Ortega-Alvarez, Francisco; Kauzlarich, Susan M.
  • Inorganic Chemistry, Vol. 51, Issue 14
  • DOI: 10.1021/ic300567c

Zintl Phases: Transitions between Metallic and Ionic Bonding
journal, September 1973

  • Schäfer, Herbert; Eisenmann, Brigitte; Müller, Wiking
  • Angewandte Chemie International Edition in English, Vol. 12, Issue 9
  • DOI: 10.1002/anie.197306941

Seebeck and Figure of Merit Enhancement by Rare Earth Doping in Yb14-xRExZnSb11 (x = 0.5)
journal, March 2019

  • Kunz Wille, Elizabeth; Grewal, Navtej; Bux, Sabah
  • Materials, Vol. 12, Issue 5
  • DOI: 10.3390/ma12050731

Thermal air-oxidized coating on Yb14−xRExMnSb11 ceramics: The role of rare earth dopants
journal, August 2018

  • Vasilyeva, Inga; Abdusalyamova, Maxsuda; Makhmudov, Farchod
  • Journal of Thermal Analysis and Calorimetry, Vol. 136, Issue 2
  • DOI: 10.1007/s10973-018-7659-z

Cation−Anion Interactions as Structure Directing Factors:  Structure and Bonding of Ca 2 CdSb 2 and Yb 2 CdSb 2
journal, April 2007

  • Xia, Sheng-qing; Bobev, Svilen
  • Journal of the American Chemical Society, Vol. 129, Issue 13
  • DOI: 10.1021/ja069261k

The effect of light rare earth element substitution in Yb 14 MnSb 11 on thermoelectric properties
journal, January 2015

  • Hu, Yufei; Bux, Sabah K.; Grebenkemper, Jason H.
  • Journal of Materials Chemistry C, Vol. 3, Issue 40
  • DOI: 10.1039/C5TC02326B

On the Extended Series of Quaternary Zintl Phases Ca13REMnSb11 (RE = La-Nd, Sm, Gd-Dy): On the Extended Series of Quaternary Zintl Phases Ca13REMnSb11 (RE = La-Nd, Sm, Gd-Dy)
journal, May 2016

  • Prakash, Jai; Stoyko, Stanislav; Voss, Leonard
  • European Journal of Inorganic Chemistry, Vol. 2016, Issue 18
  • DOI: 10.1002/ejic.201600306

Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993

  • Dronskowski, Richard; Bloechl, Peter E.
  • The Journal of Physical Chemistry, Vol. 97, Issue 33
  • DOI: 10.1021/j100135a014

Improved Thermoelectric Performance in Yb 14 Mn 1− x Zn x Sb 11 by the Reduction of Spin-Disorder Scattering
journal, May 2008

  • Brown, Shawna R.; Toberer, Eric S.; Ikeda, Teruyuki
  • Chemistry of Materials, Vol. 20, Issue 10
  • DOI: 10.1021/cm703616q

High Seebeck Coefficient and Unusually Low Thermal Conductivity Near Ambient Temperatures in Layered Compound Yb 2– x Eu x CdSb 2
journal, December 2017


Effect of Crystal Fields on the Magnetic Properties of Samarium Intermetallic Compounds
journal, January 1973

  • de Wijn, H. W.; van Diepen, A. M.; Buschow, K. H. J.
  • Physical Review B, Vol. 7, Issue 1
  • DOI: 10.1103/PhysRevB.7.524

A local exchange-correlation potential for the spin polarized case. i
journal, July 1972


Die thermomagnetischen Eigenschaften der Elemente
journal, January 1910


SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

New bulk Materials for Thermoelectric Power Generation: Clathrates and Complex Antimonides
journal, February 2010


High thermoelectric efficiency in lanthanum doped Yb14MnSb11
journal, August 2008

  • Toberer, Eric S.; Brown, Shawna R.; Ikeda, Teruyuki
  • Applied Physics Letters, Vol. 93, Issue 6
  • DOI: 10.1063/1.2970089

Yb 14 MnSb 11 :  New High Efficiency Thermoelectric Material for Power Generation
journal, April 2006

  • Brown, Shawna R.; Kauzlarich, Susan M.; Gascoin, Franck
  • Chemistry of Materials, Vol. 18, Issue 7
  • DOI: 10.1021/cm060261t

Magnetic and structural effects of partial Ce substitution in Y b 14 MnSb 11
journal, April 2015

  • Grebenkemper, Jason H.; Kauzlarich, Susan M.
  • APL Materials, Vol. 3, Issue 4
  • DOI: 10.1063/1.4908038

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


Yb 14 MgSb 11 and Ca 14 MgSb 11 —New Mg-Containing Zintl Compounds and Their Structures, Bonding, and Thermoelectric Properties
journal, December 2014

  • Hu, Yufei; Wang, Jian; Kawamura, Airi
  • Chemistry of Materials, Vol. 27, Issue 1
  • DOI: 10.1021/cm504059t

Structure and properties of the transition-metal Zintl compounds A14MnPn11 (A = Ca, Sr, Ba; Pn = As, Sb)
journal, January 1994

  • Rehr, Anette; Kuromoto, Traci Y.; Kauzlarich, Susan M.
  • Chemistry of Materials, Vol. 6, Issue 1
  • DOI: 10.1021/cm00037a020

Improved Thermoelectric Properties in Lu-doped Yb$_{14}$MnSb$_{11}$ Zintl Compounds
journal, February 2012