On the Extended Series of Quaternary Zintl Phases Ca13REMnSb11 (RE = La–Nd, Sm, Gd–Dy)

Prakash, Jai; Stoyko, Stanislav; Voss, Leonard; Bobev, Svilen

doi:10.1002/ejic.201600306

Title: On the Extended Series of Quaternary Zintl Phases Ca13REMnSb11 (RE = La–Nd, Sm, Gd–Dy)

Journal Article · Wed May 18 00:00:00 EDT 2016 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.201600306· OSTI ID:1400459

Prakash, Jai ^[1]; Stoyko, Stanislav ^[1]; Voss, Leonard ^[1];

^[1]

Department of Chemistry and Biochemistry University of Delaware 19716 Newark DE USA

Eight new compounds with a general formula Ca _14– _x RE _x MnSb ₁₁ ( RE = La–Nd, Sm, Gd–Dy; x ≈ 1) were synthesized by the molten flux method and their structures were established via single‐crystal X‐ray diffraction. The overarching goal of this study was to investigate the effect of electron doping, via substitution of RE ³⁺ at Ca ²⁺ sites, on the crystal structure and physical properties of Ca ₁₄ MnSb ₁₁ , which is a candidate for thermoelectric applications. All studied phases are isostructural, and crystallize in the tetragonal body‐centered space group I 4 ₁ / acd (Ca ₁₄ AlSb ₁₁ structure type, Pearson index tI 208). The structure is made up of MnSb ₄ ^10– tetrahedra, randomly mixed Ca ²⁺ and RE ³⁺ cations, Sb ^3– anions, and linear Sb ₃ ^7– polyanions. Comprehensive structural work confirms high rare‐earth metal content with Ca ²⁺ / RE ³⁺ randomly mixed on all four cation sites, with the caveat that the larger RE atoms (La–Nd) prefer to occupy the Ca2 site, while the smaller RE atoms (Sm, Gd, Tb, and Dy) preferably occupy the Ca1 site. Nearly phase‐pure polycrystalline samples have been synthesized using solid‐state reactions, and have been used for physical property measurements. The resistivities of the bulk Ca _14– _x RE _x MnSb ₁₁ ( RE = La–Nd, Sm, Gd; x ≈ 1) samples reveal semiconducting behavior, consistent with the notion of electron doping in the parent p ‐type Ca ₁₄ MnSb ₁₁ material. Magnetic susceptibilities suggest complex magnetic ordering at temperatures below ca. 50 K, likely originating from coupling between two or more magnetic sub‐lattices.

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Sponsoring Organization:: USDOE

OSTI ID:: 1400459

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Vol. 2016 Journal Issue: 18; ISSN 1434-1948

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 22 works

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References (41)

${Yb}_{14} {ZnSb}_{11}$ : Charge Balance in Zintl Compounds as a Route to Intermediate Yb Valence Fisher, I. R.; Bud'ko, S. L.; Song, C. Physical Review Letters, Vol. 85, Issue 5 https://doi.org/10.1103/PhysRevLett.85.1120	journal	July 2000
Optical Study of Interactions in a $d$ -Electron Kondo Lattice with Ferromagnetism Burch, K. S.; Schafgans, A.; Butch, N. P. Physical Review Letters, Vol. 95, Issue 4 https://doi.org/10.1103/PhysRevLett.95.046401	journal	July 2005
Structure, Magnetism, and Magnetoresistance of the Compounds Eu ₁₄ MnAs ₁₁ and Eu ₁₄ MnP ₁₁ Payne, Amy C.; Olmstead, Marilyn M.; Kauzlarich, Susan M. Chemistry of Materials, Vol. 13, Issue 4 https://doi.org/10.1021/cm0007050	journal	April 2001
Super-Paramagnetic Blocking Phenomena and Room-Temperature Ferromagnetism in Wide Band-Gap Dilute Magnetic Semiconductor (Ga, Mn)N Sato, Kazunori; Fukushima, Tetsuya; Katayama-Yoshida, Hiroshi Japanese Journal of Applied Physics, Vol. 46, Issue No. 28 https://doi.org/10.1143/JJAP.46.L682	journal	July 2007
High-temperature thermoelectric studies of A11Sb10 (A=Yb, Ca) Brown, Shawna R.; Kauzlarich, Susan M.; Gascoin, Franck Journal of Solid State Chemistry, Vol. 180, Issue 4 https://doi.org/10.1016/j.jssc.2007.02.007	journal	April 2007
High Temperature Thermoelectric Properties of Yb ₁₄ MnSb ₁₁ Prepared from Reaction of MnSb with the Elements Grebenkemper, Jason H.; Hu, Yufei; Barrett, Dashiel Chemistry of Materials, Vol. 27, Issue 16 https://doi.org/10.1021/acs.chemmater.5b02446	journal	August 2015
The Crystal Structure and Magnetic Properties of a New Ferrimagnetic Semiconductor: Ca ₂₁ Mn ₄ Sb ₁₈ Holm, Aaron P.; Olmstead, Marilyn M.; Kauzlarich, Susan M. Inorganic Chemistry, Vol. 42, Issue 6 https://doi.org/10.1021/ic020530r	journal	March 2003
Structure, Heat Capacity, and High-Temperature Thermal Properties of Yb ₁₄ Mn _{1− x} Al _x Sb ₁₁ Cox, Catherine A.; Toberer, Eric S.; Levchenko, Andrey A. Chemistry of Materials, Vol. 21, Issue 7 https://doi.org/10.1021/cm803252r	journal	April 2009
Exploring the Limits of the Zintl Concept for the A14MPn11 Structure Type with M = Zn, Cd Young, Dianna M.; Torardi, Charles C.; Olmstead, Marilyn M. Chemistry of Materials, Vol. 7, Issue 1 https://doi.org/10.1021/cm00049a015	journal	January 1995
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
Structure, Magnetism, and Colossal Magnetoresistance (CMR) of the Ternary Transition Metal Solid Solution Ca ₁₄ _- _x Eu _x MnSb ₁₁ (0 < x < 14) Kim, Hyungrak; Olmstead, Marilyn M.; Klavins, Peter Chemistry of Materials, Vol. 14, Issue 8 https://doi.org/10.1021/cm020065w	journal	August 2002
Effect of Ca Doping on the Thermoelectric Performance of Yb14MnSb11 Cox, Catherine A.; Brown, Shawna R.; Snyder, G. Jeffrey Journal of Electronic Materials, Vol. 39, Issue 9 https://doi.org/10.1007/s11664-010-1149-9	journal	August 2010
XMCD Characterization of the Ferromagnetic State of Yb ₁₄ MnSb ₁₁ Holm, Aaron P.; Kauzlarich, Susan M.; Morton, Simon A. Journal of the American Chemical Society, Vol. 124, Issue 33 https://doi.org/10.1021/ja020564y	journal	August 2002
A Novel Ferromagnet: Ca _l4 MnBi ₁₁ Kuromoto, Tracl Y.; Kauzlarich, Susan M.; Webb, David J. Molecular Crystals and Liquid Crystals Incorporating Nonlinear Optics, Vol. 181, Issue 1 https://doi.org/10.1080/00268949008036019	journal	April 1990
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
X-ray photoelectron spectroscopy studies of Yb14MnSb11 and Yb14ZnSb11 Holm, Aaron P.; Ozawa, Tadashi C.; Kauzlarich, Susan M. Journal of Solid State Chemistry, Vol. 178, Issue 1 https://doi.org/10.1016/j.jssc.2004.07.009	journal	January 2005
Bonding, moment formation, and magnetic interactions in ${Ca}_{14} {MnBi}_{11}$ and ${Ba}_{14} {MnBi}_{11}$ Sánchez-Portal, D.; Martin, Richard M.; Kauzlarich, S. M. Physical Review B, Vol. 65, Issue 14 https://doi.org/10.1103/PhysRevB.65.144414	journal	March 2002
Darstellung und Struktur der Verbindung Ca14AlSb11 Cordier, Gerhard; Sch�fer, Herbert; Stelter, Michael Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 519, Issue 12 https://doi.org/10.1002/zaac.19845191219	journal	December 1984
Effects of Sc and Y substitution on the structure and thermoelectric properties of Yb14MnSb11 Grebenkemper, Jason H.; Klemenz, Sebastian; Albert, Barbara Journal of Solid State Chemistry, Vol. 242 https://doi.org/10.1016/j.jssc.2016.03.015	journal	October 2016
Traversing the Metal-Insulator Transition in a Zintl Phase: Rational Enhancement of Thermoelectric Efficiency in Yb ₁₄ Mn _{1− x} Al _x Sb ₁₁ Toberer, Eric S.; Cox, Catherine A.; Brown, Shawna R. Advanced Functional Materials, Vol. 18, Issue 18 https://doi.org/10.1002/adfm.200800298	journal	September 2008
Effective Field Theories of Magnetism Smart, J. Samuel; Van Vleck, J. H. Physics Today, Vol. 19, Issue 8 https://doi.org/10.1063/1.3048415	journal	August 1966
Indirect exchange interaction in semiconductors Liu, L. Solid State Communications, Vol. 35, Issue 2 https://doi.org/10.1016/0038-1098(80)90241-0	journal	July 1980
Zintl Phases: Transitions between Metallic and Ionic Bonding Schäfer, Herbert; Eisenmann, Brigitte; Müller, Wiking Angewandte Chemie International Edition in English, Vol. 12, Issue 9 https://doi.org/10.1002/anie.197306941	journal	September 1973
Structure, Magnetism, and Magnetoresistance of the Rare-Earth Transition Metal Compounds Eu ₁₃ AMnSb ₁₁ (A = Ca, Sr, Ba, and Yb) Kim, Hyungrak; Klavins, Peter; Kauzlarich, Susan M. Chemistry of Materials, Vol. 14, Issue 5 https://doi.org/10.1021/cm011624m	journal	May 2002
Structural analysis of the phase separation in magnetic semiconductor (Zn, Cr)Te Kobayashi, Hiroaki; Nishio, Yôtarô; Kanazawa, Ken Physica B: Condensed Matter, Vol. 407, Issue 15 https://doi.org/10.1016/j.physb.2011.08.023	journal	August 2012
Colossal Magnetoresistance in the Transition-Metal Zintl Compound Eu ₁₄ MnSb ₁₁ Chan, Julia Y.; Kauzlarich, Susan M.; Klavins, Peter Chemistry of Materials, Vol. 9, Issue 12 https://doi.org/10.1021/cm9704241	journal	December 1997
Preparation and thermoelectric properties of polycrystalline nonstoichiometric Yb14MnSb11 Zintl compounds Yu, C.; Zhu, T. J.; Yang, S. H. physica status solidi (RRL) - Rapid Research Letters, Vol. 4, Issue 8-9 https://doi.org/10.1002/pssr.201004193	journal	June 2010
Improved Thermoelectric Performance in Yb ₁₄ Mn _{1− x} Zn _x Sb ₁₁ by the Reduction of Spin-Disorder Scattering Brown, Shawna R.; Toberer, Eric S.; Ikeda, Teruyuki Chemistry of Materials, Vol. 20, Issue 10 https://doi.org/10.1021/cm703616q	journal	May 2008
Interplay between Size and Electronic Effects in Determining the Homogeneity Range of the A ₉ Zn ₄₊ _x Pn ₉ and A ₉ Cd ₄₊ _x Pn ₉ Phases (0 ≤ x ≤ 0.5), A = Ca, Sr, Yb, Eu; Pn = Sb, Bi Xia, Sheng-qing; Bobev, Svilen Journal of the American Chemical Society, Vol. 129, Issue 32 https://doi.org/10.1021/ja0728425	journal	August 2007
Zintl-Phasen: Übergangsformen zwischen Metall- und Ionenbindung Schäfer, Herbert; Eisenmann, Brigitte; Müller, Wiking Angewandte Chemie, Vol. 85, Issue 17 https://doi.org/10.1002/ange.19730851704	journal	September 1973
STRUCTURE TIDY – a computer program to standardize crystal structure data Gelato, L. M.; Parthé, E. Journal of Applied Crystallography, Vol. 20, Issue 2 https://doi.org/10.1107/S0021889887086965	journal	April 1987
Yb14−xTmxMnSb11 (0<x<0.5): Structure and magnetic properties Roudebush, John H.; Grebenkemper, Jason; Hu, Yufei Journal of Solid State Chemistry, Vol. 211 https://doi.org/10.1016/j.jssc.2013.12.023	journal	March 2014
Non-stoichiometric compositions arising from synergistic electronic and size effects. Synthesis, crystal chemistry and electronic properties of A ₁₄ Cd _1+x Pn ₁₁ compounds (0 ≤ x ≤ 0.3; A = Sr, Eu; Pn = As, Sb) Makongo, Julien P. A.; Darone, Gregory M.; Xia, Sheng-Qing Journal of Materials Chemistry C, Vol. 3, Issue 40 https://doi.org/10.1039/C5TC01605C	journal	January 2015
High thermoelectric efficiency in lanthanum doped Yb14MnSb11 Toberer, Eric S.; Brown, Shawna R.; Ikeda, Teruyuki Applied Physics Letters, Vol. 93, Issue 6 https://doi.org/10.1063/1.2970089	journal	August 2008
The Zintl-Klemm Concept - A Historical Survey: The Zintl-Klemm Concept - A Historical Survey Nesper, Reinhard Zeitschrift für anorganische und allgemeine Chemie, Vol. 640, Issue 14 https://doi.org/10.1002/zaac.201400403	journal	November 2014
Yb ₁₄ MnSb ₁₁ : New High Efficiency Thermoelectric Material for Power Generation Brown, Shawna R.; Kauzlarich, Susan M.; Gascoin, Franck Chemistry of Materials, Vol. 18, Issue 7 https://doi.org/10.1021/cm060261t	journal	April 2006
Magnetic and structural effects of partial Ce substitution in Y b ₁₄ MnSb ₁₁ Grebenkemper, Jason H.; Kauzlarich, Susan M. APL Materials, Vol. 3, Issue 4 https://doi.org/10.1063/1.4908038	journal	April 2015
Structure and properties of the transition-metal Zintl compounds A14MnPn11 (A = Ca, Sr, Ba; Pn = As, Sb) Rehr, Anette; Kuromoto, Traci Y.; Kauzlarich, Susan M. Chemistry of Materials, Vol. 6, Issue 1 https://doi.org/10.1021/cm00037a020	journal	January 1994
Yb ₁₄ MgSb ₁₁ and Ca ₁₄ MgSb ₁₁ —New Mg-Containing Zintl Compounds and Their Structures, Bonding, and Thermoelectric Properties Hu, Yufei; Wang, Jian; Kawamura, Airi Chemistry of Materials, Vol. 27, Issue 1 https://doi.org/10.1021/cm504059t	journal	December 2014
Improved Thermoelectric Properties in Lu-doped Yb$_{14}$MnSb$_{11}$ Zintl Compounds Yu, Cui; Chen, Yi; Xie, Hanhui Applied Physics Express, Vol. 5, Issue 3 https://doi.org/10.1143/APEX.5.031801	journal	February 2012
Kondo lattice behavior in the ordered dilute magnetic semiconductor ${Yb}_{14 - x} {La}_{x} {MnSb}_{11}$ Sales, B. C.; Khalifah, P.; Enck, T. P. Physical Review B, Vol. 72, Issue 20 https://doi.org/10.1103/PhysRevB.72.205207	journal	November 2005

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